1

Paints and Coatings

Dieter Stoye, Hüls AG, Marl, Federal Republic of Germany (Chap. 1)
Werner Funke, Institut für Technische Chemie, Stuttgart, Federal Republic of Germany (Chap. 2.1)
Lutz Hoppe, Wolff Walsrode AG, Walsrode, Federal Republic of Germany (Chap. 2.2.1)
Jürgen Hasselkus, Krahn Chemie GmbH, Hamburg, Federal Republic of Germany (Chap. 2.2.2)
Larry G. Curtis, Eastman Chemical Products, Kingsport, Tennessee, United States (Chap. 2.2.2)
Klaus Hoehne, Bayer AG, Leverkusen, Federal Republic of Germany (Chap. 2.3)
Hans-Joachim Zech, Hüls AG, Marl, Federal Republic of Germany (Chap. 2.4.1 and 2.4.2)
Peter Heiling, Wacker-Chemie GmbH, Burghausen, Federal Republic of Germany (Chap. 2.4.1, 2.4.2, 2.4.3,
2.4.4, 2.4.5, 2.4.6, 2.4.7 and [Link])
Masaaki Yamabe, Asahi Glass Co. Ltd., Hazawa-cho, Kanagawa-ku, Yokohama, Japan (Chap. [Link])
Klaus Dören, Hüls AG, Marl, Federal Republic of Germany (Chap. 2.4.8)
Hans Schupp, BASF AG, Ludwigshafen, Federal Republic of Germany (Chap. 2.5)
Rolf Küchenmeister, Bayer AG, Leverkusen, Federal Republic of Germany (Chap. 2.6)
Martin Schmitthenner, Hüls AG, Witten, Federal Republic of Germany (Chap. 2.7)
Wolfgang Kremer, Bayer AG, Krefeld-Uerdingen, Federal Republic of Germany (Chap. 2.8)
Wolfhart Wieczorrek, Bayer AG, Leverkusen, Federal Republic of Germany (Chap. 2.9)
Hans Gempeler, Ciba-Geigy AG, Basel, Switzerland (Chap. 2.10)
Wolfgang Schneider, Ciba-Geigy AG, Basel, Switzerland (Chap. 2.10)
James W. White, Dow Corning Ltd., Barry, South Glamorgan, CF6 7YL, United Kingdom (Chap. 2.11)
Anthony G. Short, Dow Corning Ltd., Barry, South Glamorgan, CF6 7YL, United Kingdom (Chap. 2.11)
Werner J. Blank, King Industries, Norwalk, Connecticut, United States (Chap. 2.12)
Leonard J. Calbo, King Industries, Norwalk, Connecticut, United States (Chap. 2.12)
Dieter Plath, Hoechst AG, Wiesbaden, Federal Republic of Germany (Chap. 2.13)
Friedrich Wagner, Sika-Chemie, Stuttgart, Federal Republic of Germany (Chap. 2.14)
Werner Haller, Henkel KGaA, Düsseldorf, Federal Republic of Germany (Chap. 2.15.1)
Karl-Martin Rödder, Hüls AG, Troisdorf, Federal Republic of Germany (Chap. 2.15.2)
Hans-Joachim Streitberger, BASF Corporation, Southfield, Michigan, United States (Chap. 3.1 and 3.8)
Edmund Urbano, Vianova Kunstharz AG, Graz, Austria (Chap. 3.2)
Richard Laible, Akzo Coatings GmbH, Stuttgart, Federal Republic of Germany (Chap. 3.3)
Bernd D. Meyer, VP Resicoat GmbH, Reutlingen, Federal Republic of Germany (Chap. 3.4 and 8.3.5)
Engin Bagda, Deutsche Amphibolin-Werke, Ober-Ramstadt, Federal Republic of Germany (Chap. 3.5)
Frederick A. Waite, ICI Paints, Slough, Berkshire SL2 5DS, United Kingdom (Chap. 3.6)
Michel Philips, Radcure Specialties, Drogenbos, Belgium (Chap. 3.7)
Klaus Köhler, Bayer AG, Krefeld-Uerdingen, Federal Republic of Germany (Chap. 4.1)
Peter Simmendinger, Ciba-Geigy AG, Basel, Switzerland (Chap. 4.2)
Wolfgang Roelle, Bassermann & Co., Mannheim, Federal Republic of Germany (Chap. 4.3)
Wilfried Scholz, BYK-Chemie GmbH, Wesel, Federal Republic of Germany (Chap. 5 and 5.7)
Andreas Valet, Ciba-Geigy AG, Basel, Switzerland (Chap. 5.7)

c 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a18 359.pub2
2 Paints and Coatings

Mario Slongo, Ciba-Geigy AG, Basel, Switzerland (Chap. 5.7)

Thomas Molz, Hüls AG, Troisdorf, Federal Republic of Germany (Chap. 6)
Rainer Hiller, BASF Lacke + Farben AG, Münster-Hiltrup, Federal Republic of Germany (Chap. 7)
Klaus Werner Thomer, Opel, Bochum, Federal Republic of Germany (Chap. 8 and 8.3.5)
Klaus Vogel, Herberts GmbH, Wuppertal, Federal Republic of Germany (Chap. 9)
Ulrich Schernau, BASF Lacke + Farben AG, Münster, Federal Republic of Germany (Chap. 10)
Bernhard Hüser, BASF Lacke + Farben AG, Münster, Federal Republic of Germany (Chap. 10)
Alfred Brandt, ICI Lacke Farben GmbH, Hilden, Federal Republic of Germany (Chap. 11.1, 11.2, 11.3,
11.5, 11.6, 11.7 and 11.8)
Alex Milne, Courtaulds Coatings Ltd., Felling, Gateshead NE10 0JY, United Kingdom (Chap. 11.4)
Helmut Weyers, ICI Lacke Farben GmbH, Hilden, Federal Republic of Germany (Chap. 11.9)
Wolfgang Plehn, Umweltbundesamt, Berlin, Federal Republic of Germany (Chap. 12)
Hanns-Adolf Lentze, CEPE, Brussels, Belgium (Chap. 13)

Related Articles → Artists’ Colors; → Metals, Surface Treatment; → Printing Inks; → Solvents; → Wood,
Surface Treatment are separate keywords.

1. Introduction . . . . . . . . . . . . . 4 2.4.2. Coatings Based on Polyolefins and

1.1. Fundamental Concepts . . . . . . 4 Polyolefin Derivatives . . . . . . . . 20
1.2. Historical Development . . . . . . 5 2.4.3. Poly(Vinyl Halides) and Vinyl
1.3. Composition of Paints . . . . . . . 6 Halide Copolymers . . . . . . . . . 21
1.3.1. Binders and Resins . . . . . . . . . 6 [Link]. Poly(Vinyl Chloride) and Vinyl
1.3.2. Plasticizers . . . . . . . . . . . . . . 7 Chloride Copolymers . . . . . . . . 21
1.3.3. Pigments and Extenders . . . . . . 7 [Link]. Vinylidene Chloride Copolymers . 23
1.3.4. Paint Additives . . . . . . . . . . . . 7 [Link]. Fluoropolymer Coatings . . . . . . 23
1.3.5. Solvents . . . . . . . . . . . . . . . . 8 2.4.4. Poly(Vinyl Esters) . . . . . . . . . . 25
1.4. Paint Application . . . . . . . . . . 9 [Link]. Solid Resins . . . . . . . . . . . . . . 25
1.5. Drying and Film Formation . . . 9 [Link]. Dispersions . . . . . . . . . . . . . . 26
2.4.5. Poly(Vinyl Alcohol) . . . . . . . . . 27
1.6. Multicoat Systems . . . . . . . . . 10
2.4.6. Poly(Vinyl Acetals) . . . . . . . . . 27
1.7. Economic Aspects . . . . . . . . . 10
2.4.7. Poly(Vinyl Ethers) . . . . . . . . . . 28
1.8. Future Outlook . . . . . . . . . . . 10
2.4.8. Polystyrene and Styrene
2. Types of Paints and Coatings
Copolymers . . . . . . . . . . . . . . 28
(Binders) . . . . . . . . . . . . . . . 11
2.5. Acrylic Coatings . . . . . . . . . . 29
2.1. Oil-Based Coatings . . . . . . . . 11
2.6. Alkyd Coatings . . . . . . . . . . . 33
2.2. Cellulose-Based Coatings . . . . . 12 2.6.1. Alkyd Resin Binders and Uses . . 33
2.2.1. Nitrocellulose Lacquers . . . . . . 12 2.6.2. Additional Raw Materials . . . . . 37
[Link]. Raw Materials . . . . . . . . . . . . 12 2.6.3. Production . . . . . . . . . . . . . . . 38
[Link]. Application and Uses . . . . . . . . 14 2.6.4. Environmental and Health
2.2.2. Organic Cellulose Ester Coatings 14 Protection Measures . . . . . . . . . 39
[Link]. Cellulose Acetate Butyrate . . . . . 15 2.7. Saturated Polyester Coatings . . 39
[Link]. Cellulose Acetate Propionate . . . 17 2.7.1. Properties . . . . . . . . . . . . . . . 40
2.3. Chlorinated Rubber Coatings . 17 2.7.2. Production of Polyester Resins and
2.3.1. Starting Products . . . . . . . . . . 17 Paints . . . . . . . . . . . . . . . . . . 41
2.3.2. Chlorinated Rubber Paints . . . . . 18 2.7.3. Cross-Linking of Polyester Resins 41
2.3.3. Chlorinated Rubber Combination 2.7.4. Uses . . . . . . . . . . . . . . . . . . . 42
Paints . . . . . . . . . . . . . . . . . . 19 2.8. Unsaturated Polyester Coatings 44
2.4. Vinyl Coatings . . . . . . . . . . . . 20 2.8.1. Unsaturated Polyester Binders . . 44
2.4.1. General Properties . . . . . . . . . . 20 2.8.2. Other Raw Materials . . . . . . . . 45
 Paints and Coatings 3

2.8.3. Production, Properties, and Uses . 46 3.4.3. Properties . . . . . . . . . . . . . . . 87

2.8.4. Transportation and Handling . . . 47 3.4.4. Testing . . . . . . . . . . . . . . . . . 88
2.9. Polyurethane Coatings . . . . . . 48 3.4.5. Storage and Transportation . . . . 89
2.9.1. Raw Materials . . . . . . . . . . . . 48 3.4.6. Environmental Aspects and Safety 90
2.9.2. Polyurethane Systems . . . . . . . . 49 3.4.7. Uses . . . . . . . . . . . . . . . . . . . 90
[Link]. One-Pack Systems . . . . . . . . . . 49 3.5. Waterborne Dispersion Paints
[Link]. Two-Pack Systems . . . . . . . . . . 50 (Emulsion Paints) . . . . . . . . . 92
2.9.3. Properties and Uses . . . . . . . . . 51 3.6. Nonaqueous Dispersion Paints . 95
2.10. Epoxy Coatings . . . . . . . . . . . 51 3.7. Radiation-Curing Systems . . . . 99
2.10.1. Epoxy Resin Types . . . . . . . . . 52 3.7.1. Introduction . . . . . . . . . . . . . . 99
2.10.2. Curing Agents . . . . . . . . . . . . 53 3.7.2. Radiation-Curable Systems Based
2.10.3. Chemically Modified Epoxy on Acrylates . . . . . . . . . . . . . . 99
Resins . . . . . . . . . . . . . . . . . 54 3.7.3. Equipment . . . . . . . . . . . . . . . 100
2.10.4. Uses . . . . . . . . . . . . . . . . . . . 55 3.7.4. Fields of Application . . . . . . . . 100
[Link]. Curing at Ambient Temperature . 55 3.8. Electrodeposition Paints . . . . . 101
[Link]. Curing at Elevated Temperature . 56 4. Pigments and Extenders . . . . . 103
[Link]. Radiation Curing . . . . . . . . . . . 58 4.1. Inorganic Pigments . . . . . . . . 103
[Link]. Occupational Health . . . . . . . . . 58 4.2. Organic Pigments . . . . . . . . . 106
2.11. Silicone Coatings . . . . . . . . . . 58 4.3. Extenders . . . . . . . . . . . . . . . 108
2.12. Urea, Benzoguanamine, and 4.3.1. Introduction . . . . . . . . . . . . . . 108
Melamine Resins for Coatings . 60 4.3.2. Properties . . . . . . . . . . . . . . . 109
2.13. Phenolic Resins for Coatings . . 64 4.3.3. Modification of Extenders . . . . . 113
2.13.1. Resols . . . . . . . . . . . . . . . . . 64 5. Paint Additives . . . . . . . . . . . 113
2.13.2. Novolacs . . . . . . . . . . . . . . . . 66 5.1. Defoamers . . . . . . . . . . . . . . 113
2.13.3. Modified Phenolic Resins . . . . . 66 5.2. Wetting and Dispersing
2.14. Asphalt, Bitumen, and Pitch Additives . . . . . . . . . . . . . . . 114
Coatings . . . . . . . . . . . . . . . 67 5.3. Surface Additives . . . . . . . . . . 116
2.14.1. Asphalt and Asphalt Combination 5.4. Driers and Catalysts . . . . . . . . 117
Coatings . . . . . . . . . . . . . . . . 67 5.5. Preservatives . . . . . . . . . . . . . 118
2.14.2. Bitumen Coatings . . . . . . . . . . 67 5.6. Rheology Additives . . . . . . . . . 118
2.14.3. Bitumen Combination Coatings . 69 5.7. Light Stabilizers . . . . . . . . . . 119
2.14.4. Pitch Coatings . . . . . . . . . . . . 69 5.8. Commercial Products . . . . . . . 121
2.14.5. Pitch Combination Coatings . . . . 70 5.9. Use and Testing of Additives . . 121
2.15. Silicate Coatings . . . . . . . . . . 71 6. Paint Removal . . . . . . . . . . . . 122
2.15.1. Water Glass Coatings . . . . . . . . 71 6.1. Paint Removal from Metals . . . 122
2.15.2. Alkyl Silicates . . . . . . . . . . . . 72 6.1.1. Chemical Paint Removal . . . . . . 122
3. Paint Systems . . . . . . . . . . . . 75 6.1.2. Thermal Paint Removal . . . . . . . 123
3.1. Solventborne Paints . . . . . . . . 75 6.1.3. Mechanical and Low-Temperature
3.1.1. General Information . . . . . . . . . 75 Paint Removal . . . . . . . . . . . . 123
3.1.2. Properties and Raw Materials . . . 76 6.2. Paint Removal from Wood and
3.1.3. Environmental Protection and Mineral Substrates . . . . . . . . 123
Application Technology . . . . . . 78 7. Production Technology . . . . . . 124
3.2. Solvent-Free and Low-Solvent 7.1. Principles . . . . . . . . . . . . . . . 124
(High-Solids) Paints . . . . . . . . 78 7.2. Paint-Making Processes . . . . . 129
3.2.1. Principles . . . . . . . . . . . . . . . 79 7.2.1. Varnishes . . . . . . . . . . . . . . . . 129
3.2.2. Production and Uses . . . . . . . . . 80 7.2.2. Paints . . . . . . . . . . . . . . . . . . 129
3.3. Waterborne Paints . . . . . . . . . 81 7.2.3. Powder Coatings . . . . . . . . . . . 131
3.3.1. Properties . . . . . . . . . . . . . . . 81 7.3. Apparatus . . . . . . . . . . . . . . 131
3.3.2. Production and Application . . . . 84 7.3.1. Mixers . . . . . . . . . . . . . . . . . 131
3.3.3. Uses and Environmental Aspects . 85 7.3.2. Dissolvers . . . . . . . . . . . . . . . 131
3.4. Coating Powders . . . . . . . . . . 85 7.3.3. Kneaders and Kneader Mixers . . 132
3.4.1. Introduction and Economic 7.3.4. Media Mills . . . . . . . . . . . . . . 132
Importance . . . . . . . . . . . . . . 85 7.3.5. Roller Mills . . . . . . . . . . . . . . 135
3.4.2. Production . . . . . . . . . . . . . . . 86 7.3.6. Auxiliary Equipment . . . . . . . . 135
4 Paints and Coatings

8. Paint Application . . . . . . . . . . 136 11. Uses . . . . . . . . . . . . . . . . . . . 167

8.1. Types of Substrate . . . . . . . . . 136 11.1. Coating Systems for Corrosion
8.2. Pretreatment of Substrate Protection of Large Steel
Surfaces . . . . . . . . . . . . . . . . 136 Constructions (Heavy-Duty
8.2.1. Pretreatment of Metallic Substrates 136 Coatings) . . . . . . . . . . . . . . . 167
[Link]. Cleaning . . . . . . . . . . . . . . . . 136 11.2. Automotive Paints . . . . . . . . . 168
[Link]. Degreasing . . . . . . . . . . . . . . 138 11.2.1. Car Body Paints . . . . . . . . . . . 168
[Link]. Formation of Conversion Layers . 138 11.2.2. Other Automotive Coatings . . . . 170
8.2.2. Pretreatment of Plastics . . . . . . 140 11.3. Paints Used for Commercial
8.2.3. Pretreatment of Wood . . . . . . . 141 Transport Vehicles . . . . . . . . . 171
8.3. Application Methods . . . . . . . 141 11.3.1. Railroad Rolling Stock . . . . . . . 171
8.3.1. Spraying (Atomization) . . . . . . 141 11.3.2. Freight Containers . . . . . . . . . . 172
8.3.2. Electrostatic Atomization . . . . . 143 11.3.3. Road Transport Vehicles . . . . . . 172
8.3.3. Dipping . . . . . . . . . . . . . . . . 145 11.3.4. Aircraft Coatings . . . . . . . . . . . 173
8.3.4. Miscellaneous Wet Paint 11.4. Marine Coatings . . . . . . . . . . 173
Coating Methods . . . . . . . . . . 146 11.4.1. Substrate, Surface Preparation, and
8.3.5. Powder Coating . . . . . . . . . . . 149 Priming . . . . . . . . . . . . . . . . . 174
8.3.6. Coating of Plastics and Wood . . 150 11.4.2. Ship Paint Systems . . . . . . . . . 175
8.4. Paint Curing Methods . . . . . . 150 11.4.3. Fouling and Antifouling . . . . . . 176
9. Properties and Testing . . . . . . 152
11.5. Coil Coating . . . . . . . . . . . . . 177
9.1. Properties of Coating Materials 152
11.6. Coatings for Domestic
9.2. Properties of Coatings . . . . . . . 154
Appliances . . . . . . . . . . . . . . 178
9.2.1. Films for Testing . . . . . . . . . . . 154
11.7. Coatings for Packaging
9.2.2. Optical Properties . . . . . . . . . . 157
(Can Coatings) . . . . . . . . . . . 178
9.2.3. Mechanical Properties . . . . . . . 159
11.8. Furniture Coatings . . . . . . . . 179
9.2.4. Chemical Properties . . . . . . . . . 160
11.9. Coatings for Buildings . . . . . . 180
9.2.5. Weathering Tests . . . . . . . . . . . 161
10. Analysis . . . . . . . . . . . . . . . . 162 11.9.1. Exterior-Use Coatings . . . . . . . 180
10.1. Analysis of Coating Materials . 162 11.9.2. Interior-Use Coatings . . . . . . . . 181
10.1.1. Separation of the Coating Material 12. Environmental Protection
into Individual Components . . . . 162 and Toxicology . . . . . . . . . . . 182
10.1.2. Analysis of Binders . . . . . . . . . 163 12.1. Clean Air Measures . . . . . . . . 182
10.1.3. Analysis of Pigments and 12.2. Wastewater . . . . . . . . . . . . . . 184
Extenders . . . . . . . . . . . . . . . 165 12.3. Solid Residues and Waste . . . . 184
10.1.4. Analysis of Solvents . . . . . . . . . 165 12.4. Toxicology . . . . . . . . . . . . . . 185
10.1.5. Analysis of Additives . . . . . . . . 166 13. Economic Aspects . . . . . . . . . 186
10.2. Analysis of Coatings . . . . . . . . 166 14. References . . . . . . . . . . . . . . 187

1. Introduction or water. Physical film formation is only possi-

ble if the coating components remaining on the
1.1. Fundamental Concepts substrate are solid and nontacky. Chemical film
formation is necessary if the coating components
Paints or coatings are liquid, paste, or powder are liquid, tacky, or pasty; conversion to a solid
products which are applied to surfaces by var- nontacky film takes place by chemical reaction
ious methods and equipment in layers of given between the components. The reactive compo-
thickness. These form adherent films on the sur- nents can be constituents of the coating, and the
face of the substrate. reaction can be initiated by energy (heat or radi-
Film formation can occur physically or chem- ation) after application of the coating. However,
ically. Physical film formation from liquid coat- it is also possible to add a reaction partner while
ings is known as drying, whereas for powder applying the coating (multipack paints). A spe-
coatings, it is a melting process. Drying is always cial case of chemical film formation is the oxi-
associated with evaporation of organic solvents dation of coating component(s) by atmospheric
 Paints and Coatings 5

oxygen (air drying). Physical and chemical film The oldest recipe for a lacquer, from linseed
formation are often combined, e.g., in solvent- oil and the natural resin sandarac, dates from
containing stoving paints, where the first stage is 1100 a.d. and was due to the monk Rogerus von
solvent evaporation, after which the film is cured Helmershausen. Natural products such as veg-
by stoving. The properties of a paint are deter- etable oils and wood resins remained the most
mined by its qualitative and quantitative com- important raw materials for paint production,
position, suitable choice of which enables the into the early 1900s. Only the introduction of
viscosity, electrical conductivity, and drying be- faster production equipment such as belt convey-
havior to be matched to the application condi- ors made the development of new paints neces-
tions. Also, the properties of the coating film sary. Initially, the rapid-drying binder used was
(luster, elasticity, scratch resistance, hardness, nitrocellulose, which after World War I could be
adhesion, and surface structure) are determined manufactured on a large scale in existing gun-
by the paint properties. However, the condition cotton plants. Phenolic resins were the first syn-
of the substrate surface (cleanliness and freedom thetic binders (ca. 1920), followed by the alkyd
from dust and grease) is also important. resins (1930). The large number of synthetic
Coatings must fulfill many requirements. binders and resins now available are tailored
They protect the substrate against corrosion, for each application method and area of use.
weathering, and mechanical damage; have a dec- These paint raw materials are based on petro-
orative function (automotive coatings, house- chemical primary products. Vegetable and ani-
hold appliances, furniture); provide information mal oils and resins are now seldom used in their
(traffic signs, information signs, advertising); or natural form, but only after chemical modifica-
have other specific properties. tion. The tendency to use such “renewable” raw
“Coating” is a general term denoting a mate- materials is increasing. Consumer demand has
rial that is applied to a surface. “Paint” indicates led to a marked renaissance of natural products
a pigmented material, while “varnish” refers to (“biopaints”).
a clear lacquer (ISO 4618/1, DIN 55 945). The use of organic solvents in paint technol-
ogy was linked to the development of modern
rapid-drying binders. Whereas the liquid com-
1.2. Historical Development ponents previously used in coatings were veg-
etable oils or water and possibly ethanol, it now
The earliest evidence of well-preserved prehis- became necessary to use solvent mixtures to
toric paintings, dating from the 16th millenium give accelerated drying and optimized paint-
b.c., can be found in caves in Southern France application properties. Production of a wide
(Font-de-Gaume, Niaux, Lascaux), Spain (Al- range of solvents began worldwide in the chem-
tamira), and South Africa. The colors used were ical industry in the 1920s.
pure oil paints prepared from animal fat mixed Methods of applying paints also underwent
with mineral pigments such as ocher, manganese major changes in the 1900s. Whereas up to
ore (manganese dioxide), iron oxide, and chalk. this time coatings were applied manually with
The oldest rock paintings from North Africa a brush, even in industry, this technique is to-
(Sahara, Tassili n’Ajjer) date from between the day only used in the handicraft and DIY areas.
5th and the 7th millennium b.c. Many examples Modern mechanized and automated application
of paintings from Babylon, Egypt, Greece, and methods are used today for industrial-scale ap-
Italy dating from the 1st and 2nd millenium b.c. plication because of greater efficiency, low mate-
are also known. rial losses, qualitatively better results, and lower
The first painted objects come from China. labor costs. They include high-pressure spraying
Furniture and utensils were covered with a layer using compressed air or electrostatic charging,
of paint in an artistic design. The oldest tradition modern automatic and environmentally friendly
work dates from around 200 B.C. The lacquer dipping and electrophoretic processes, and ap-
used was the milky juice from the bark of the plication by rollers.
lacquer tree (Rhus vernicifera). This was col- Problems of environmental pollution also fol-
ored black or red with minerals, and later also lowed from the introduction of solvents. These
with gold dust or gold leaf. were recognized by the late 1960s and be-
6 Paints and Coatings

came the subject of development work. Water- 1.3.1. Binders and Resins
borne coatings, low-solvent coatings, solvent-
free powder coatings, and new radiation-curing Binders are macromolecular products with a mo-
coating systems with reactive solvents that are lecular mass between 500 and ca. 30 000. The
bound chemically during the hardening process higher molcular mass products include cellu-
were developed. These environmentally friendly lose nitrate and polyacrylate and vinyl chloride
coating systems have gained a considerable mar- copolymers, which are suitable for physical film
ket share. However, in some areas solvent-con- formation. The low molecular mass products in-
taining coatings are difficult to replace with- clude alkyd resins, phenolic resins, polyisocya-
out affecting quality. For this reason, solvent- nates, and epoxy resins. To produce acceptable
recycling and solvent-combustion plants have films, these binders must be chemically hard-
been developed to recover or incinerate the sol- ened after application to the substrate to pro-
vents in the waste air. duce high molecular mass cross-linked macro-
molecules.
Increasing relative molecular mass of the
1.3. Composition of Paints binder in the polymer film improves properties
such as elasticity, hardness, and impact deforma-
Paints are made of numerous components, de- tion, but also leads to higher solution viscosity
pending on the method of application, the de- of the binder. While the usefulness of a coating
sired properties, the substrate to be coated, and is enhanced by good mechanical film proper-
ecological and economic constraints. Paint com- ties, low viscosity combined with low solvent
ponents can be classified as volatile or non- content are also desirable for ease of applica-
volatile. tion and for environmental reasons. Therefore,
Volatile paint components include organic a compromise is necessary.
solvents, water, and coalescing agents. Non- The low molecular mass binders have low so-
volatile components include binders, resins, lution viscosity and allow low-emission paints
plasticizers, paint additives, dyes, pigments, and with high solids contents or even solvent-free
extenders. In some types of binder, chemical paints to be produced. Here, the binder consists
hardening can lead to condensation products of a mixture of several reactive components, and
such as water, alcohols, and aldehydes or their film formation takes place by chemical drying
acetals, which are released into the atmosphere, after application of the paint. If chemical harden-
thus being regarded as volatile components. ing occurs even at room temperature, the binder
All components fulfill special functions in the components must be mixed together shortly be-
liquid paint and in the solid coating film. Sol- fore or even during application (two- and multi-
vents, binders, and pigments account for most component systems).
of the material, the proportion of additives being Today, most binders are synthetic resins such
small. Low concentrations of additives produce as alkyd or epoxy resins.
marked effects such as improved flow behavior, The natural resin most commonly used as
better wetting of the substrate or pigment, and a binder today is rosin (colophony; → Resins,
catalytic acceleration of hardening. Natural), which is often tailored by chemical
Solvents and pigments need not always be modification to suit specific applications. Also,
present in a coating formulation. Solvent-free many synthetic hard resins, mainly based on cy-
paints and pigment-free varnishes are also avail- clohexanone, acetophenone, or aldehydes, are
able. used in the paints industry. Hard resin binders in-
The most important component of a paint for- crease the solids content, accelerate drying, and
mulation is the binder. Binders essentially deter- improve surface hardness, luster, and adhesion.
mine the application method, drying and harden- Most synthetic binders are softer and more
ing behavior, adhesion to the substrate, mechan- flexible than hard resins. Consequently, they im-
ical properties, chemical resistance, and resis- part good elasticity, impact resistance, and im-
tance to weathering. proved adhesion, even to critical undercoats, as
well as offering adequate resistance to weather-
ing and chemicals. These binders are produced
 Paints and Coatings 7

with a property profile tailored to suit particu- ratio of the volume of pigments and extenders to
lar application methods and to comply with a the total volume of the nonvolatile components.
range of technical requirements, including envi- Each coating system has a critical pigment vol-
ronmental protection, low toxicity, and suitabil- ume concentration (CPVC) at which the binder
ity for recycling and disposal. just fills the free space between the close-packed
pigment particles. At higher pigment concentra-
tions, the pigment particles in the coating film
1.3.2. Plasticizers are no longer fully wetted by the binder, leading
Plasticizers (→ Plasticizers) are organic liquids to a marked deterioration in coating film prop-
of high viscosity and low volatility. The esters erties such as luster, stability, strength, and anti-
of dicarboxylic acids (e.g., dioctyl phthalate) corrosion properties.
are well-known examples. Plasticizers lower the
softening and film-forming temperatures of the
binders, They also improve flow, flexibility, and 1.3.4. Paint Additives
adhesion properties. Chemically, plasticizers are
largely inert and do not react with the binder Paint additives are auxiliary products that are
components. Most binders used today are inher- added to coatings, usually in small amounts, to
ently flexible and can be regarded as “internally improve particular technical properties of the
plasticized” resins. For this reason, use of plas- paints or coating films. Paint additives are named
ticizers has declined. in accordance with their mode of action.
Leveling agents promote formation of a
smooth, uniform surface on drying of the paint.
1.3.3. Pigments and Extenders Suitable materials include certain high-boiling
solvents such as butyl ethers of ethylene gly-
Pigments and extenders in coatings are respon- col, propylene glycol and diglycols, as well as
sible for their color and covering power, and in cyclohexanone and alkylated cyclohexanones,
some cases give the coating film improved anti- and in some cases aromatic and aliphatic hydro-
corrosion properties. Pigments and extenders are carbons. Low molecular mass resins (e.g., some
finely ground crystalline solids that are dispersed polyacrylates and silicones) are also used. Solid
in the paint. They are divided into inorganic, leveling agents, such as special low molecular
organic, organometallic, and metallic pigments. mass resins, are also useful for improving the
By far the most commonly used pigment is ti- surface properties of films produced from pow-
tanium dioxide. As a rule, mixtures of pigments der coatings. Flow agents act by reducing the
are used for technical and economic reasons. The paint viscosity during drying. The effectiveness
hiding power and tinting strength of a paint de- of a particular flow agent depends on the type of
pend on the particle size of the pigment. The binder and the drying or hardening temperature.
usual size range aimed at is 0.1–2.0 µm, which Film-formation promoters, which are closely
means that the pigment has a high surface area related to flow agents, reduce the film-forming
that must be wetted as effectively as possible by temperature for film formation from dispersions,
the binder components to give the coating film leading to a surface that is as pore-free and uni-
good stability, weathering resistance, and luster. form as possible. Certain high-boiling glycol
This is achieved by bringing the pigment and ethers and glycol ether esters are used, often in
binder into intimate contact under the influence combination with hydrocarbons.
of high shear forces. The high hiding power of Wetting Agents, Dispersants, and Antisettling
some pigments enables them to be partially re- Agents. Wetting agents form one of the largest
placed by the cheaper extenders such as barium groups of coating additives. These are surfac-
sulfate, calcium carbonate, or kaolin. Extenders tants which aid wetting of the pigments by the
have a particle size distribution similar to that binders and prevent flocculation of the pigment
of the pigments and are incorporated into the particles. This leads to the formation of a uni-
coating in the same way. The concentration of form, haze-free color and a uniformly high luster
pigment in coating films is expressed by the pig- of the coating film. This group also includes the
ment volume concentration (PVC). This is the
8 Paints and Coatings

dispersants, which give good pigment wetting clude natural mineral products such as talc or
and hence optimum dispersion of the pigments diatomites and synthetic materials such as py-
in the paint, thereby preventing sedimentation rogenic silicas or polyolefin waxes. Matting can
particularly of high-density pigments. As well also be obtained by special formulations that ex-
as good wetting properties, some pseudoplas- ploit the incompatibility between binder compo-
ticity is also necessary. Antisettling agents have nents and their cross-linked structures.
similar characteristics to dispersants. Neutralizing agents are used in waterborne
Antifoaming agents are used to prevent paints to neutralize binders and stabilize the
foaming during paint manufacture and appli- product. Ammonia and various alkylated ami-
cation and to promote release of air from the noalcohols are used, depending on the type of
coating film during drying. Various products are binder and method of application. On harden-
used, including fatty acid esters, metallic soaps, ing, the amines mainly evaporate along with the
mineral oils, waxes, silicon oils, and siloxanes, water.
sometimes combined with emulsifiers and hy- Thickening agents control the rheological
drophobic silicas. properties of paints of various types. They in-
Catalysts are added to paints to acceler- clude inorganic (mainly silicates), organome-
ate drying and hardening. They include drying tallic (titanium and zirconium chelates), natu-
agents (driers, siccatives), which, in the case rally occurring organic (mainly cellulose ethers)
of the air-drying binders (including some alkyd and synthetic organic products (polyacrylates,
resins or unsaturated oils), accelerate decom- polyvinylpyrrolidone, polyurethanes).
position of the peroxides and hydroperoxides Preservatives (biocides, fungicides) prevent
that form during the drying process, thereby en- the attack of paint systems, principally water-
abling radical polymerization of the binders to based, by microorganisms.
take place. The driers used are mainly metallic Corrosion inhibitors are used to prevent the
soaps such as cobalt naphthenate; manganese, formation of corrosion products when water-
calcium, zinc, and barium salts; and zirconium borne paints are applied to metallic substrates
compounds. (flash rust). They include oxidizing salts such
Various products are used to catalyze the as chromates, metaborates, nitrites, and nitrates;
cross-linking of binder systems at room tem- organic amines or sulfur-containing products;
perature. For acid-catalyzed systems such as and organic salts (benzoates, naphthenates, oc-
polyester–melamine resin systems, free acids, toates).
their ammonium salts, or labile esters are suit-
able, while for base-catalyzed systems such as
polyester–isocyanate, tertiary amines or dibutyl- 1.3.5. Solvents
tin dilaurate are used. The amount of catalyst
used must be such that the pot life is not im- Solvents (→ Solvents) are compounds that are
paired. normally liquid at room temperature. Those
Antifloating and antiflooding agents prevent most commonly used in coatings technology are
horizontal and vertical segregation of pigments aromatic and aliphatic hydrocarbons, esters of
with different densities and surface properties. acetic acid, glycol ethers, alcohols, and some
This prevents differences in the color and luster ketones. Solvents dissolve solid and highly vis-
of the surface of the film, which can lead to a cous binder components. They enable incom-
blotchy appearance. patibility between paint components to be over-
Antiskinning agents are added to air-drying come, improve pigment wetting and dispersion,
paints to prevent surface skin formation caused and control storage stability and viscosity of the
by contact with atmospheric oxygen. In the film, coating. They promote the release of included air
they produce uniform drying and prevent shrink- from the liquid coating film, control the drying
age (wrinkling). Chemically, these materials are behavior of the coating, and optimize flow prop-
antioxidants such as oximes, which evaporate erties and luster. Organic solvents are used in
with the solvents during the drying process. most liquid coatings systems, including water-
Matting agents are used to produce coatings borne coatings, in which they perform important
with a matt, semi-matt, or silk finish. They in- functions.
 Paints and Coatings 9

After paint application, the solvents should Physical Drying Physical drying takes place
evaporate as quickly as possible, leaving the mainly for paints with high molecular mass
film. If no special precautions are taken, the sol- polymer binders such as cellulose nitrate, cel-
vents enter the atmosphere as pollutants. To pro- lulose esters, chlorinated rubber, vinyl resins,
tect operating personnel from the toxic effects polyacrylates, styrene copolymers, thermoplas-
of evaporating solvents, safety measures such tic polyesters, and polyamide and polyolefin
as ventilation and air exhaust are necessary. To copolymers. These materials give good flexibil-
protect the environment, incineration and some- ity and stability because of their high molecular
times solvent-recovery plant is installed to pre- mass. Their glass transition temperature should
vent solvents entering the atmosphere. Other be above room temperature to ensure adequate
measures for the protection of the workplace hardness and scratch resistance. With these poly-
and the environment from solvent vapors include mers, film formation can also take place from
the development and use of new low-solvent solutions or dispersions in organic solvents or
or solvent-free coatings, e.g., high-solids paints, water, from which the solvent or water evapo-
waterborne coatings, and powder coatings. rates, leaving behind the chemically unchanged
polymer film.
Film formation can be accelerated by drying
1.4. Paint Application at elevated temperatures (forced drying). Phys-
ically drying solvent-containing paints have a
Paint application can be performed manually, for low solids content because the molecular mass
example with brushes or rollers, or by mechan- of the binder is relatively high. Higher solids
ical methods such as spraying, atomization by contents are obtained by dispersing the binder in
rotating disks or cones, dipping, pouring, rotat- water (dispersions, emulsions) or in organic sol-
ing drums and tumbling equipment, and auto- vents (nonaqueous dispersion or NAD systems).
mated application by rollers. Powder coatings Films formed from physically drying paints,
are applied by electrostatic spraying or by dip- especially those formed from solutions, are
ping components into the powders. Multicom- sensitive to solvents (dissolution or swelling).
ponent coatings are applied with multicompo- The physically drying coatings also include
nent spraying equipment. many powder coatings that contain thermoplas-
tic binders. Film formation takes place by heat-
ing the powder that has been applied to the sub-
1.5. Drying and Film Formation strate above its melting point. This ensures that
a sealed film of polymer is formed.
As the paint dries on the substrate, a firmly Plastisols and organosols are a special case
bonded film is formed. The properties of this of physically drying coatings systems in which
film are determined both by the substrate and its the binders consist of finely dispersed poly(vinyl
pretreatment (cleaning, degreasing) and by the chloride) or thermoplastic poly(meth)acrylates
composition of the coating and the application suspended in plasticizers. Organosols also con-
method used. tain some solvent. On drying at elevated temper-
Drying of the paint on the substrate takes atures, the polymer particles are swollen by the
place physically (1–3) or chemically (4): plasticizer, a process known as gelation.

1) Evaporation of the organic solvents from Chemical Drying. Chemically drying paints
solvent-containing paints contain binder components that react together
2) Evaporation of water from waterborne paints on drying to form cross-linked macromolecules.
3) Cooling of the polymer melts (powder coat- These binder components have a relatively low
ings) molecular mass, so that their solutions can have
4) Reaction of low molecular mass products a high solids content and a low viscosity. In
with other low or medium molecular mass some cases, solvent-free liquid paints are posi-
binder components (polymerization or cross- ble. Chemical drying can occur by polymeriza-
linking) to form macromolecules tion, polyaddition, or polycondensation.
10 Paints and Coatings

When polymerization is used as the harden- to accelerate it by heat, radiation, and addition
ing principle, reactive components combine to of catalysts.
form the binder, e.g., unsaturated polyesters with
styrene or acrylate monomers. Here, one com-
ponent often behaves as a reactive solvent for the 1.6. Multicoat Systems
other, and low-emission coating systems are the
result. Cross-linking can be carried out at room Because dried coating films are not always pore-
temperature (cold curing) or by radiation curing. free, optimal protection of the substrate is not al-
In drying by polyaddition, low molecular ways ensured by one coat. A single coat can sel-
mass reactive polymers such as alkyd resins, dom fulfill all requirements such as good adhe-
saturated polyesters, or polyacrylates react with sion, corrosion protection, elasticity, hardness,
polyisocyanates or epoxy resins to form cross- decorative effect, coloration, and resistance to
linked macromolecules. Because this reaction weathering and chemicals. Coatings with differ-
can take place at room temperature, the binder ent compositions and functions are therefore of-
components must be mixed shortly before appli- ten applied in succession. For example, primers
cation. The period of time during which a coat- provide good adhesion to the substrate and maxi-
ing of this type remains usable after mixing of mum corrosion protection, whereas color stabil-
the components is known as the pot life. These ity, gloss, and resistance to weathering are better
are known as two-pack coatings, differing from provided by a top coat which is specially de-
the one-pack systems, which can be stored for signed for this purpose but may not have partic-
months or even years. ularly good corrosion resistance.
Chemically blocking one of the polyaddi- Intermediate coatings between the top coat
tion binder components (e.g., the polyisocya- and the primer are also applied if the highest
nate) gives a coating system stable at room tem- quality is required, e.g., in the automobile in-
perature. Heat is required to deblock the compo- dustry. These have the task of providing adhe-
nent and enable cross-linking to occur. Stoving sion between the primer and the top coat, and
paints of this type are used in industry and in they also smooth out irregularities on the sub-
powder coatings. strate, thereby indirectly helping to ensure good
Polycondensation drying requires the addi- flow of the top coat and a high gloss with no
tion of catalysts or the use of higher tempera- defects.
tures. Acid-catalyzed coatings are well-known
cold-curing paint systems used in the furniture
1.7. Economic Aspects
industry, while heat-curing and stoving paints
are used as industrial and automotive coatings. In the industrialized countries of Europe and
The binding agents used are functional alkyd in North America, annual paint consumption of
resins, saturated poylesters, or polyacrylates in coatings per capita is >20 kg, and high growth
combination with urea resins, melamine resins, rates can be expected in the less industrialized
or phenolic resins. On cross-linking, water, low countries of Eastern Europe, Asia, and South
molecular mass alcohols, aldehydes, acetals, and East Asia. The volume of coatings produced
other volatile compounds are released. in Western Europe in 1991 was ca. 5 x 106 t,
In practice drying of coatings and paints and, in the United States, 4.7 x 109 L. The an-
does not take place by one method alone. With nual growth rates of solvent- containing conven-
solvent- containing and waterborne heat-curing tional coatings are estimated to be 1–2 %, and, of
coatings, physical drying by solvent evaporation environmentally friendly coatings (high solids,
always precedes chemical drying. Depending on water-based, powder coatings, etc.), ca. 5 %.
the composition of the binder system, physical
and chemical drying can take place simultane-
ously, and the various mechanisms of chemi- 1.8. Future Outlook
cal drying can proceed concurrently or consec-
utively, depending on the nature of the binder. A In the past, the development of coatings was
knowledge of binder composition is important in mainly based on technical, quality, and eco-
order to assess the drying of a coating and able nomic considerations. These factors are just as
 Paints and Coatings 11

important today from a business point of view ing oils (e.g., linseed oil, China wood or tung
and will continue to be so in the future. How- oil, and soybean oil) which undergo autoxidative
ever, other considerations are now very much in polymerization in the presence of catalytic dri-
the foreground, i.e., environmental protection, ers and atmospheric oxygen (→ Drying Oils and
toxicology, environmentally friendly disposal of Related Products). Further constituents may in-
paint residues and coated articles at the end of clude hard resins (e.g., alkylphenolic resins) that
their life cycle, the recycling of coated articles, generally react with the drying oils at elevated
and the conservation of raw materials and en- temperature (230–280 ◦ C) to form oleoresinous
ergy. binders. On account of the air sensitivity of the
Thus, numerous low-emission paints have oils, heating mainly takes place under an inert
been developed, including high-solids paints, gas atmosphere.
waterborne paints, aqueous dispersions for in- Auxiliaries may be added to oil paints to im-
dustrial use, powder coatings, and radiation- prove their wetting and flow properties. The de-
curing coatings. At the forefront in adopting sired handling consistency is generally adjusted
these environmentally friendly products is heavy with aliphatic hydrocarbon solvents such as min-
industry, in particular the automobile and house- eral spirits and in certain cases with toluene or
hold appliance industries. Medium-sized and xylenes.
smaller businesses will profit from this experi- With clear varnishes 5–10 wt % of solvent is
ence, adapting it for their own needs. sufficient, with paints 10–20 wt % is sufficient.
To conserve raw materials based on mineral There are very few restrictions in the choice of
oil, renewable raw materials derived from nat- pigment; basic pigments (e.g., zinc oxide) can
ural oils and resins will be investigated and as- be used.
sessed for potential use in paints. Conventional dispersion equipment (e.g.,
Nevertheless, the principal development goal ball, roller, or sand mills) are suitable for pro-
is still to secure further improvements in the ducing oil paints.
quality of paint systems and to prolong the dura- Oil paints are relatively environmentally
bility of coating films. The longer the renewal friendly as long as harzardous solvents and toxic
of a coated surface can be delayed, the less the pigments (e.g., red lead or zinc chromate) are not
environment is polluted, and the smaller are the used. The oils used in such paints have a low vis-
amounts of waste produced and of raw materials cosity. They are therefore particularly suitable
and energy consumed. for priming coats on manually derusted steel sur-
The continuous increase in automation and faces since they wet and penetrate the residual
electronic control of paint production and ap- layers of rust well, resulting in thorough cover-
plication are equally relevant, enabling products age. Oil paints are easily applied by conventional
to be manufactured that are consistently of the methods (e.g., brushing, roller coating, spraying
highest quality. and dipping).
During film formation (curing), atmospheric
oxygen reacts with the oil to form hydroperox-
2. Types of Paints and Coatings ides which decompose into radicals and then ini-
tiate polymerization of the binder. Driers (metal-
(Binders) lic soaps such as cobalt, lead, and manganese
naphthenates or octoates) catalyze formation
In this chapter paints and coatings will be dis-
and decomposition of the hydroperoxides and
cussed according to their binders.
thereby accelerate film formation. A combina-
tion of several driers is normally used to control
the curing reaction at the surface and in the in-
2.1. Oil-Based Coatings [11] terior of the coating.
The thickness of an oil-paint coating is re-
Composition. Oil-based paints (oil paints) stricted on account of the atmospheric oxy-
are among the oldest organic coating materials; gen required for curing. With thick layers (25–
in China, they have been known for more than 30 µm on vertical surfaces and 40–50 µm on
2000 years. Oil paints consist of natural dry- horizontal surfaces), the oxygen penetrates too
12 Paints and Coatings

slowly and the lower region of the paint layer 2.2. Cellulose-Based Coatings
remains soft. Since the shrinkage of the coat-
ing differs in various layer regions during ox- 2.2.1. Nitrocellulose Lacquers
idative drying, wrinkles may form if the layer
is too thick. The drying time is highly temper- Nitrocellulose (cellulose nitrate) lacquers are a
ature dependent and may increase substantially mixture of binders (nitrocellulose and resins),
in the absence of light. At room temperature, oil plasticizers, and (optionally) pigments dissolved
paint films dry in ca. 12–24 h depending on the in organic solvents. The nonvolatile components
amount of drier added, whereas several weeks are:
are required in the vicinity of the freezing point 1) Nitrocellulose
of water. 2) Resin
During drying the films take up ca. 10– 3) Plasticizer
20 wt % of oxygen (relative to the pure oil). The 4) Pigment (extender, dye)
smell detected during drying is partly due to The volatile components are
decomposition products of the binder that are
formed during autoxidative polymerization. 1) Active solvents
Coatings derived from oil paints are tough but 2) Latent solvents
not excessively hard, and exhibit limited weather 3) Nonsolvents (diluents such as benzene or
resistance. They lose their high gloss relatively toluene)
quickly (ca. two years) and yellow much more Physical evaporation of the solvents results
than other binders, both in the light and dark as in formation of the desired solid film on the sub-
well as at elevated temperature. The coatings are strate surface. Films may also be obtained from
readily hydrolyzed and are therefore unsuitable, aqueous, low-solvent, or solvent-free nitrocellu-
at least as a topcoat, in applications involving lose emulsions or dispersions [12].
exposure to strong chemical influences.
On account of these disadvantages and the
relatively long drying time, oil paints have al- [Link]. Raw Materials
most completely lost their former importance
since the 1960s in favor of oxidatively dry- The compositions of cellulose nitrate lacquers
ing alkyd resins. Being “naturally-based paints”, are summarized in Table 1.
renewed interest has, however, recently been
Nitrocellulose. For the preparation and prop-
shown in oil paints owing to ecological reasons.
erties of nitrocellulose [9004-70-0] (cellulose
Chemically modified, oxidatively drying oils
nitrate) see → Cellulose Esters, Chap. 1.2. Ni-
(e.g., polyurethane oils, Section [Link]) are be-
trocellulose is an outstanding film-forming sub-
ing increasingly used as binders for high-solids
stance which displays rapid solvent evaporation
coatings (e.g., for wood protection). Binders for
(short drying time). It is compatible with most
oil paints include low molecular mass 1,4-cis-
coating raw materials.
polybutadienes, known as polyoils and produced
Nitrocellulose is characterized by its nitrogen
by Hüls (→ Hydrocarbons, Chap. 2.2.2). Rela-
content and solubility. The nitrogen contents are:
tively short drying times (8–12 h) are achieved
as a result of the polybutadiene component.
Ester-soluble nitrocellulose 11.88–12.2 wt %
The polyoils are heated with oxidatively dry- Alcohol-soluble nitrocellulose 10.9 –11.3 wt %
ing oils or modified with maleic anhydride;
the maleic anhydride units being converted into
imide groups with amines. Such oil paints are High-viscosity, medium-viscosity, and low-
suitable as priming coats for corrosion protec- viscosity formulations of each type are avail-
tion of manually derusted steel surfaces because able [13]. Important producers of nitrocellulose
they stabilize residual rust layers. used in lacquers include Hercules ( USA), ICI
(UK), SNPE (France), Wolff Walsrode (FRG),
and NQB (Brazil).
Films formed from high-viscosity nitrocellu-
lose have good flexibility combined with a high
 Paints and Coatings 13
Table 1. Formulation of nitrocellulose and lacquers

crack resistance. They are therefore employed nitrocellulose (which is also soluble in esters and
where high mechanical stress is to be expected ketones) is used for odorless lacquers, particu-
(e.g., in leather coatings, putty, adhesives). Only larly for printing inks and sealing waxes.
lacquers with low solids contents can be ob- According to international agreement, in-
tained from high-viscosity nitrocellulose. dustrial nitrocelluloses must have a maximum
Low-viscosity nitrocellulose is used to pre- nitrogen content of 12.6 wt % and are stabi-
pare high-solids lacquers. Since low-viscosity lized ( phlegmatized) for commercial use. Wet-
nitrocellulose produces hard to brittle coating ted nitrocellulose cotton (with water, ethanol, 2-
films, plasticizers and elastifying resins must be propanol, or butanol) contains 65 (or 70) wt %
added to the lacquer formulation. They are used nitrocellulose and 35 (or 30) wt % wetting agent.
in putty, dipping paints, and printing inks. Nitrocellulose is also available in the form of
The medium-viscosity nitrocelluloses have chips containing ≤ 82 wt % nitrocellulose and
the broadest application range, a major field be- ≥ 18 wt % plasticizers (e.g., dibutyl phthalate);
ing furniture lacquers. They are also employed pigments may also be incorporated if desired.
in paper and metal coatings as well as in reac- Wetted nitrocellulose must not be allowed to
tion lacquers (e.g., acid-catalyzed lacquers and dry out because of the risk of explosion.
polyurethane paints).
Ester-soluble nitrocelluloses are mainly used Plasticizers. Plasticizers that are compatible
in the lacquers described above. Alcohol-soluble with nitrocellulose and resins are used in coat-
ings for the following purposes:
14 Paints and Coatings

1) To improve adhesive strength and gloss Nitrocellulose lacquers can be sprayed effi-
2) To improve mechanical properties such ciently with compressed air or by an “airless”
as elongation, pliability, buckling strength, technique. Electrostatic spraying is employed
crease resistance, and deep-drawing ability to reduce the overspray and for good coverage
3) To increase resistance to light, heat, cold, (e.g., when coating chairs). Flat articles, thin
and sudden temperature changes (cold-check sheets (foils), or paper can be coated inexpen-
test) sively on casting machines. High-viscosity lac-
quers are frequently applied by roller coating.
Plasticizers may be solvents or nonsolvents for
Smaller objects are often coated by the dipping
nitrocellulose. The type used depends on the
method. The pushing-through process is used for
application. Nitrocellulose is for example solu-
coating pencils.
ble in dibutyl phthalate, dioctyl phthalate, dicy-
An important use of nitrocellulose lacquers
clohexyl phthalate, tricresyl phosphate, and tri-
is in printing inks employed in flexographic,
phenyl phosphate. Plasticizers in which nitro-
gravure, or silk-screen printing.
cellulose is insoluble include crude and blown
The most important areas of use of nitrocel-
vegetable oils, stearates, and oleates.
lulose lacquers are for coating wood, metal (e.g.,
automotive repair), paper, foil (cellophane, alu-
Resins. A large number of synthetic coating minum), leather, and textiles and in nail polish.
resins (e.g., alkyd, ketone, urea, maleate, and Aqueous nitrocellulose lacquers that contain
acrylic resins) are available for formulating ni- small amounts of solvent are used in the form
trocellulose combination lacquers. Selection cri- of emulsions or dispersions to coat leather [14]
teria include price, color, influence on solvent and decorative foils. Solvent-free dispersions are
release, gloss, hardness, sandability, yellowing, cured by UV radiation after evaporation of the
and durability of the final coating. water and are used to coat furniture, profiled
Nitrocellulose (generally in the form of boards, and paper.
chips) is used in polyurethane coatings to im-
prove drying behavior, to increase bulk, and to
obtain good flow. 2.2.2. Organic Cellulose Ester Coatings
[15–17]
Solvents. The solvent mixture has a large in-
fluence on the quality of the coated film. The Cellulose acetate [9004-35-7], the simplest or-
solvent that evaporates last should be a solvent ganic cellulose ester, offers excellent proper-
for all raw materials in the lacquer formulation. ties in coating films (e.g., flame resistance, high
The most important active (true) solvents are ac- melting point, toughness, and clarity). These es-
etate esters (e.g., ethyl, butyl, or propyl acetate) ters have limited solubility and compatibility
and ketones (e.g., acetone, methyl ethyl ketone, with other resins; this is, however, necessary for
methyl isobutyl ketone). widespread use.
Latent solvents, which become effective only Cellulose butyrate contains the bulkier bu-
in the presence of active or true solvents, include tyryl group; these esters are more compatible
alcohols (e.g., methanol, ethanol, and propanol). and soluble than acetates, but are too soft for
Like the nonsolvents these are used to reduce most coating applications. Cellulose esterified
costs. The lower alcohols (e.g., methanol or eth- with blends of alkyl groups can provide many
anol) are, of course, true solvents for alcohol- intermediate properties needed in coatings. Se-
soluble nitrocellulose. lection of the appropriate cellulose acetate bu-
tyrate [9004-36-8] (CAB) and cellulose acetate
propionate [9004-39-1] (CAP) content must be
[Link]. Application and Uses based on specific application requirements.
A detailed description of organic cellulose
The preparation of nitrocellulose lacquers is esters is given elsewhere, → Cellulose Esters,
simple and involves dissolution and mixing pro- Chap. 2. Production starts by mixing the ap-
cedures. The viscosity should be compatible propriate organic acids and anhydrides, sulfuric
with the equipment used.
 Paints and Coatings 15

acid catalyst, and purified cellulose. Esterifica- 2) Moisture Resistance. The greater the hy-
tion proceeds rapidly until all three anhydroglu- droxyl content, the more hydrophilic are
cose hydroxyls are esterified with acyl groups. films formed from it.
Anhydride mixtures produce mixed esters (e.g., 3) Toughness. Fully substituted esters are not
CAB and CAP). Fully acylated cellulose is of as tough and flexible as those with a low hy-
limited value in the coatings and plastics indus- droxyl content.
tries. Some free hydroxyl groups along the cel- 4) Reactivity. The degree of reactivity increases
lulose chain are necessary to provide solubility, as hydroxyl content increases. When cross-
flexibility, compatibility, and toughness. Since linked with other resins, the cross-link den-
termination of the esterification reaction is not sity of resultant films increases correspond-
feasible, the fully acylated triester is slowly hy- ingly.
drolyzed to give the desired hydroxyl content.
The higher viscosity form of a particular es-
Following esterification and hydrolysis, the
ter type is associated with a higher molecular
product undergoes additional manufacturing
mass and longer chain length. Increasing mo-
steps that include filtration, precipitation, wash-
lecular mass of a particular ester (and coatings
ing, and drying. The final product is usually a
formulated with it) slightly lowers its solubility
dry, free-flowing powder.
and compatibility but does not affect hardness or
density. Melting ranges and toughness increase
[Link]. Cellulose Acetate Butyrate with molecular mass.

Tennessee Eastman is presently the world’s only Uses. Protective and decorative coatings for
manufacturer of CAB and CAP. Table 2 lists the metals can be formulated as converting or curing
properties of the commercially available CAB systems or as air-drying lacquer systems. Cellu-
and CAP products. lose acetate butyrate is included in many such
coatings as a modifying resin to impart specific
Properties. The large size and low polar- properties. It can also be used as the primary
ity of the butyryl groups separate the cellulose film-forming resin. Cellulose acetate butyrate is
chains and lowers the attraction between them. usually included in coatings for metal to accel-
As butyryl content increases, properties are af- erate solvent release from the film. This signifi-
fected as follows: cantly reduces the dry-to-touch time and conse-
1) Solubility increases quently reduces dirt pickup. The cellulose resin
2) Tolerance for diluents increases (tolerance may be added at levels of 1–5 wt % to improve
signifies the ability to withstand inclusion film leveling and reduce cratering.
of a nonsolvent in the solvent system before Clear-on-base (basecoat–clearcoat) auto-
haze or precipitation occurs) motive coatings are stoving enamels that are
3) Water tolerance decreases used worldwide. Proper application of the
4) Compatibility increases basecoat is critical for obtaining the desired ap-
5) Flexibility increases pearance of the coating. Normally, aluminum
6) Moisture resistance increases flake is used for pigmentation and must be
7) Grease resistance decreases oriented parallel to the substrate. This can be
8) Tensile strength decreases achieved by inducing maximum shrinkage of
9) Hardness decreases the basecoat during solvent evaporation. Cellu-
10) Melting range decreases lose acetate butyrate (20–30 wt % of total resin
The hydroxyl content of CAB is perhaps the solids) greatly assists film shrinkage and metal-
most important chemical variable on the cellu- lic flake orientation by increasing coating vis-
lose chain. It affects properties as follows: cosity following atomization during painting op-
1) Solubility. At hydroxyl levels of <1 %, sol- erations (Fig. 1). The viscosity increase permits
ubility is limited. Solubility increases as the the application of a relatively thick, wet coating
hydroxyl content increases. At hydroxyl lev- without sagging and running. Subsequent sol-
els of ca. 5 %, CAB is soluble in lower mo- vent evaporation results in film shrinkage caus-
lecular mass alcohols. ing the aluminum to assume a position relatively
16 Paints and Coatings
Table 2. Properties of cellulose acetate butyrates (CAB) and cellulose acetate propionates (CAP) (Tennessee Eastman)
Cellulose ester Viscosity* , Pa Acetyl** Butyryl Propionyl Hydroxyl Melting Mr T g , ◦ C Density,
·s content, wt % content, content, wt % content, range, ◦ C g/cm3
wt % wt %
CAB-171–15S 5.7 29.5 17 1.5 230–240 65 000 161 1.26
CAB-321–0.1 0.038 17.5 32.5 1.3 165–175 22 000 127 1.20
CAB-381–0.1 0.038 13.5 38 1.3 155–165 20 000 123 1.20
CAB-381–0.5 0.19 13.5 38 1.3 155–165 30 000 130 1.20
CAB-381–2 0.76 13.5 38 1.3 170–185 40 000 133 1.20
CAB-381–2BP 0.84 14.5 35.5 1.8 175–185 40 000 135 1.20
CAB-381–20 7.6 13.5 37 1.8 195–205 70 000 141 1.20
CAB-381–20BP 6.08 15.5 35.5 0.8 185–195 65 000 128 1.20
CAB-500–5 1.9 4.0 51 1.0 165–175 57 000 96 1.18
CAB-531–1 0.722 3.0 50 1.7 135–150 40 000 115 1.17
CAB-551–0.01 0.0038 2.0 52 1.5 127–142 16 000 85 1.16
CAB-551–0.2 0.076 2.0 51 1.8 130–140 30 000 101 1.16
CAB-553–0.4 0.114 2.0 46 4.8 150–160 20 000 136 1.20
CAP-482–0.5 0.152 2.5 45 2.6 188–210 25 000 142 1.22
CAP-482–20 7.6 2.5 46 1.8 188–210 75 000 147 1.22
CAP-504–0.2 0.076 0.6 42.5 5.0 188–210 15 000 159 1.26
* ASTM D 817 (Formula A) and D 1343.
** ASTM D 817.

parallel to the substrate. The CAB prevents re- The surface of molded plastic parts is often
dissolution of the basecoat when the clear top- coated to obtain properties that the plastic does
coat is subsequently applied. not have (e.g., mar resistance, solvent resistance,
reduced dirt pickup in barrier coatings). (Mar
resistance is the ability to withstand scratching
and scuffing caused by sliding a rough object
or cracking upon impact of a hard object.) Cel-
lulose acetate butyrate is used in coatings for
plastic because of its toughness, low color, color
stability, good abrasion resistance, and generally
good bonding characteristics.
The development of urethane elastomers has
allowed the formulation of tough, abrasion-
resistant coatings for many flexible substrates
including textiles. One widely used application
of CAB-modified urethane elastomeric systems
is for coating lightweight outdoor backpacking
and camping equipment (e.g., portable tents).
Cellulose acetate butyrate is beneficial in
radiation-curing systems. CAB 551–0.01 with
Figure 1. The function of CAB in automotive clear-on-base its high butyryl content and low viscosity is sol-
finishes uble in many vinyl monomers used in this area.
A) Viscosity of CAB permits application of heavy Levels as low as 1–5 wt % provide good flowout
basecoat; B) Solvent evaporates, film shrinks, and flake ori- and leveling of the coating which often tends to
entation begins; C) The CAB prevents solvents in the clear
topcoat from redissolving the basecoat form craters and pull back at edges.
Another very important application is the dis-
persion of pigments that are difficult to disperse
Cellulose acetate butyrate is used in a wide
(e.g., carbon black, transparent iron oxides, ph-
variety of coatings for wood because they pro-
thalocyananine blue and green, and perylene
vide many desirable properties (fast solvent re-
red). The use of CAB and two-roll milling is
lease, flowout, and leveling; excellent spray
the most efficient method of dispersion.
characteristics, nonyellowing, and cold crack re-
sistance).
 Paints and Coatings 17

Application. Cellulose acetate butyrate lac- Commercial Products. Chlorinated rubber

quers are usually applied by spraying (air atom- from natural rubber or synthetic polyisoprene
ization, airless, spinning disk). Application by is only produced by a few manufacturers. Trade
brush or dip is possible but less commonly used. names include Adeka (Asahi Denka), Alloprene
(ICI), Amolac (VEB Chemische Werke Buna),
Chlortex (Caffaro), Pergut (Bayer) [18], Super-
[Link]. Cellulose Acetate Propionate chlor (Sanyo-Kokusaku Pulp). These products
are available in various viscosity grades, whose
Cellulose acetate propionates (CAP) have the
ranges largely coincide for the aforementioned
same characteristics as CAB, including high
commercial products (Table 3).
solubility and compatibility with other resins.
They also have a very low odor; this is impor-
Table 3. Viscosity grades of Pergut, an example of a commercial
tant in printing applications and in reprographic chlorinated rubber product
processes. Commercially available products and Designation Viscosity* , mPa · s Mean molecular
their typical properties are listed in Table 2. mass** (M w ),
Cellulose acetate propionate is used mainly in g/mol

printing inks where a low odor is required (e.g., Pergut S 5 4.5– 7.5 60 000
Pergut S 10 10.0– 12.0 124 000
in food packaging). It is also used for coating Pergut S 20 16.0– 24.0 160 000
leather clothing and for printing gift wrapping Pergut S 40 33.0– 51.0 213 000
paper. Pergut S 90 75.0–110.0 302 000
Pergut S 130 120.0–150.0 327 000
Pergut S 170 150.0–190.0 359 000
* Measured in a 20 % solution in toluene at 23 ◦ C in a Höppler
2.3. Chlorinated Rubber Coatings viscometer (DIN 53 015).
** Measured by a combination of gel permeation chromatography
2.3.1. Starting Products [18–20] and viscometry.

Chlorinated rubber was originally produced by Depending on production technology, chlo-

chlorination of natural rubber that had previ- rinated rubbers supplied by the manufacturers
ously been degraded to low molecular mass may contain 5–8 % carbon tetrachloride. Some
compounds by mastication or addition of radi- manufacturers have reduced the carbon tetra-
cal formers. Chlorine contents are typically 64– chloride content to 1 %, which means that paints
68 wt %. Modern polymer technology now pro- (formulations) can be produced that do not have
vides other synthetic substances that make pro- to be labeled according to the GefStoffV (De-
duction of chlorinated rubber independent of cember 16, 1987, Appendix I.2.1., solvents)
natural rubber. For example, synthetic polyiso- with the warning “contains carbon tetrachlo-
prene, polyethylene, polypropylene, and other ride”. Carbon tetrachloride is not only impor-
polyolefins are now used exclusively or in part tant for occupational health and safety reasons.
as starting materials. For a detailed description It is one of the chlorine-containing compounds
of chlorinated rubber, see → Rubber, 4. Chem- that are responsible for the formation of the
icals and Additives. “ozone hole”. A worldwide ban on these sub-
Chlorination products containing >64 wt % stances is now imminent. Since 1991 supply
chlorine and with mean molecular masses forms that contain <0.1 % carbon tetrachloride
of 50 000–350 000 exhibit similar properties (Bayer, ICI) were commercially available. It is
(DIN 53 243). Chlorinated polyisoprene is as- expected that an exemption order will be granted
sumed to have the following structure [20]: for the use of these products.
18 Paints and Coatings

Properties. The high degree of chlorination grades) and ca. 35 % plasticizer. Chlorinat-
substantially alters the properties of the start- ed paraffins (Hordaflex, Hoechst; Chlorparaf-
ing polymers. A hard, granular, white powder fine and Witaclor, Hüls; Cereclor, ICI) are
with the following properties is obtained: high used as plasticizers. Special nonhydrolyzable
resistance to oxidizing agents (e.g., ozone or plasticizers may be added if necessary, e.g.,
peroxide), water, inorganic salts, acids, alkalis, bisphenoxyethylformal (Desavin, Bayer) or
and gases; good solubility in almost all conven- resin-modified phenyl alkylsulfonates (Lero-
tional solvents except water, aliphatic hydrocar- moll, Bayer). This composition ensures the
bons, and alcohols; good compatibility with a “nonhydrolyzability” of the binder (resistance
wide range of paint resins and plasticizers; low to water, acid, and alkali), which is not the
flammability; fungistatic and bacteriostatic be- case if hydrolyzable phthalate or adipate plas-
havior; pigmentability with almost all inorganic ticizers are used. Nonhydrolyzable resins (e.g.,
pigments and extenders, as well as many organic coumarone–indene resins or other hydrocarbon
pigments. resins) are often added as “extenders”.
Disadvantages resulting from the high chlo- Red lead has proved outstandingly suitable
rine content include low temperature resistance as a pigment for priming coats on steel, and
(60 ◦ C wet, 90 ◦ C dry) on account of elimi- is fully effective in chlorinated rubber coatings.
nation of hydrochloric acid. Chlorinated rubber For reasons of environmental protection and oc-
also tends to undergo yellowing and chalking cupational health, the use of toxic lead com-
more readily when exposed to atmospheric influ- pounds is diminishing. Zinc phosphate is used
ences than do lightfast binders such as aliphatic instead, although it does not have the same corro-
polyurethanes or polyacrylates. (Chalking refers sion protection effect. Conventional metal pig-
to the degradation of the binder on the surface ments (e.g., lead dust, aluminum bronze, and
of the coating. The pigment is set free, forming zinc dust) produce diffusionproof coatings with
a white deposit that can be wiped off.) good mechanical properties. In the case of alu-
Other Areas of Application. In addition to minum bronze and zinc dust, stabilization of the
its principal use as a paint binder, chlorinated paint is required to prevent gelatinization. Iron
rubber is added to rotary gravure inks; it facil- oxide, chromium oxide, and titanium dioxide
itates transport of the pigments from the ink- pigments, commonly used in the paint indus-
ing device to the print carrier and good set- try, are suitable for finishing and topcoats. Zinc
ting. This results in good printability, fast drying, oxide, white lead, and lithopone are, however,
and a shiny, smudgeproof print. These properties unsuitable.
are important for printing illustrated magazines, All inert minerals are suitable as extenders.
prospectuses, and catalogs with large circulation Carbonate-containing extenders may only be
numbers. used if no stringent requirements have to be sat-
In polychloroprene-based adhesives, addi- isfied as regards resistance to water and chemi-
tion of ca. 10 % chlorinated rubber (based on cals.
the polychloroprene content) increases the ini- The choice of solvent is practically unlimited.
tial adhesive strength (contact adhesives) and Xylene or other alkylbenzenes are generally rec-
improves heat stability. ommended. Mixtures of esters and mineral spirit
can be used to avoid compulsory warning labels.
Hydrogenated and modified castor oil is used
2.3.2. Chlorinated Rubber Paints as an additive to adjust the viscosity and fa-
cilitate application with a brush or spray gun
Chlorinated rubber and related chlorinated poly- (compressed air or airless); layer thicknesses of
mers form coating films by physical drying. ≥ 100 µm are thereby achieved [21–23].
Plasticizers or resins have to be added since oth-
erwise brittle films are formed. Production. Chlorinated rubber paints are
produced by conventional means. The plasti-
Composition. The binder consists of ca. cizer, resins, and in some cases a proportion of
65 % chlorinated rubber (usually low-viscosity the chlorinated rubber are first dissolved in the
solvent. The high-boiling solvent contained in
 Paints and Coatings 19

the formulation is preferred for this step. The added to an alkyd resin, acrylic resin, or bitu-
hydrogenated castor oil is then added and the minous substances to improve properties such
resultant mixture is dispersed in a dissolver. In as drying rate, water resistance, or chemical re-
order to obtain optimum “digestion”, the instruc- sistance. This application only accounts for a
tions of the castor oil supplier should be strictly small proportion of the total chlorinated rubber
observed; the temperature should not be allowed consumption.
to exceed ca. 60 ◦ C. Dispersion is followed by The proportion of chlorinated rubber in the
the formation of a paste with the pigments and binder varies from 10 to 50 wt % depending
extenders, and grinding. Conventional appara- on the intended application; plasticizers and/or
tus including dissolvers is suitable as grinding alkyd resins and/or acrylic resins account for the
equipment; grinding with steel balls should be remainder.
avoided since the iron dust that is formed can In combinations with bituminous substances
cause the final paint to gelatinize after prolonged the proportion of chlorinated rubber ranges from
storage. The ground material is then combined 1:10 to 10:1. The ratio depends on whether the
with the separately prepared chlorinated rubber goal is to improve the bitumen-based coating
solution. without any substantial increase in cost, or to re-
duce the cost of the chlorinated rubber coating.
Application. Chlorinated rubber paints can Adhesion is improved but with the disadvantage
be applied with all conventional coating equip- of darker shades caused by the black bitumen.
ment. The suppliers’ (manufacturers’) instruc-
tions must, however, be observed since the coat- Production corresponds to that of pure chlo-
ing material (chlorinated rubber paint) is specif- rinated rubber paints (see Section 2.3.2).
ically formulated for the recommended applica-
tion equipment. Chlorinated Rubber–Alkyd Resin Combi-
nations. In these combinations chlorinated rub-
Uses. On account of their high water resis- ber accounts for 25–50 % of the binder. Chlori-
tance, chlorinated rubber paints are used for un- nated rubber is used to increase the drying rate
derwater coatings on steel and concrete (e.g., and/or improve the chemical resistance. These
water storage vessels, swimming baths, sewage paints also exploit the benefits of the alkyd resin,
systems, harbor installations, and docks). The e.g., good brushability and nonsolubilization.
chemical resistance is exploited in vessels, They are used for corrosion protection in indus-
tanks, and constructional parts used in mines, trial plants or marine environments to protect
chemical plants, etc., in which aqueous solutions steel, galvanized steel, and aluminum; air-drying
of inorganic chemicals are handled. Coatings for or forced-dried industrial paints (e.g., for agri-
concrete require chlorinated rubber as a binder cultural machinery); and road marking paints.
due to the alkalinity of the concrete surface.
The main area of use of chlorinated rubber Chlorinated Rubber–Acrylic Resin Com-
paints is for underwater coatings on ships (see binations. Physically drying acrylic resins are
also Section 11.4). Favorable properties for this used for these combinations. These combina-
application are high water resistance, rapid dry- tions have the same drying rates as normal
ing (which is independent of the external temper- chlorinated rubber paints (see Section 2.3.2).
ature in the shipyard), good mutual adhesion of They have improved flow properties (particu-
the individual layers, and the fact that old coats larly when applied by pouring techniques), im-
of paint can easily be renewed. proved weather resistance (chalking and yellow-
ing), and favorable mechanical properties (ad-
hesion and extensibility). Applications include
2.3.3. Chlorinated Rubber Combination topcoats for ship superstructures and priming
Paints coats on galvanized surfaces.

Composition. Chlorinated rubber combina- Combinations with Bituminous Sub-

tion paints contain a second resin as the property- stances. Chlorinated rubber can be combined
determining binder. The chlorinated rubber is with bitumen and tars but compatibility has to
20 Paints and Coatings

be checked. Addition of chlorinated rubber re- The properties of vinyl resins, paints, and
duces thermoplasticity, accelerates drying, and coatings are chiefly determined by the nature
prevents cracking of the final coating in adverse and number of substituents. The substituents
weather conditions, without, however, adversely influence the crystallization behavior and thus
affecting the good adhesion, water resistance, the properties of interest in paint technology
and chemical resistance of the bituminous sub- such as the softening range, mechanical prop-
stance. erties (film flexibility, cold embrittlement ten-
Bituminous coatings reinforced with chlori- dency, film hardness), the film-forming temper-
nated rubber are used in silos, tanning pits, drink- ature in dispersions, solubility, and compatibil-
ing water containers, and on ships’ hulls (on ity with other binders. Chemical behavior also
the underwater part). Bituminous substances for depends on the substituents: ester groups can
coatings are supplied as special products that are be hydrolyzed, free carboxyl groups improve
free from carcinogenic constituents. adhesion to metals, and hydroxyl groups per-
mit cross-linking with reactants such as isocya-
nates. Pigment wetting, pigment loading, water
2.4. Vinyl Coatings swelling capacity, diffusion of water vapor and
other gases, solvent retention, and many other
This section deals with paints based on vinyl phenomena are also largely determined by the
resins (including vinyl copolymers) which are substituents.
synthesized by polymerization of monomers Copolymerization and the associated intro-
containing terminal CH2 =CH groups. Poly- duction of further substituents allows individual
olefins, poly(vinyl halides) and vinyl halide properties to be modified. For example, internal
copolymers, poly(vinyl esters), poly(vinyl al- plasticization can be achieved by copolymeriz-
cohol), poly(vinyl acetals), poly(vinyl ethers), ing “rigid” monomers with “soft” monomers.
and polystyrene are discussed. Polyacrylates Vinyl paints are produced by conventional
(acrylic resins) are treated in Section 2.5. techniques (see Chap. 7) and can be applied by
all conventional methods (e.g., spraying, brush-
ing, roller coating, and dipping). They are dried
2.4.1. General Properties at room temperature; heating can be used to
shorten the drying process.
Paints and coating materials based on vinyl
resins are generally physically drying. Only in a
few cases can vinyl resins be chemically cross- 2.4.2. Coatings Based on Polyolefins and
linked with other reactants via incorporated re- Polyolefin Derivatives
active groups. The properties of the paints are
therefore primarily determined by the chemical Polyolefins are described in detail elsewhere,
and physical nature of the vinyl resin. Despite → Polyolefins.
the large number of available vinyl resins this
class of binders has some common features. Polyethylene can only dissolve in hydrocar-
All vinyl resins have a linear carbon chain bons above its melting point. On account of its
with lateral substituents and exhibit a range of low solubility it is used in coatings solely in the
molecular masses. Increasing molecular mass is form of powders and dispersions.
accompanied by improved mechanical proper- On account of their paraffinic nature, polyeth-
ties, a decrease in solubility, and an increase ylene coatings are highly resistant to chemicals.
in the viscosity of their solutions. Vinyl resins They are, however, attacked by strong oxidiz-
of high molecular mass can therefore only be ing agents. Polyethylene coatings are elastically
used in the form of dispersions or powders for tough, flexible (even at low temperature), resis-
paint applications. Solvent-containing paints re- tant to hot water, and nontoxic.
quire vinyl resins of considerably lower molec- Polyethylenes of lower molecular mass are
ular mass than plastics, since only then can a added as slip and matting agents to paints and
sufficient binder content be achieved in the vis- printing inks and can also produce dirt-repellent
cosity range required for paint application.
 Paints and Coatings 21

and abrasion-resistant effects. The wax disper- Commercial products include chlorinated
sions are produced by hot dissolution and precip- polyolefins CP (Eastman) and Hardlen (Toyo
itation in aromatic hydrocarbons. This is not nec- Kasei Kogyo).
essary with commercial microcrystalline grades.
Aqueous dispersions of polyethylene are impor- Chlorosulfonated polyethylene is obtained
tant as polishing agents. from polyethylene by simultaneous treatment
with chlorine and chlorosulfonic acid. The
Polyisobutenes do not crystallize. Poly- binder is cross-linked via its sulfonyl group with
isobutenes of low molecular mass are flexible metal oxides, preferably lead oxide, in the pres-
resins, and those of high molecular mass are ence of organic acids and sulfur-containing or-
elastomers. Their use in the paint sector is re- ganic accelerators. The paints may be formu-
stricted on account of their aliphatic nature and lated as air- and oven-drying, one- and two-pack
limited compatibility with other binders. They systems with a pot life of one to two weeks.
are employed in combination with hydrocarbons Cross-linked films of chlorosulfonated polyeth-
such as paraffins, rubber, and bitumen. They are ylene have an extremely high chemical resis-
used as plasticizing components. tance, particularly against oxidizing agents (it is
used in internal coatings of chromic acid baths).
Ethylene Copolymers. Ethylene–vinyl ac-
etate copolymers differ according to their vinyl
acetate content and molecular mass. With in- 2.4.3. Poly(Vinyl Halides) and Vinyl Halide
creasing vinyl acetate content, compatibility Copolymers
with paraffin waxes decreases, but that with
other binders increases. Low molecular mass [Link]. Poly(Vinyl Chloride) and Vinyl
types containing 25–40 % vinyl acetate are read- Chloride Copolymers
ily or sufficiently soluble in solvents. With
a 40 % vinyl acetate content, they can be For a detailed description of poly(vinyl chlo-
combined with polar resins and nitrocellulose. ride), see → Poly(Vinyl Chloride)).
Terpolymers with free carboxyl groups ex-
hibit improved adhesion. Ethylene–vinyl acetate Poly(vinyl chloride) [9002-86-2] (PVC) is
copolymers are primarily added to waxes to im- sparingly soluble in the solvents used in the
prove their properties, but are also used to in- paint industry, and so is rarely used as a paint
crease flexibility and adhesion in paints, print- binder. It is used to a significant extent in the
ing inks and adhesives, and for hot melt coat- form of paste-forming PVC powders in plasti-
ings. Ethylene–vinyl acetate copolymers have sols and organosols. Plastisols are PVC disper-
low water vapor and gas permeabilities (barrier sions in plasticizers that also contain stabiliz-
effect). ers, extenders, pigments, and processing agents.
Powder coatings are also formed from ethyl- Organosols additionally contain solvent-soluble
ene–vinyl acetate copolymers (see Section 3.4). binders. Since plastisols and organosols adhere
Copolymers of ethylene with maleic acid (anhy- poorly to metals, adhesion promoters are nec-
dride) of low molecular mass are water-soluble, essary; organosols can also be combined with
form salts, and undergo cross-linking reactions. adhesive resins when applied to metals.
Film formation takes place at gelation tem-
Chlorinated Polyethylene and Polypro- peratures from 160 to 200 ◦ C. The properties
pylene. Totally chlorinated polyethylene and of the coating depend on the type and amount
polypropylene have a chlorine content of 64– of PVC, plasticizer, and extender. A foam-
68 %. Their properties largely correspond to ing effect can be achieved during gelation by
those of chlorinated rubber (see Section 2.3). adding blowing agents. Poly(vinyl chloride) is
Chlorinated polypropylenes can be used for also used in powder coatings, which are applied
chemical-resistant and weather-resistant coat- by fluidizedbed coating and electrostatic spray-
ings. These binders are important in adhesion ing (corrosion protection for metal furniture,
priming coats and heat-sealing lacquers for wire, aluminum front elements for buildings,
polypropylene sheets.
22 Paints and Coatings

and road-marking posts). PVC coatings have fa- ents. Alcohols and aliphatic hydrocarbons do not
vorable mechanical properties, a high abrasion dissolve vinyl chloride copolymers.
resistance, and high chemical resistance. Both monomeric and polymeric plasticizers
Commercial products include Ekavyl, Lu- are suitable for plasticization. Practically all
covyl (Atochem); Geon (Goodrich); Hostalit monomeric plasticizers for PVC can be used.
(Hoechst); Solvic (Solvay); Vestolit (Hüls); and Suitable polymeric plasticizers include polyadi-
Vinnol (Wacker). pates, chlorinated paraffins, carbamide resins,
and epoxides. Vinyl chloride copolymers are
Chlorinated Poly(Vinyl Chloride). Post- compatible with most conventional pigments
chlorinated PVC combines the advantageous and extenders. Despite their high intrinsic sta-
properties of PVC e.g., good chemical and bility, paints based on vinyl chloride copolymers
weather resistance with good solubility in most have to be stabilized against dehydrochlorina-
conventional solvents. Its importance has, how- tion in the presence of heat and/or UV radiation
ever, continually decreased in the paints sector. for some applications. Epoxy compounds are of-
ten sufficient for thermal stabilization.
Vinyl Chloride Copolymers. Vinyl chlo- The composition of vinyl chloride copoly-
ride copolymers can be used in a wide variety mers without functional groups influences their
of paint technology applications. The solubility solubility behavior and compatibility with other
of vinyl chloride copolymers is considerably paint binders. For example, copolymers with
higher than that of the PVC homopolymer. Im- isobutyl vinyl ether or maleate esters dissolve
portant examples are copolymers without ad- in aromatic hydrocarbons, whereas copolymers
ditional functional groups formed with vinyl with vinyl acetate merely swell in these sol-
acetate, dibutyl maleate, or isobutyl vinyl ether; vents. Paint films formed from vinyl chloride
terpolymers with carboxyl groups formed with copolymers without functional groups are heat-
dibutyl maleate or vinyl acetate and a dicarbox- sealable on account of their thermoplastic char-
ylic acid; and copolymers and terpolymers with acter. Since the films adhere poorly to nonab-
hydroxyl groups formed with hydroxyacrylates sorbing substrates such as metals, they are suit-
or with vinyl acetate and vinyl alcohol. able as binders for strippable coatings. On ac-
Commercially available PVC copolymers count of their good chemical resistance, vinyl
differ in composition and molecular mass. They chloride copolymers are also extremely suit-
are physically drying binders that undergo film able as binders for exterior-use paints, traffic
formation by solvent evaporation. (The types paints, and paper and foil lacquers; their lack
with hydroxyl groups can, however, also be of taste and odor means that they can be used as
used as combination binders in reactive sys- pasteurization-resistant coatings for can interi-
tems. They can be cross-linked, for example, ors.
with melamine resins or polyisocyanate resins.) Vinyl chloride terpolymers containing car-
The films are tough, abrasion resistant, thermo- boxyl groups adhere extremely well to metals.
plastic, of low flammability, colorless, odorless, Due to their special properties (outstanding ad-
tasteless, and physiologically harmless. Flexi- hesion to aluminum, good chemical resistance,
bility and abrasion resistance improve with in- heat-sealable from ca. 140 ◦ C – the sealing tem-
creasing molecular mass. Vinyl chloride copoly- peratures can be lowered by adding plasticiz-
mers exhibit a good water resistance and out- ers) these copolymers are ideal binders for heat-
standing resistance to alkalis, dilute mineral sealable finishes of aluminum foils used in the
acids, salt solutions, oils, fats, greases, alcohols, packaging sector.
and gasoline. Paints can readily be formulated Vinyl chloride copolymers containing hy-
with this group of binders and can be applied by droxyl groups can be used in combination with
conventional methods. other binders in reactive systems. The non-
Preferred solvents include ketones, esters, cross-linked paint films are thermoplastic and
and chlorinated hydrocarbons. Aromatic hydro- therefore heat-sealable. Cross-linking (e.g., with
carbons have a swelling effect on most vinyl melamine resins or polyisocyanate resins) low-
chloride copolymers, but are widely used as dilu- ers the thermoplasticity and improves adhe-
sion and resistance. The hydroxyl groups are
 Paints and Coatings 23

also responsible for very good adhesion to or- pylene copolymer [25067-11-2] (FEP), and eth-
ganic substrates; these copolymers are there- ylene–tetrafluoroethylene copolymer [25038-
fore used as intermediate layers in marine coat- 71-5] (ETFE) have been used as antistick or an-
ings. In two-component polyurethane lacquers, ticorrosive coatings. Only poly(vinylidene fluo-
hydroxyl-containing vinyl chloride copolymers ride) [24937-79-9] (PVDF) has so far been used
can be used alone or in combination with poly- in paints. The major difficulties in employing
ols. In the latter case, lacquer viscosity can be thermoplastic fluoropolymers in paints and coat-
adjusted and initial physical drying can be ac- ings result from their poor solubility in organic
celerated. As a result of their outstanding pig- solvents and also from the necessity to bake them
ment wetting and stabilization properties, their at a rather high temperature (> 200 ◦ C). How-
high pigment loading, and compatibility with ever, novel fluoropolymers with curable charac-
polyester and polyurethane resins, hydroxyl- teristics have also been developed (one of them
containing PVC copolymers are used as binders was successfully commercialized), mainly as
for magnetic storage media. highly weather-resistant paints [24, 25].
Commercial products include Corvic (ICI);
Hostaflex (Hoechst); Laroflex, Lutofan (BASF); Coatings with Thermoplastic Fluoropoly-
S-Lec (Sekisui); Ucar, Vinylite (Union Carbide); mers. Poly(vinylidene fluoride), PVDF, is the
Vilit (Hüls); and Vinnol (Wacker). only conventional thermoplastic fluoropoly-
mer that is used as a commercial prod-
uct for weather-resistant paints. This crys-
[Link]. Vinylidene Chloride Copolymers talline polymer is composed of -CH2 CF2 - re-
peating units; it is soluble in highly polar
On account of its low thermal stability, solvents such as dimethylformamide or di-
poly(vinylidene chloride) is seldom used in methylacetamide (→ Fluoropolymers, Organic,
paints. Vinylidene chloride copolymers with Chap. 2.8). Poly(vinylidene fluoride) is usually
vinyl chloride, acrylonitrile, or acrylates are blended with 20–30 wt % of an acrylic resin
mainly employed. These heat-sealable copoly- such as poly(methyl methacrylate) to improve
mers are efficient gas barriers and have an out- melt flow behavior at the baking temperature
standing resistance to chemicals. They are mar- and substrate adhesion. The blended polymer is
keted as solid resins and dispersions. Vinylidene dispersed in a latent solvent (e.g., isophorone,
chloride copolymers are mainly used for coating propylene carbonate, dimethyl phthalate). The
food-packaging foils. They are also important in dispersion is applied to a substrate and baked at
paint coatings where good chemical resistance ca. 300 ◦ C for ca. 40–70 s. The weather resis-
is required. tance of the paints exceeds 20 years [26–28].
Copolymers of vinylidene fluoride with
Commercial products include Diofan tetrafluoroethylene or hexafluoropropylene have
(BASF); Haloflex (ICI); Ixan (Solvay); and been developed as an air-drying paint mainly
Saran (Dow Chemical). for repair coating of the PVDF finish [29–31].
Poly(vinylidene fluoride) is now widely used for
coil coating of galvanized iron and aluminum
[Link]. Fluoropolymer Coatings sheets, and as a maintenance-free coating for
walls of skyscraper buildings and roofing of in-
Organic fluoropolymers have been used in dustrial constructions.
many fields because they have special prop- Polytetrafluoroethylene. See also → Fluoro-
erties that no other polymers can provide polymers, Organic, Chap. 2.2. An aqueous dis-
(→ Fluoropolymers, Organic). persion of PTFE is produced by emulsion poly-
Coating is one of the important uses of flu- merization of tetrafluoroethylene followed by
oropolymers, since it enables them to exhibit thermal concentration of the latex up to ca.
their characteristics on the surface of a sub- 60 wt %. Since the polymer has a very high melt
strate. Some of the conventional fluoropoly- viscosity and does not adhere to many substrates,
mers such as polytetrafluoroethylene [9002-84- the properties of the finish are greatly influenced
0] (PTFE), tetrafluoroethylene–hexafluoropro- by pretreatment of the substrate. On physically
24 Paints and Coatings

or chemically pretreated iron or aluminum, the applied as an excellent scratch-resistant coating

PTFE coating is rather vulnerable to scratch- on plastic objects [37, 38].
ing (soft coat). If, however, the treated substrate Although these fluoropolymers are soluble
is first coated with a ceramic-powder primer to in organic solvents and can be applied at a
form a coarse, hard surface, the subsequently rather low temperature (< 200 ◦ C), character-
applied PTFE finish becomes tough and scratch- istic properties of the coating seem to be too
resistant (hard coat). These coatings are used in specialized to be widely used in the coating area.
hot cookware (e.g., frying pans) with the advan- A fluoroolefin–vinyl ether terpolymer (Lu-
tage of being nonstick and easily lubricated [32, miflon) has recently been developed [24]. This
33]. Recently, mixtures of PTFE dispersions and polymer is an amorphous, alternating copolymer
heat-resistant hydrocarbon polymers (e.g., poly- of a fluoroolefin with several vinyl monomers
imide, polyether sulfone, or polyphenylene sul- (Fig. 2). The alternating sequence is responsible
fide) have been developed to improve the poor for the high performance of the resultant finish.
adhesion of fluoropolymer to a substrate and ap- The combination of vinyl monomers provides
plied as a primer or one-coat enamel [34]. the polymer with various properties necessary
Tetrafluoroethylene Copolymers. Tetrafluoroeth- for a coating material.
ylene–hexafluoropropylene copolymer (FEP)
and tetrafluoroethylene – perfluoroalkoxyethyl-
ene (PFA) are used as dispersion coatings in the
same way as PTFE, taking advantage of their
low melt viscosity and low viscosity at bak-
ing temperature. (See also → Fluoropolymers,
Organic, Chap. 2.3.)
Powder coating is another popular tech-
nique in fluoropolymer coating. Tetrafluoroeth-
ylene–ethylene copolymer (ETFE) has a
highly alternating sequence with a low melt-
ing point (280 ◦ C) and low melt viscos-
ity (→ Fluoropolymers, Organic, Chap. 2.5).
Tetrafluoroethylene–ethylene copolymer pow-
der has a better melt processability than PTFE;
electrostatic coating gives thick finishes with-
out pinholes that have excellent anticorrosive
and antistick characteristics. Tetrafluoroethyl-
ene–perfluoroalkoxyethylene is also applied as a
powder coating, exploiting its low melt viscosity
in the same way as ETFE.

Coatings with Curable Fluoropolymers.

In order to facilitate the application of fluo-
ropolymers, extensive studies have been per-
formed on curable fluoropolymers. A block
copolymer containing 65 % vinylidene fluoride, Figure 2. Structure of Lumiflon polymer
25 % tetrafluoroethylene, and 10 % vinyl es-
ter forms a highly weatherable, strongly adher-
ing, solventborne coating on metals or cellulosic The outstanding characteristics of this poly-
materials after photoinitiated cross-linking (UV mer as a coating material are its excellent
curing) [35, 36]. weatherability and its ease of handling and pro-
Hydroxyl-containing fluoropolymers made cessing [33, 39–41]. The hydroxyalkyl groups in
of fluoroolefin and hydroxyalkyl vinyl ether, the polymer react with polyisocyanates at room
hexamethoxymethylmelamine, and silica form temperature and with melamine resin or blocked
highly cross-linkable liquid mixtures and can be isocyanates at higher temperature. Lumiflon can
 Paints and Coatings 25

therefore be formulated for both on-site coat- sions. For a detailed description of poly(vinyl
ings that are cured at ambient temperature and esters), see → Poly(Vinyl Esters).
for thermoset coatings in the factory. Practical
application to plastics, buildings, various archi-
tectural structures, bridges, and automotives is [Link]. Solid Resins
now proceeding and the market is expanding an-
nually. Poly(vinyl acetate) and vinyl acetate copolymers
Several fluoroolefin–vinyl monomer terpoly- with crotonic acid, vinyl laurate, and dibutyl
mers have been developed based on the Lumiflon maleate are important solid resins; some are
polymer [42–45]: available in solution.

Poly(Vinyl Acetate). Commercial grades of

poly(vinyl acetate) [9003-20-7] differ in molec-
ular mass and therefore in their viscosity when
dissolved. Poly(vinyl acetate) is a physically
drying binder that forms transparent, lightfast
films with good hardness, gloss, and adhesive
strength. It dissolves in lower alcohols, glycols,
esters, ketones, and toluene. Thanks to their elas-
tic properties, paints and adhesives based on
poly(vinyl acetate) generally require little plas-
ticizer. Plasticizers not only increase elasticity
but also lower the glass transition temperature,
which adversely affects blocking stability and
can lead to sticky surfaces.
The neutral behavior of poly(vinyl acetate)
allows the use of all conventional pigments.
Poly(vinyl acetate) is highly compatible with
Recently waterborne coatings based on ester-soluble nitrocellulose and improves the ad-
fluoroolefin–vinyl ether terpolymers have been hesion and lightfastness of the latter. Poly(vinyl
reported, in which a macromonomer with a hy- acetate) can also be readily combined with phe-
drophilic side chain was copolymerized with flu- nolic resins, ketone resins, and colophony resins.
oroolefin [46]. On account of their excellent lightfastness,
A unique fluoroepoxy compound is liquid at high gloss, and physiological harmlessness,
ambient temperature and can be cured by incor- poly(vinyl acetates) are used as binders in nitro-
poration of suitable agents (e.g., amino silicone cellulose combination paints for paper, labels,
compounds) [47]. It forms finishes with low fric- cardboard, wood, leather, and certain plastics.
tion, oil and water repellency, and antifouling Low molecular mass grades are used in impreg-
properties [48, 49]. nation coatings that are resistant to oil, grease,
and moisture, and in priming coats on cardboard
or masonry. On account of the thermoplastic
properties, heat-sealable lacquers can also be
formulated. Poly(vinyl acetate) is an extremely
important raw material in the adhesives industry.
Commercial products include Gelva (Mon-
santo); Mowilith (Hoechst); Rhodopas (Rhône–
Poulenc), Vinac (Air Products); Vinavil (Monte-
2.4.4. Poly(Vinyl Esters)
dison); and Vinnapas (Wacker).
Poly(vinyl esters) used in paints and adhesives
Vinyl Acetate Copolymers. Copolymeriza-
are available as homopolymers and copolymers
tion of vinyl acetate with other monomers al-
in the form of solid resins, solutions, and disper-
lows specific improvement of certain properties.
26 Paints and Coatings

Copolymers generally exhibit a broader com- colloids such as poly(vinyl alcohol) and cellu-
patibility than the homopolymer. For example, lose derivatives or emulsifiers] influences behav-
softer, permanently flexible polymers with a ior under mechanical stress, pigment and exten-
lower water uptake and higher alkali resistance der compatibility, pigment loading, water resis-
are obtained by polymerizing vinyl acetate with tance, and rheology.
vinyl laurate. On account of their thermoplastic Film formation in polymer dispersions occurs
properties these copolymers are used in heat- as a result of the agglomeration and fusion of
sealable finishes on paper, cardboard, and alu- the polymer particles (diameter 100–1000 nm)
minum foil. In cellulose nitrate lacquers they after evaporation of the water. The minimum
increase adhesion, lightfastness, and the body temperature at which the particles fuse to form
fullness of the paint film. They can also be used a film (minimum film-forming temperature) is
for priming coats and for stabilizing porous or related to the glass transition temperature. It
absorbent substrates. can be lowered to facilitate paint application
Copolymers of vinyl acetate and dibutyl by adding plasticizers or solvents. Poly(vinyl
maleate are used in adhesives and as binders in acetate) dispersions form lightfast, dry, hard,
deep sealers. Copolymers of vinyl acetate and brittle films. Plasticizers therefore have to be
crotonic acid dissolve in aqueous alkalis with used (external plasticization), which are, how-
salt formation. The carboxyl groups confer bet- ever, volatile and lead to embrittlement of the
ter metal adhesion. films after a relatively short time. Internally plas-
Vinyl acetate copolymers are also used as a ticized dispersions of copolymers of vinyl ac-
raw material for wash-off adhesives, textile fin- etate with vinyl laurate, butyl maleate, Versatic
ishing agents, and marking inks with extremely Acid esters, or ethylene form permanently flexi-
good adhesion on a wide variety of substrates. ble, nonaging films that are not, however, always
Commercial products include Mowilith sufficiently resistant to hydrolysis. Terpolymer
(Hoechst) and Vinnapas (Wacker). (vinyl acetate–ethylene–vinyl chloride) disper-
sions form films that are more resistant to hydro-
lysis than homopolymer and copolymer disper-
[Link]. Dispersions sions. The films also have a higher mechani-
cal strength and lower flammability. The glass
Poly(vinyl ester) dispersions are quantitatively transition temperature of the terpolymer can be
more important than solid resins. Homopoly- varied within wide limits and properties can be
mer and copolymer dispersions are used for matched to requirements by using a suitable
binders in emulsion (dispersion) paints, plastic- choice of comonomers. The same is true of vinyl
bonded plasters, and water-thinnable adhesives. propionate copolymer dispersions.
Poly(vinyl acetate) dispersions are less impor- Poly(vinyl ester) dispersions are important
tant than vinyl acetate copolymer dispersions. binders for indoor (conventional, solvent-free)
The most important comonomers of vinyl ac- and outdoor paints, special coatings, and tex-
etate are vinyl laurate, dibutyl maleate, Versatic tured finishes. Special types are used for wood
Acid esters (VeoVa, Shell), ethylene, vinyl chlo- paints and for coating paper and cardboard.
ride, and butyl acrylate. Poly(vinyl propionate) Poly(vinyl ester) dispersions are also important
and copolymers of vinyl propionate with butyl in the adhesives and textile finishing industries.
acrylate, styrene, or vinyl chloride are also mar-
keted and used as dispersions. Commercial products include Airflex (Air
The properties of the films and coatings ob- Products); Dilexo (Texaco); Elotex (Ebnöther);
tained from dispersions depend primarily on the Emultex (Revertex); Ertimul (ERT); Mowilith
polymer composition, stabilization system, and (Hoechst); Propiofan (BASF); Ravemul
particle size. The type of polymer determines (ANIC); Rhodopas (Rhône–Poulenc); Uba-
film-forming properties, resistance to hydroly- tol (Cray Valley Kunstharze); Ucar (Union
sis, and to some extent the water resistance, Carbide); Vinamul (Vinyl Products); Viking
flammability, and mechanical properties such (Kirkless Chemicals); Vinnapas (Wacker); and
as flexibility, elongation at break, and tensile Walpol (Reichhold).
strength. The stabilization system [protective
 Paints and Coatings 27

2.4.5. Poly(Vinyl Alcohol) terpolymers of vinyl alcohol, vinyl acetal, and

vinyl acetate.
Poly(vinyl alcohol) [9002-89-5] is obtained by Poly(vinyl formals) and poly(vinyl butyrals)
hydrolysis of poly(vinyl acetate) (→ Polyvinyl are of importance in the paint industry. Com-
Compounds, Others). Commercial grades of mercial products differ in the degree of poly-
poly(vinyl alcohol) differ in the degree of poly- merization and acetalation, but especially in the
merization (molecular mass) and degree of residual poly(vinyl alcohol) content.
hydrolysis [residual poly(vinyl acetate) con-
tent]. Poly(Vinyl Formals). Poly(vinyl formals)
The water solubility of these polymers de- [63148-64-1] are physically drying binders.
clines with decreasing hydrolysis and increasing The films exhibit high resistance to chemicals
molecular mass. Poly(vinyl alcohols) containing and favorable mechanical properties. Relatively
up to 20 wt % vinyl acetate are insoluble in or- powerful organic solvents are required for dis-
ganic solvents. Poly(vinyl alcohol) is resistant solution (e.g., chlorinated hydrocarbons, cyclic
to oils, fats, greases, and waxes. Films obtained ethers, and mixtures of alcohols and aromatic
from aqueous solutions are clear and colorless, hydrocarbons). The free hydroxyl groups of the
have a high crack resistance, exhibit good light- polymers confer good pigment wetting and ad-
fastness, and are impermeable to water vapor. hesion to various substrates. Poly(vinyl formals)
Water-soluble organic compounds with can be cross-linked via the hydroxyl groups; this
highly polar groups and a high boiling point may improves chemical resistance.
be used as plasticizers. Poly(vinyl alcohol) has Poly(vinyl formals) are compatible with a
a good pigment binding capacity and is compat- range of plasticizers (that are used, for example,
ible with the pigments and extenders conven- to improve the low-temperature flexibility) and
tionally used in the paint industry. Resistance to binders, in particular polyisocyanate, phenolic,
water can be improved by reacting the hydroxyl epoxy, and melamine resins.
groups with aldehydes or by cross-linking with The most important use of poly(vinyl for-
urea resins or melamine resins in the presence mals) is for coating wire. They are also used for
of acid catalysts. coating magnetic recording media and as adhe-
Poly(vinyl alcohol) is used in the coating sec- sives for metal–metal composites used in con-
tor (e.g., as a thickening agent for aqueous sys- struction.
tems), in adhesives, for finishing paper and card- Commercial products include Form-
board, for coating paper, as a binder for strip- var (Monsanto); Pioloform FN (Wacker);
pable coatings, and as a protective colloid for Polyvinylformal (Siva); and Vinylec F (Chisso).
dispersions.
Poly(Vinyl Butyrals). Poly(vinyl butyrals)
Commercial products include Airvol (Air [63148-65-2] are physically drying binders. On
Products); Elvanol (Du Pont); Ertivinol (ERT); account of their free hydroxyl groups they can
Gohsenol (Nippon Gohsei); Mowiol (Hoechst); also be used in reactive systems. Non-cross-
Polyviol (Wacker); Poval (Kuraray, Denka, linked films are thermoplastic and therefore
Shinet-Su); and Rhodoviol (Rhône–Poulenc). heat-sealable. As well as having a high heat re-
sistance and lightfastness, poly(vinyl butyrals)
also exhibit good resistance to fats, greases, oils,
2.4.6. Poly(Vinyl Acetals) bitumen, and gasoline. Outstanding properties
are their good adhesion to metals, glass, ab-
Poly(vinyl acetals) are produced by re- sorbent substrates, and plastics sheets, as well as
acting poly(vinyl alcohol) with aldehydes their excellent pigment wetting properties. Alco-
(→ Polyvinyl Compounds, Others). Since ac- hols are preferred as solvents; esters and ketones
etalation does not proceed quantitatively and a have a somewhat lower solvent power.
proportion of the acetyl groups remains after Poly(vinyl butyrals) form very flexible films.
hydrolysis of poly-(vinyl acetate) to poly(vinyl Plasticizers can be used to improve cold flexi-
alcohol), poly(vinyl acetals) may be regarded as bility and reduce solution viscosity. Poly(vinyl
butyrals) are also compatible with a wide range
28 Paints and Coatings

of resins (e.g., epoxy, urea, melamine, phe- used mainly as plasticizing and in some cases
nolic, polyisocyanate, nitrocellulose, polyeth- as adhesion-improving resins for chlorine-con-
yleneimines, and ketone resins). The resis- taining binders, styrene polymers, nitrocellu-
tance of poly(vinyl butyral) to chemicals can lose, and brittle resins. An example of a com-
be improved by cross-linking. As an additive mercial product is Lutonal (BASF).
poly(vinyl butyral) reduces the brittleness of
highly cross-linked coatings and improves the
adhesion, particularly to metals. Polymer com- 2.4.8. Polystyrene and Styrene Copolymers
patibility, the solubility, and plasticizer compat-
ibility depend on molecular mass and polarity For a detailed description of polystyrene and
(degree of acetalation). Poly(vinyl butyrals) are styrene copolymers, see → Polystyrene and Sty-
compatible with the pigments and extenders nor- rene Copolymers.
mally used in the paint industry. The free hy-
droxyl groups confer outstanding pigment wet- Polystyrene Dispersions. On account of
ting. their glass transition temperature (T g ) of ca.
Poly(vinyl butyrals) are an important class 100 ◦ C, polystyrene dispersions do not form
of binders. One of their main uses is in prim- films at room temperature. These rigid polymers
ing coats for corrosion protection. Poly(vinyl can only be applied with means of heat drying
butyrals) are employed together with corrosion (e.g., to stiffen fabrics and nonwovens). Film
protection pigments and phosphoric acid as ad- formation is not required in agents used to pro-
hesion priming coats (wash primers); combina- tect floor coverings and paper coatings (plastic
tion with a suitable finishing coat confers pro- pigments); in this case polystyrene is therefore
tection against corrosion and subsurface rust- applied in the form of a dispersion at room tem-
ing in metals. Reactive primers or reinforced perature.
primers are obtained by combining poly(vinyl
butyrals) with phenolic resins that contain cor- Styrene Copolymer Dispersions. The T g
rosion protection pigments and phosphoric acid. and hardness of polystyrene can be adjusted over
On account of their very high solubility in sol- a wide temperature range by copolymerization
vents such as ethanol, their good flow proper- of styrene with soft monomers such as butadiene
ties, and excellent pigment wetting, poly(vinyl and acrylate esters. Styrene–butadiene (SB) dis-
butyrals) are used for formulating flexographic persions are quantitatively the most important.
and gravure printing inks for food packaging. With a styrene–butadiene weight ratio of 85:15
High molecular mass grades are used to produce the T g is ca. 80 ◦ C, at a ratio of 45 : 55 the T g
glass composites (laminated safety glass) on ac- is ca. −25 ◦ C. On account of the cross-linking
count of their lightfastness and good adhesive capability of butadiene, SB copolymers are not
power. Poly(vinyl butyrals) are also important thermoplastics, but elastomers. Elasticity can be
as binders for primer sealers (e.g., to prevent the modified by controlling the molecular mass and
migration of bitumen) and as a temporary binder degree of cross-linking.
in ceramics production. Styrene–butadiene dispersions are generally
Commercial products include Butvar stabilized with anionic, or anionic and non-
(Monsanto); Denka Butyral (Denki Kagaku); ionic emulsifiers. Carboxylation (incorporation
Mowital (Hoechst); Pioloform B (Wacker); and of a small proportion of unsaturated carboxylic
S-Lec-B (Sekisui). acids) of SB dispersions increases their stabil-
ity and improves adhesion to various substrates.
Almost all SB dispersions used in the coating
2.4.7. Poly(Vinyl Ethers) sector are carboxylated.
Styrene–butadiene dispersions may undergo
Poly(vinyl ethers) [→ Poly(Vinyl Ethers)] oxidative post-cross-linking via the double bond
formed from methyl ethyl ether or isobutyl in the butadiene unit. Uncontrolled oxidation
ether are used as soft plasticizing resins. Sol- leads to embrittlement and, finally, to breakdown
ubility and compatibility depend on the alkyl of the binder (chalking). The dispersions are thus
group. In the paint sector, poly(vinyl ethers) are
 Paints and Coatings 29

unable to satisfy stringent requirements regard- and printing inks. Styrene–allyl alcohol copoly-
ing color stability and UV resistance. mers may also be used as cross-linkable polyol
In conventional exterior-use paints SB dis- components.
persions have largely been replaced by styrene–
acrylate dispersions, and their use is now re- Commercial Products.
stricted to special applications (corrosion pro- Soluble systems include Amoco Resins
tection primers, wood primers, mortar modifi- (Amoco); Hercoflex, Kristaflex, Piccolas-
cation) where low film permeability to gases, tic, Piccotex (Hercules); Pliolite, Pliowag
water vapor etc. and complete resistance of (Goodyear); RJ-Products (Montesano);
the polymer to hydrolysis are necessary. In or- andSupraval (BASF).
der to achieve a uniform surface and thus im- Dispersions. The main suppliers of SB dis-
prove printability, paper and card are coated with persions are: BASF, Bayer, Doverstrand, Dow
paper-coating colors. Carboxylated SB disper- Chemical, Enichem, Hüls, Rhône–Poulenc,
sions are used in these paints as binders. Synthomer. Commercial coating products in-
The many uses of SB copolymer dispersions clude Butonal, Styrofan (BASF); Dow-Latices
in the textile sector include tufting, textile, and (Dow Chemical); Lipaton (Hüls); Rhodopas
carpet coatings; needle felt and card web rein- (Rhône–Poulenc); andSynthomer-Latices (Syn-
forcement; textile finishes; and impregnation. thomer).
In addition to butadiene, other monomers can
be used for internal plasticization of polystyrene.
In the paper sector, styrene–butadiene–acrylate 2.5. Acrylic Coatings
terpolymers have advantages in special applica-
General Properties. Paints containing
tions.
acrylic resins as binders have been known since
Soluble Polystyrene. Styrene homopoly- the 1930s. They are now one of the largest prod-
mers (generally in admixture with other binders) uct classes in the paint and coatings sector. For
are used in special applications such as zinc a detailed description of acrylate polymers, see
dust primers and bronze lacquers, in paints for → Polyacrylates, → Polymethacrylates.
mineral substrates and paper, as well as in ad- Polyacrylates as binders consist of copoly-
hesives. Polystyrene and poly(α-methylstyrene) mers of acrylate and methacrylate esters. Other
have good water resistance, low permeabil- unsaturated monomers (e.g., styrene and vinyl-
ity, resistance to chemicals and light, and also toluene) may also be incorporated, but usu-
dry quickly. Suitable solvents include aliphatic ally to a lesser extent. Copolymers formed ex-
and aromatic hydrocarbons, in some cases con- clusively from acrylates and/or methacrylates
taining ketones or esters. are termed pure acrylics. The comonomers dif-
fer as regards the alcohol residues of the ester
Soluble Styrene Copolymers. Copolymers group, which also allow incorporation of ad-
internally plasticized by acrylate esters, buta- ditional functional groups. Choice of suitable
diene, maleate esters, or acrylonitrile are of monomers allows wide variation of the physical
greater importance than the homopolymers. and chemical properties of the resulting poly-
The proportion, nature, and molecular mass mer. Hydrophilicity, hydrophobicity, and acid–
of the comonomer determine the softening base properties can be adjusted; resins con-
point, solubility, flexibility, drying rate, and taining hydroxyl, amine, epoxy, or isocyanate
resistance to water, UV light, and chemicals. groups can also be produced.
Incorporation of butadiene decreases lightfast- The resin products may be solids, solutions
ness, while acrylic acid confers solubility in in organic solvents or water, emulsions, or dis-
alcohol. The range of potential uses extends persions.
from soft resins for adhesives and paper, to rigid Acrylate resins have several advantages over
resins for paints and hot-melt adhesives. Sty- other paint binders [50–54]:
rene–and vinyltoluene–acrylate polymers are 1) Polyacrylates are only slightly attacked by
used particularly in exterior-use paints, paints chemicals, and confer a high degree of resis-
for concrete and road-marking, metal lacquers, tance to paints.
30 Paints and Coatings

2) Polyacrylates are colorless, transparent, and The styrene content in the binder reduces
do not yellow, even after prolonged thermal resistance to yellowing and weathering [59],
stress. but improves resistance to chemicals, hydropho-
3) Polyacrylates do not absorb above 300 nm bic properties, adhesion, and pigment wetting.
and are therefore not degraded by UV radi- Styrene is therefore largely avoided in topcoat
ation (as long as they do not contain styrene paints for exterior use and in clearcoats.
or similar compounds). The development of low-solvent (high-
4) Polyacrylates do not have unstable double solids) paints requires resins with a very low
bonds. viscosity. The principal viscosity-determining
5) Polyacrylates have outstanding gloss and parameters for such binders are the molecular
gloss retention. mass and molecular mass distribution [55–57,
6) Acrylates, and especially methacrylates, are 60–63]. Oligomers with a molecular mass of ca.
stable to hydrolysis. 1000–3000 are required for high-solids paints
[58, 64]. An acrylate binder with a molecular
The following properties of the coating
mass of 100 000 can be processed to form a
can be ascribed to individual monomers [51].
paint with 12.5 % solids content at the applica-
Methyl methacrylate promotes weather resis-
tion viscosity; a molecular mass of ca. 6000 re-
tance, lightfastness, hardness, gloss, and gloss
sults in a paint with 50 % solids content [56]. A
retention. Styrene increases hardness and resis-
narrow molecular mass distribution is beneficial
tance to water, chemicals, and salt spray, but
in achieving low viscosity [55, 60]. However,
reduces lightfastness and gloss retention. Alkyl
the mechanical properties of a paint are favored
acrylates and alkyl methacrylates impart flexi-
by a high molecular mass [54]. Low molecu-
bility and hydrophobicity, while acrylic acid and
lar mass binders that cross-link after application
methacrylic acid improve adhesion to metals.
are therefore used exclusively for high-solids
The increasing importance of environmental
paints. When it is applied, the paint contains low-
considerations places new requirements on paint
viscosity oligomers; a highly polymeric system
resins and has broadened the range of paint sys-
is formed after cross-linking and curing [58, 60].
tems. Paints are now required that have a low sol-
Further possibilities of reducing the viscosity in-
vent content (medium-solids, high-solids coat-
clude specific interactions between the binder
ings) or are solvent-free (powder coatings), that
molecules [65] and choice of a low-viscosity sol-
can be adjusted by dilution with water (water-
vent [57] that does not interact significantly with
borne paints), and that are thermoplastic or ca-
the resin [58]. The melt viscosity is an especially
pable of undergoing cross-linking. All of these
important criterion in powder coatings; acrylic
properties must be obtained via the polymer
resins have disadvantages in this respect when
structure of the binders. Important parameters
compared with polyesters [55].
are described below.
Incorporation of functional groups in the
The glass transition temperature (T g ) affects
polymer skeleton is necessary for the produc-
adhesion, flaking and peeling from the substrate,
tion of dispersions. Most water-dispersable sys-
crack formation, and resistance to impact shock
tems are polymers with free carboxyl groups.
[54]. In acrylates adjustment of T g is achieved
Water thinnability is achieved by neutralizing
relatively easily via the ratio of methyl methac-
the acid groups with aqueous alkali or amines.
rylate (T g of the homopolymer +105 ◦ C) to n-
Binders may also contain basic nitrogen-con-
butyl acrylate (T g of the homopolymer −54 ◦ C)
taining groups; dispersion can then occur after
[50, 51, 55]. The T g also influences properties
neutralization (e.g., with acetic or lactic acid).
of dispersions [55] and the viscosity of solutions
Since the viscosity of dispersions is very low ir-
[56–58]. A high T g value is associated with a
respective of the molecular mass, polymers of
faster drying rate [59]. In the low molecular mass
very high molecular mass are generally used;
range (< ca. 6000), which is of interest partic-
dispersions are therefore ideal for physically
ularly for high-solids paints, the T g depends on
drying coatings.
the molecular mass. Subsequent cross-linking
Solvent emission from paints can be reduced
leads to an increase of T g which is dependent
without lowering the molecular mass by us-
on the cross-linking density.
ing nonaqueous dispersions (NAD) (see Section
 Paints and Coatings 31

3.6). Acrylates have been described as binders of such polyurethane paints (see also Section
for NADs, but apart from a low viscosity they 2.9) are superior to those of most other coat-
offer few advantages over conventional coat- ing materials, and they are used in an increasing
ings [60] and moreover must compete with high- range of applications. One-pack polyurethane
solids paints and powder coatings [66]. paints are also available and are based on
hydroxyl-containing acrylates; blocked isocya-
Cross-Linking of Acrylate Resins. In con- nates are used as hardeners. Such systems gener-
trast to linear polymers, cross-linked poly- ally require relatively high stoving temperature
mers are insoluble and are also harder and (> 150 ◦ C).
more resistant to chemicals; these properties A third group of cross-linking reactions in-
are extremely important for high-grade coatings. volves acrylic resins containing free carboxylic
Cross-linking reactions became important in the acid groups. Polyepoxides are mainly used as
1950s with the introduction of acrylic resins in cross-linking agents in paints dissolved in or-
the automotive sector. ganic solvents or powder coatings. This combi-
A further impetus was given by increasingly nation is superior to other combinations (e.g.,
stringent environmental legislation; lower sol- isocyanate cross-linking or melamine resins) as
vent contents and the replacement of conven- regards hardness and resistance to detergents,
tional solventborne paints by medium-solids and lyes, and solvents. Extremely high stoving tem-
high-solids paints mean that the molecular mass peratures (≥ 200 ◦ C) are required; the tem-
of the binders had to be lowered to a range where perature can be reduced to ca. 120–150 ◦ C if
the required paint properties (e.g., film forma- tetrabutylammonium iodide or tertiary amines
tion, hardness, and flexibility) no longer exist. are used as catalysts [67–70]. Use of catalysts is,
These properties must be obtained by increasing however, offset by a low storage stability (only
the molecular mass by cross-linking after appli- a few weeks).
cation. Chemical reaction after application also If less stringent requirements with regard to
provides advantages for high molecular mass chemical resistance, abrasion, and hardness are
dispersions; the glass transition temperature and placed on the cross-linking density, carboxyl-
film hardness are increased. containing acrylates can also be cross-linked
A widely used method for cross-linking by salt formation (e.g., with diamines [54] or
paint films consists of reacting hydroxyl-con- metal complexes [71]). This procedure is widely
taining acrylates with melamine–formaldehyde employed, particularly for aqueous dispersions.
resins or urea–formaldehyde resins [50, 63, Cross-linking with bisoxazolines has also been
67]. The hydroxyl-containing acrylates are pre- reported [55]. Epoxy groups can be incorporated
pared using comonomers such as hydroxy- into the binder via glycidyl (meth)acrylate and
ethyl (meth)acrylate or butanediol monoacry- cross-linked with dicarboxylic acids [50].
late. Amino resins are to some extent self-cross- Aqueous acrylic dispersions are being in-
linking, but also form cross-links with acrylates creasingly used for corrosion protection coat-
via the hydroxyl groups [62]. Cross-linking can ings. These paints are often not baked; in-
be effected by curing at ca. 130 ◦ C or by acid stead, mechanical properties are improved by
catalysis. The paints exhibit outstanding gloss cross-linking at room temperature. Aziridines or
and weather resistance [68]. bishydrazides are generally used as the cross-
A second important cross-linking method is linking agent and are mixed with the dispersion
the combination of hydroxyl-containing acry- after the production process.
lates with polyisocyanates as hardener. This Many other cross-linking processes exist that
mixture forms cross-links at room temperature are not widely adopted or have only recently
and must therefore be produced and stored as a been developed. Cross-linking of epoxy-con-
two-component (two-pack) system [50]. Reac- taining acrylates with amino resins and reactions
tion between aromatic isocyanates and the hy- with polysulfonazides have been reported [67].
droxyl-containing acrylates proceeds extremely Reactions of unsaturated acrylic groups with ke-
rapidly; as aliphatic isocyanates react slowly, the timines and reaction of acetoacetate-containing
reaction has to be catalyzed (e.g., with dibutyl tin polymers with ketimines should also be men-
dilaurate, amines, or acids) [69]. The properties tioned [62, 72].
32 Paints and Coatings

An alternative way of curing paints is to pro- enthalpy of 2.26 kJ/g and thus requires substan-
duce self-cross-linking acrylic resins that react tially more energy for drying than organic sol-
internally at elevated temperature without the vents (evaporation enthalpies ca. 500 J/g). Pit-
addition of an external cross-linking agent. Such ting and blistering often occur at stoving tem-
systems have advantages as regards resistance peratures above 100 ◦ C. In physically drying
to chemicals, hardness, and elasticity, but are paints the drying behavior depends strongly on
less variable in their formulation and can present the atmospheric humidity and the application
problems as regards storage stability. Further- zone often has to be air-conditioned. The stabil-
more, in order to achieve a sufficiently high de- ity of acrylate dispersions depends on a delicate
gree of cross-linking a minimum molecular mass equilibrium between factors such as pH, emul-
is required that is higher than that of resins which sifier content, and sedimentation stability [72].
do not self-cross-link; high-solids paints accord- The formulation of a paint dispersion (emul-
ingly cannot be produced with such systems. sion paint) therefore requires additional compo-
nents (e.g., amines as solubility promoters, dis-
Applications. Acrylic paints are used in persants, defoamers, thickening agents) and is
many different areas and applied by all com- much more complicated than that of a conven-
monly used methods. Low-solvent paints and tional solvent-based paint [56]. Aqueous disper-
aqueous dispersions require special formulation. sions generally contain a few per cent of high-
Acrylic paints with a low-solvent content boiling solvents which act as temporary plas-
(medium- and high-solids systems) present ticizers and lower the minimum film-forming
some difficulties in application. Only a very temperature, thus allowing film formation to oc-
small amount of solvent evaporates from the wet cur. A film of sufficient hardness is obtained only
film, the increase in viscosity during drying is after complete evaporation of the solvent. The
slight, and the paint remains liquid with a low film may, however, be somewhat hydrophilic
viscosity for a long time. If an excessively thick due to the presence of carboxyl groups and emul-
coating is applied, this can easily lead to sag- sifier residues; this reduces its water resistance,
ging and evaporation is also hindered; control gloss, and gloss retention.
of the layer thickness therefore becomes dif-
ficult. During stoving, viscosity initially falls; Uses. The largest application sector for acry-
viscosity and thus paint stability only increase late binders are emulsion paints for ceilings,
after initiation of the cross-linking reaction and walls, and building fronts. These emulsion
the associated increase in molecular mass. The paints are generally physically drying and only
rheology of high-solids paints must therefore be contain a small amount of binder; the main con-
finely controlled with appropriate additives dur- stituents are pigments and extenders. Acrylate
ing application and stoving. These additives act dispersions for paints have a good water vapor
as thixotropic agents and ensure good leveling permeability and good water resistance.
during application without adversely affecting Acrylic resins have been used in the automo-
the stability of thick layers [57, 62]. Sagging tive sector since 1957. They are now important
can also be avoided by applying the paint at el- binders in automotive finishes and topcoats, and
evated temperature (e.g., 50–60 ◦ C). The low have replaced alkyd resins in many cases. Ad-
molecular mass of high-solids paints also affects vantages for automotive finishes and coatings
the stoving process. The cure window (i.e., the are high transparency, weather resistance, gloss
temperature and time ranges used for stoving) is retention, and yellowing stability [50]. Automo-
therefore smaller the lower the molecular mass tive finishes are always cross-linked; melamine
of the binder [63]. Paints produced from car- resins are generally used as hardeners [54],
boxyl-containing acrylic resins and diepoxides polyisocyanates are being increasingly used for
as cross-linking agents exhibit better rheologi- clearcoats [62]. Automotive fillers and metal-
cal behavior during application and stoving, pre- lic basecoats may be formulated with acrylate
sumably on account of the reversible formation dispersions to reduce solvent emission. Solvent-
of intermolecular hydrogen bonds [70]. containing systems are, however, still indispens-
Problems are also associated with water- able in the topcoat sector.
borne acrylic paints. Water has an evaporation
 Paints and Coatings 33

In the industrial coatings sector, acrylates are acid, styrene, vinyltoluene, isocyanates, acrylic,
used to satisfy special requirements. Self-cross- epoxy, or silicone compounds.”
linking acrylates are used for domestic appli- Worldwide alkyd resin production in 1988
ances on account of their good resistance to de- (including captive-use amounts) was estimated
tergents and lyes as well as their temperature and to be ca. 2.4×106 t. Detailed information on
yellowing stability. Metal substrates are stoved commercially available alkyd resins can be
with combinations of acrylate and melamine or found in [73].
urea resins; recently, stoving dispersions have The properties of alkyd resins can be widely
also become available. Wood surfaces subjected modified by selecting appropriate vegetable oils
to a high degree of wear (e.g., in kitchens) are be- and fats/fatty acids, varying their content in the
ing increasingly coated with polyurethane paints resin, and by using special synthetic acids and a
based on acrylic resins and isocyanates. variety of modifying agents.

Classification. Normal alkyd resins con-

2.6. Alkyd Coatings taining oil/fatty acid, dicarboxylic acid (mainly
phthalic acid or phthalic anhydride), and poly-
The binders used in the production of alkyd hydric alcohol are classified as short oil (≤ 40 %
paints, namely alkyd resins, are oil-modified or oil content), medium oil (41–60 % oil content),
fatty-acid-modified condensation polymers of and long oil (61–70 % oil content) resins. Very
polybasic acids and polyhydric alcohols. For fur- long oil alkyd resins with 71–85 % oil content
ther details, see → Alkyd Resins. Alkyd resins are mainly synthesized using isophthalic acid.
account for ca. 45 % of the total world produc- The term oil content denotes the triglyceride
tion of paint raw materials, excluding plastics (fatty acid) content relative to the solvent-free
latexes and polyvinyl dispersions. resin. Alkyd resins are subdivided into drying
Production of alkyd resins began in 1930. and nondrying resins according to the nature of
They owe their importance to their universal ap- the oils/fatty acids used. See → Alkyd Resins.
plicability. In the architectural coatings sector, Long oil drying alkyd resins are used as
alkyd resins replaced stand oils on account of binders for architectural and do-it-yourself
their faster drying and curing rates as well as paints, and are mainly modified with soybean
their better film hardness and gloss retention. oil. In the absence of direct light, they do not
Alkyd paints are used for protection and dec- yellow as much as linseed oil alkyd resins and
oration in virtually all sectors including coat- are less expensive than safflower oil types. Long
ings in the steel, sheet, and metal processing sec- oil linseed oil alkyd resins are principally used
tor, house and decorative paints, do-it-yourself in corrosion protection coatings and colored
paints, wood varnishes, wood protection agents, architectural coatings.
and automotive finishes. Alkyd resins are ex- Medium oil alkyd resins (oil content ca.
tremely important for corrosion protection coat- 50 %) are based on drying oils or fatty acid
ings. mixtures, and are used as binders for air-drying
and forced-drying machinery coatings and in-
dustrial coatings. They are also used in car re-
2.6.1. Alkyd Resin Binders and Uses pair finishes (refinishes), for original equipment
manufacturing (OEM) finishes, and refinishes
DIN 53 183 defines an alkyd resin as follows: of trucks and large-capacity vehicles.
“Alkyd resins are synthetic polyester resins pro- Short oil alkyd resins are used in combina-
duced by esterifying polyhydric alcohols with tion with amino resins for industrial stoving fin-
polybasic carboxylic acids. At least one of the al- ishes (e.g., for metal furniture, radiators, bicy-
cohols must be trihydric or higher. Alkyd resins cles, garage doors, and small steel items). Dehy-
are always modified with natural fatty acids or drated castor oil types mixed with alkyd resins
oils and/or synthetic fatty acids. In order to ob- based on synthetic acids are combined with
tain particular application technology proper- melamine resin for OEM automotive finishes.
ties, alkyd resins may be additionally modified Short oil resins are also combined with urea
with compounds such as resin acids, benzoic resins to produce acid-curing paints for wood
34 Paints and Coatings

and mixed with nitrocellulose for inexpensive, methylstyrene are also used for a more reliable
easily applied furniture lacquers and automotive reaction; vinyltoluene yields copolymers with
refinishing systems. improved thinnability in mineral spirit and pig-
ment absorption.
Combination of Alkyd Resins with Other Advantages of styrenated alkyd resins com-
Binders. Alkyd resins can be combined in many pared with nonstyrenated resins are faster dry-
different ways with other paint raw materials. In ing, better resistance to water and chemicals,
one method alkyd resins are mixed with prefor- and a lower yellowing tendency of their films.
mulated products; this is normally carried out in Disadvantages include the poor drying and low
the paint factory. Alternatively, the reactivity of solvent resistance of the paint films, which fre-
the initial products can be employed to modify quently lead to “lifting” during recoating. A de-
the alkyd resin during production. fect of styrene–alkyd resin topcoats is their high
Alkyd resins can be mixed with nitro- surface sensitivity, especially to scratching; they
cellulose, chlorinated rubber, highly chlori- are therefore mainly used in the primer sector
nated poly(vinyl chloride), amino resins, and where the danger of lifting can be avoided by
colophony-modified phenolic and maleic resins. appropriate pigmentation.
Chlorinated rubber and highly chlorinated
poly(vinyl chloride) are combined with alkyd Modification with Other Vinyl Com-
resins with the addition of plasticizers for cor- pounds. Low molecular mass acrylate and
rosion protection coatings. These combinations methacrylate esters are used to modify alkyd
have a higher resistance to chemicals than pure resins containing oil/fatty acid [75, 76]. Meth-
alkyd resin coatings. Combinations with amino acrylates give products that are more interest-
resins are used in oven-drying industrial coat- ing from the paint technology aspect. Acry-
ings and automotive finishes. The gloss, body, lated alkyd resins have a good pigment absorp-
adhesion, and the resistance to preserving wax tion capacity and yield paints with fast dry-
are determined by the alkyd resin. Amino resins ing properties, a high permanent elasticity, and
allow rapid drying at elevated temperature and very good adhesion (e.g., to aluminum, brass,
improve the mechanical resistance of the coat- and some plastics). Special advantages include
ings. better weather resistance and gloss retention;
Chemical reactions with alkyd resins can take through drying and surface (scratch) resistance
place via their hydroxyl or carboxyl groups as are superior to those of styrenated alkyd resins.
well as via the double bonds of the unsatu-
rated fatty acids. Isocyanates, epoxy resins, or Silicone-Modified Alkyd Resins. Hydroxy-
colophony, for example, may be reacted with the functional silicone precondensates can be used
hydroxyl groups. The carboxyl groups can be re- to produce air-drying alkyd resins. Methoxy-
acted with polyamidoamines (reaction products functional silicone precondensates are used for
formed from dimerized linoleic acid and ethyl- oven-drying silicone-modified alkyd resins [77].
enediamine) to form thixotropic resins, or can Air-drying coatings have outstanding chalking
react with hydroxy-functional silicone precon- resistance and gloss retention, and thus sub-
densates. The double bonds of the unsaturated stantially improved weather resistance. They are
fatty acids permit copolymerization with vinyl therefore often used on inaccessible objects that
compounds [e.g., styrene or (meth)acrylic acid can only be repainted at long intervals. The U.S.
derivatives]. Navy Specification TTE 049 prescribes silicone
alkyd resins for marine coatings. In the oven-
Styrene-Modified Alkyd Resins. Styrene drying coatings sector, the improved gloss re-
was first copolymerized with drying oils in tention and the substantially higher thermosta-
the early 1940s. These binders had a substan- bility/yellowing resistance are important.
tially improved drying behavior and resistance
to water and chemicals compared with untreated Thixotropic Alkyd Resins. Thixotropic
oils. The first patents for the production of flow is always associated with structural viscos-
styrenated alkyd resins were granted in Eng- ity. Thixotropic paints can be obtained by var-
land in 1942 [74]. Mixtures of styrene and α- ious methods. Use of a thixotropic alkyd resin
 Paints and Coatings 35

is the best way of ensuring reproducible flow seals, marine paints, and varnishes for the join-
properties. The alkyd resins become thixotropic ery and do-it-yourself sectors. They are used
after reaction with 10–20 % polyamidoamines in pigmented paints to produce high-gloss and
at elevated temperature (ca. 200 ◦ C) [78, 79]. matt decorative coatings with extremely good
Thixotropic resins are mainly used for dec- mechanical resistance as well as resistance to
orative paints and primers, and in corrosion cleaning agents and many disinfectants. They
protection coatings. Thixotropic alkyd resins allow sanding to be carried out at an early stage
prevent the formation of precipitates, improve in rapid-drying primers. They open up interest-
brushability, and reduce the sagging of paints ing possibilities in the corrosion protection sec-
on vertical surfaces and from edges and corners. tor because their drying is less sensitive to tem-
Thixotropic coatings (including those based on perature and atmospheric humidity than that of
thixotropic urethane alkyd resins) are frequently standard resins.
used in corrosion protection because the re-
quired layer thickness and good edge covering Alkyd Resins with Highly Branched Car-
can be achieved with a small number of layers. boxylic Acids. Highly branched carboxylic
Thixotropic air-drying and oven-drying acids are produced industrially from olefins, car-
alkyd resins with low oil contents are used as bon monoxide, and water [81]. They are mar-
binders for one-coat industrial paints with a keted by Shell under the name Versatic Acids
high dry-film thickness of 50–75 µm. In special- (→ Carboxylic Acids, Aliphatic, Chap. 10.8).
effect paints (e.g., hammer finishes, soft-feel Their esters have an outstanding resistance to
coatings, textured finishes) they facilitate fixa- hydrolysis. Highly branched fatty acids are,
tion of the desired effect and prevent smudging. however, difficult to esterify; their sodium salts
are therefore reacted with epichlorohydrin to
Urethane Alkyd Resins. Attempts to mod- form glycidyl esters which can then react as
ify drying oils with isocyanates date from the the epoxides, for example, with carboxylic acids
early 1940s [80] and led to the development of [82]. These products are marketed by Shell un-
urethane alkyd resins. Urethane alkyd resins are der the name Cardura resins. The glycidyl esters
generally produced by reacting long oil alkyd are esterified with phthalic anhydride or adipic
resins containing excess hydroxyl groups with acid and glycerol. Cardura resins are nondry-
diisocyanates. Since conversion is quantitative, ing alkyd resins modified with Versatic Acid.
the properties of the long oil alkyd resins are Their fatty acid content is generally ca. 40 %.
largely retained in the final products. For ex- They are soluble in aromatic solvents, ketones,
ample, urethane alkyd resins are readily solu- and esters, and are compatible with many amino
ble in mineral spirit, are compatible with many resins, short oil alkyd resins, oven-drying acrylic
other paint raw materials, and have a good stor- resins, epoxy resins, and nitrocellulose. Their
age stability. Their advantages in paint technol- main areas of use are stoving finishes, combin-
ogy are rapid drying, high hardness, very good ing extremely good hardness with high elastic-
film elasticity, and above-average abrasion re- ity and resistance to chemicals. The coatings are
sistance. Paint films are highly waterproof and resistant to overstoving and have a good gloss
show improved resistance to chemicals, even in retention and chalking resistance under weather-
the alkaline range. ing conditions. Their very good adhesion (even
Toluene diisocyanate and isophorone diiso- on untreated metal) is an important advantage.
cyanate are mainly used to modify alkyd resins. They are used in enamels and coatings for do-
Isophorone diisocyanate yields products with a mestic appliances, washing machines, and re-
lower yellowing tendency, higher pigment ab- frigerators, as well as for OEM automotive fin-
sorption, and considerably improved chalking ishes.
resistance under weathering conditions; how-
ever, its use is limited by its considerably higher Waterborne Alkyd Resins [83]. Alkyd
price. resins can be converted into a waterborne form
Urethane alkyd resins are used as varnish in two ways:
binders for the interior and exterior coating of 1) Alkyd resins with high acid numbers (> 50)
wood. Further applications include parquet floor are neutralized with amines (normal air-
36 Paints and Coatings

drying resins have an acid number < 10, agents, and house paints. They are particularly
oven-drying resins 20–35); solubility in wa- suitable for combination with polymeric, espe-
ter is due to salt formation. cially acrylate, dispersions. The use of alkyd
2) Alkyd resins are emulsified in water after ad- resin emulsions in industrial coatings is still in-
dition of emulsifying agents and stabilizers. significant, an exception being furniture coat-
ings and varnishes.
Neutralization with amines is mainly em-
ployed with medium and short oil resins that are
Alkyd Resins for High-Solids Paints. See
modified with drying and semidrying oils/fatty
also Section 3.2. Alkyd resins have been de-
acids and supplied as 70–80 % solutions in butyl
veloped for producing high-solids paints to re-
glycol, or mixed with 1-methoxy-2-propanol
duce solvent emission. One-pack, oven-drying
or N-methylpyrrolidone. Neutralization is gen-
high-solids paints have solids contents of 65–
erally performed with triethylamine to obtain
70 wt % in the ready-for-use formulation. Air-
air-drying alkyd resins; dimethylethanolamine
drying high-solids paints have solids contents
is used for oven-drying alkyd resins [84]. The
of 85–90 wt %. A high solids content can be ob-
amines used for neutralization represent an eco-
tained in three ways:
toxicological problem, and attempts are there-
fore being made to find more environmentally 1) Use of solvents with stronger solvent power,
compatible agents. In contrast to alkyd resin so that resin solutions with lower viscosities
emulsions, waterborne alkyd resins permit the are obtained with less solvent. This method
production of high-gloss paints. Sensitivity of is used for stoving paints based on conven-
the resins to hydrolysis during storage of the tional alkyd–melamine resin combinations; it
paints may cause problems and generally re- can also be applied with certain restrictions
sults in a decrease in viscosity. With air-drying to air-drying systems.
systems the drying ability can also be adversely 2) Use of reactive diluents that are incorporated
affected. These disadvantages are largely over- into the film by condensation when the stov-
come by incorporating acids such as trimellitic ing paints harden.
acid which is less susceptible to hydrolysis for 3) Use of low-viscosity, reactive alkyd resins
steric reasons; paints based on this system are that have a lower solvent requirement than
therefore more stable. Coating materials based conventional products.
on amine-neutralized alkyd resins are used for With high-solids stoving paints, sagging gen-
forced-drying and oven-drying industrial paints erally has to be prevented when coating verti-
(e.g., in combination with waterborne amino cal surfaces. Rheology-controlling additives can
resins), for wood protection, and for corrosion provide a remedy, but generally lead to a reduc-
protection. tion in the solids content.
Alkyd resin emulsions or “self-emulsifying” The solids contents of air-drying paints (i.e.,
alkyd resins can be produced relatively easily architectural and do-it-yourself paints) can be
(resin content 40–60 %). However, optimization adjusted relatively easily to 75–80 %. However,
of their properties requires a great deal of ex- for a solids content of 90 %, very low viscos-
perience and careful selection of additives [85]. ity binders with a low degree of condensation
In order to obtain satisfactory water resistance are necessary and often do not satisfy require-
and drying behavior, the content of emulsifiers ments concerning drying, hardness, and resis-
should be kept as low as possible. The size of the tance of the coatings. Developments have been
emulsified particles is in the range 5–15 µm. A aimed at overcoming the deterioration in dry-
small particle size ensures good storage stability ing and mechanical properties by incorporating
of the coating materials and improved gloss of 10–20 % of an allyl ether [86–88].
the dried films; it also improves miscibility with
polymer dispersions. The more homogeneous Commercial products include Alftalat
the system, the better the weather resistance of (Hoechst); Alkydal (Bayer); Beckosol (Reich-
the resultant coating films. Alkyd resin emul- hold Chemie); Beetle (BIB Chemical); Dyno-
sions are mainly used in architectural paints, tal (Dyno Industries); Heso-Alkyd (Hendricks +
corrosion protection coatings, wood protection Sommer); Rhenalyd (RWE–DEA); Setal (Syn-
 Paints and Coatings 37

these); Synolac (Cray Valley Products); Syntha- used in thixotropic paints because they destroy
lat (Synthopol Chemie); Uralac (DSM Resins); the thixotropy.
and Vialkyd (Vianova Kunstharz). Mineral spirit is the most important solvent
for medium oil alkyd resins in industrial air-
Testing. See also Chapters 9 and 10. drying and forced-drying paints. On account of
DIN 53 183 (Alkyd Resin Testing) describes the high viscosity of these resins, mineral spirit
the most important tests for alkyd resins in must be combined with solvents of stronger sol-
the Federal Republic of Germany. A com- vent power or with viscosity-lowering solvents
parable U. S. standard is ASTM D 2689–88 (e.g., xylene, solvent naphtha, lower alcohols,
(Standard Practices for Testing Alkyd Resins). and glycol ethers). These solvents promote lev-
ISO 6744 (Binders for Paints and Varnishes– eling and stabilize the paints during storage.
Alkyd Resins–General Methods of Tests) de- Short oil alkyd resins require special sol-
fines and classifies the term alkyd resins and vent mixtures for each area of use. Principal
contains a summary of international standards solvents include aromatic hydrocarbons (e.g.,
for testing alkyd resins. ASTM D 4712–87 xylene), solvent naphtha fractions, and glycol
(Standard Guide for Testing Industrial Water- ethers. Lower alcohols, even in small amounts,
Reducible Coatings) may also be mentioned; it have a powerful viscosity-lowering effect. The
includes standards covering the testing of wet choice of solvent depends on the solvent power
paints (properties, storage, application, film for- for the resins and the application method. The
mation) and paint films. last solvent to evaporate during drying must be
a true solvent for the binders because otherwise
the paint film becomes opaque or inhomoge-
2.6.2. Additional Raw Materials neous.
For their largest use sector (oven-drying in-
See also Chapter 5. dustrial coatings) the short oil alkyd resins are
combined with amino resins (melamine, urea, or
Solvents. Alkyd resins are generally sup- benzoguanamine resins). The paints are cured at
plied as concentrated (≥60 %) solutions (except 80–250 ◦ C. The amino resins are generally sol-
in the case of aqueous dispersions and emul- uble in alcohols and glycol ethers; aromatic hy-
sions). Further solvent must be added to bring drocarbons are used as diluents for amino resins.
the paints into a ready-for-use state. The choice Effective solvent mixtures often consist of aro-
of solvent is determined by the solubility of the matic hydrocarbons, glycol ethers, and alcohols
alkyd resin and ecological compatibility. in a volume ratio of 7 : 1 : 2 in the ready-for-use
Mineral spirit is the most commonly used sol- paint. The glycol ethers and alcohols improve
vent for long oil alkyd resins. Additions of other the leveling and surface of the coat as well as
solvents during paint production modify spe- the storage stability of the paints. With spraying
cific properties. The brushability and wet edge and roller paints, relatively high-boiling solvents
time can be improved by addition of higher boil- should also be used to achieve good leveling and
ing mineral spirit fractions (bp 180–210 ◦ C), avoid boiling phenomena (bubble formation). In
aromatics-free petroleum fractions, or isoparaf- dipping paints, small additions of low-boiling
fins [89]. (The wet edge time denotes the pe- solvents can prevent sagging.
riod that the paint can be brushed side by side Short oil alkyd resins can also be combined
without leaving overlap marks.) Additions of with nitrocellulose. They are readily soluble in
small amounts of glycol ethers (2.5–5 % of to- typical nitrocellulose solvents (esters and ke-
tal solvent content) also improve the leveling tones). Special short oil alkyd resins that are sol-
and application of the paints. Lower alcohols uble in lower alcohols are often processed into
and glycol ethers reduce and stabilize the vis- furniture lacquers and acid-curing paints, and
cosity. Additions of aromatic hydrocarbons of are also used in paper (spray) coatings and in
the solvent naphtha or xylene type improve ad- flexoprinting inks.
hesion of corrosion protection coatings to exist- The choice of solvents for waterborne alkyd
ing coats. Polar solvents should not generally be resins is restricted. Resins neutralized with
amines are normally supplied in glycol ethers or
38 Paints and Coatings

glycol ether–alcohol mixtures [90]. After neu- behavior. They should therefore be used with
tralization they are generally diluted with water. care.
Small amounts of propylene glycol are added to
alkyd resin emulsions to prolong the wet edge Wetting Agents. A stable mixture of binder
time. Coalescing agents are used in dispersions solution, pigments, and extenders is essential
with high latex contents. These specially for- for the production of storable pigmented paints
mulated high-boiling solvents lower the film- and primers. Pigments and extenders are usu-
forming temperature. ally covered by a layer of water molecules that
makes wetting difficult or even impossible. Car-
Driers are added to drying oils and drying bon black and some organic pigments can only
alkyd resins to accelerate oxidative drying. Dri- be wetted with difficulty by weakly polar or non-
ers include oil- and solvent-soluble and solvent- polar binder solutions due to their polar struc-
soluble metallic soaps. The naphthenate and oc- ture.
toate salts of cobalt, lead, and manganese with Wetting agents are surfactants and reduce the
the auxiliary metals calcium, zinc, and cerium surface tension between the binder solution and
are generally used. Calcium and zinc salts are the pigment particles. Wetting agents used in
added to the comminuted material during paint paint technology include calcium or zinc oc-
production to exploit their action as wetting toate or naphthenate, fatty alcohol sulfonates,
agents. castor oil acid derivatives and conversion prod-
For environmental reasons modern alkyd ucts, poly(glycol ethers), and low-viscosity sili-
paints are dried without lead driers and with min- cone oils.
imum amounts of cobalt driers [91]. Manganese Wetting agents are also often used as anti-
driers are only used in colored paints and cor- floating agents. Floating of pigments may occur
rosion protection coatings because they affect in combinations of pigments of widely differing
the shade of white and pastel coatings. Special densities, particle sizes, differing polarities, and
nondiscoloring driers (e.g., Dapro 5005, Daniel with unsatisfactory wetting.
Products, USA) are used to obtain particularly
pale white paints or honey-yellow varnishes.
2.6.3. Production
Antiskinning agents suppress skin forma-
tion on air-drying alkyd paints in the can, par- See also Chapter 7.
ticularly after the can has been opened. An- In liquid coating materials, pigments and ex-
tiskinning agents may be phenol derivatives tenders have to be uniformly distributed and
(e.g., 4-tert-butylphenol) or oximes (e.g., methyl fully wetted in the binder solution or disper-
ethyl ketone oxime or butanaloxime). Oximes sion. The pigment agglomerates are therefore
are used almost exclusively, at a concentration comminuted (grinding, dispersion) into primary
of 0.5–1.5 % relative to the solvent-free alkyd particles and simultaneously incorporated into
resin. They are colorless, do not affect paint the binder solution. Grinding is usually carried
color, and have a negligible effect on drying out with a dissolver and agitator ball mill, but in
time. some cases only with a dissolver. Grinding can
be carried out in roller mills after predispersion
Antisettling Agents. High-density pig- of the pigments and extenders with kneaders
ments and extenders tend to settle, especially or stirrers. Three-roll mills are used to produce
in low-viscosity paints. They form deposits that highly viscous materials (e.g., fillers or printing
are difficult to dislodge. Antisettling agents are inks).
used to overcome this problem. They may be Agitator ball mills (i.e., sand or bead mills)
minerals (e.g., pyrogenic silica), organically permit continuous operation and shorter disper-
treated minerals (e.g., montmorillonite treated sion times. Particle sizes of < 10 µm can be
with stearic acid), or organic compounds (e.g., achieved with relatively fast throughputs. These
hydrogenated castor oil). Excessive amounts mills are therefore also used for high-quality
of antisettling agents frequently cause thicken- paints (e.g., for automotive finishes or car re-
ing and have an adverse effect on rheological finishing).
 Paints and Coatings 39

Production with a dissolver and a sand mill Combustible materials contaminated with
proceeds as follows: air-drying and oven-drying alkyd paints, and
1) Dilution of the required amount of binder so- spray dusts, may tend to exhibit spontaneous
lution ignition due to autoxidation. Storage under ex-
2) Addition of wetting and antisettling agents clusion of air and regular cleaning of the spray
required for incorporation of pigments and cabins improves safety.
extenders
3) Addition of the pigments and extenders in a
relatively slowly running dissolver 2.7. Saturated Polyester Coatings
4) Dispersion of the pigments and extenders
with the sand mill Polyester resins are condensation products of
5) Monitoring of particle fineness di- or polyfunctional monomers containing hy-
6) Addition of the remaining auxiliaries (e.g., droxyl groups and carboxyl groups. The devel-
driers and antiskinning agents) opment of saturated polyesters began in 1901
7) Adjustment of the viscosity with “Glyptal resins”, formed from glycerol and
8) Sieving phthalic anhydride (Smith, United States). For a
9) Testing, approval, and packaging detailed description, see → Polyesters. Soluble
resins obtained with fatty acids were first em-
ployed in 1925. Alkyd resins formed from un-
2.6.4. Environmental and Health Protection saturated fatty acids can be cured by atmospheric
Measures oxidation (see Section 2.6). Other unsaturated
polyester resins are discussed in Section 2.8.
The solvents in the as-supplied alkyd resin solu- The subsequent development of saturated
tions and in the paint composition represent a po- polyester resins for paints and other uses (e.g.,
tential hazard due to their (eco)toxicological ef- adhesives, foams, fibers) was largely dependent
fects and flammability. Manufacturers and sup- on the introduction of new raw materials. A
pliers of resin solutions and paints must indicate broad range of raw materials are now available,
the potential dangers involved in the handling, examples follow:
transportation, and storage of solvents by label-
ing drums and containers according to national Polycarboxylic acids
and international regulations. Terephthalic acid (dimethyl ester) hard
Health risks depend on the nature of the sol- Isophthalic acid hard
Phthalic anhydride hard
vents and their concentration in the paint. Risks Hexahydrophthalic anhydride hard
arise from solvent vapors during paint applica- Trimellitic anhydride hard
tion. Working areas must be adequately venti- Adipic acid soft
Sebacic acid soft
lated to prevent vapor accumulation and respi-
Dodecanoic acid soft
rators must be worn during spraying to prevent Dimerized fatty acid soft
inhalation of paint aerosols. Polyalcohols
Paint residues require special handling and Ethylene glycol hard
1,2-Propanediol hard
disposal (special tips). Paints, solvents, and Neopentyl glycol hard
resins must under no circumstances be allowed 1,4-Cyclohexanedimethanol hard
to pollute the ground or effluent. Legal provi- Trimethylolpropane hard
sions concerning emission limits must be ob- Diethylene glycol soft
1,4-Butanediol soft
served when applying paints. 1,6-Hexanediol soft
Solvents differ as regards their miscibility Glycerol soft
with water and flash point and thus their po-
tential fire hazards (flammability, combustibil- Paint polyesters are generally copolyesters
ity). Explosive solvent vapor–air mixtures may composed of several polycarboxylic acids and
be formed when applying paints. Spark forma- polyalcohols. The glass transition temperature
tion (e.g., by static charging) must be avoided of copolyester resins can be varied within wide
and hot surfaces or naked flames must be re- limits by choosing appropriate raw materials.
moved.
40 Paints and Coatings
Table 4. Classification of saturated polyester resins for paints

Different polymer units (e.g., polyethers, poly- Linear, low molecular mass polyester resins
siloxanes) can be incorporated by condensa- are available with molecular mass up to 7000;
tion into the molecular chain. Instead of termi- branched grades have a molecular mass of up
nal hydroxyl or carboxyl groups, the molecules to 5000. These resins are not suitable for phys-
may also contain other functional groups (e.g., ically drying paints; they should be regarded
acrylic or epoxide groups) that can be cross- as prepolymers for reaction systems with cross-
linked with suitable reactants during paint hard- linking resins. Classes of polyester prepolymers,
ening (curing) to form thermosetting paints. Sat- their preferred cross-linking agents, and uses are
urated polyester resins for paints are available in summarized in Table 4.
various formulations [92]: low to high molecular
mass, linear or branched, as solid or liquid resins, Terminal Groups. The polyester–amine
soft/elastic or rigid/brittle, and amorphous or system, consisting of hydroxy-functional
crystalline. This versatility, together with their polyester resins and, for example, melamine
good resistance to light, moisture, heat, oxygen, resins, is extremely important for the produc-
and many other substances, accounts for the im- tion of heat-curable industrial stoving enamels
portance of saturated polyester resins as paint [93].
binders. Polyurethane systems based on hydroxypoly-
ester resins and free polyisocyanate resins (two-
pack polyurethane paints, Section 2.9) are used
2.7.1. Properties particularly for finishes of road vehicles, rail-
Molecular Mass. High molecular mass road vehicles, aircraft, and plastics. Blocked
copolyesters (M r 10 000–30 000) are gener- polyisocyanate resins are available for formu-
ally linear. They are formed from terephthal- lating one-pack stoving enamels which are par-
ic and isophthalic acids, aliphatic dicarboxyl- ticularly suitable for coil and can coatings [94].
ic acids, and various diols. Good solubility in The reaction system consisting of “acid” (i.e.,
conventional paint solvents is achieved by suit- carboxy-functional) polyester resins and epoxy
able formulation. In some cases (heat-sealable resins is important for powder coatings [95].
foil lacquers, printing inks, etc.), high molec- Acid polyester resins can be neutralized (e.g.,
ular mass copolyesters are used as physically with amines), diluted with water, and processed
drying binders. Optimum paint film properties into aqueous stoving enamels [96].
are, however, only obtained in combination with Acrylate-modified polyester resins have
cross-linking resins. Special, crystalline, high proved suitable as binders for radiation-curable
molecular mass copolyesters are ground and coatings [97].
used in thermoplastic powder coatings.
 Paints and Coatings 41

Glass Transition Temperature. The T g of distillation (azeotropic process) is of lesser im-

saturated polyester resins can be varied by a portance. High molecular mass copolyesters are
suitable choice of aromatic or aliphatic raw produced in two stages as is used for poly(ethyl-
materials. The T g of nonplasticized aromatic ene terephthalate). A precondensate is first ob-
copolyesters is ca. 70 ◦ C, and that of copoly- tained by transesterification of dimethyl tere-
esters formed from cycloaliphatic glycols ex- phthalate with an excess of diols. In the second
ceeds 100 ◦ C. Aliphatic polyesters with long stage, the molecular mass of the precondensate
methylene chains between the ester groups have is adjusted to the desired value by polycondensa-
T g values as low as −100 ◦ C (limiting value, tion in special reactors with the maximum pos-
polyethylene −125 ◦ C). sible elimination of water and excess diols in
vacuo at ca. 250 ◦ C.
Solubility, Crystallinity, and Compatibil- Saturated paint polyester resins are soluble in
ity. Polyester solubility is largely determined by esters, ketones, and in some cases aromatic hy-
the nature and proportions of the constituent drocarbons, but are insoluble in aliphatic hydro-
monomers. Polyesters with a regular structure carbons and alcohols. Solvent-containing paints
are crystalline. Examples of highly crystalline based on high molecular mass resins have solids
polyesters are poly(ethylene terephthalate) and contents of 35–50 wt % at application viscos-
poly(butylene terephthalate). Although medium ity. Paint solids contents for low molecular mass
to highly crystalline copolyesters are insoluble polyesters are 50–70 wt %.
in paint solvents, they can be processed into ad- Polyester resins for waterborne paints mostly
hesives and paints in the hot-melt process [98]. contain anionic groups (e.g., carboxyl groups)
Slightly crystalline copolyesters are soluble, for and become water soluble after amine neutral-
example, in ketones and are mainly used for lam- ization. Waterborne paints based on polyesters
inate adhesives. also contain cosolvents, preferably glycol ethers.
A low molecular mass and a low T g gener- Powder coatings based on low molecular mass
ally favor the compatibility of polyester resins resins are solvent-free, like radiation-curable
with other binders (e.g., acrylic resins, epoxy polyester paints.
resins, precondensed amino resins, cellulose es- Conventional grinding methods are used
ters). Not all polyester resins are mutually com- to incorporate pigments into solventborne and
patible; for example, polyesters based on ph- waterborne polyester resins as well as into
thalic acid are not always compatible with other radiation-curable polyester paints containing re-
polyester resins. active diluents. Pigmented powders are pro-
duced by coextrusion of polyester granulate with
pigments, followed by grinding.
2.7.2. Production of Polyester Resins and
Paints
2.7.3. Cross-Linking of Polyester Resins
The polycondensation of polycarboxylic acids
and polyalcohols proceeds via esterification Amino Resins. Formaldehyde-modified
with the elimination of water [92]. Transester- amino resins (i.e., melamine, benzoguanamine,
ification reactions should be taken into account and urea resins, → Amino Resins) are the most
in copolyester resins derived from more than two important resins for the heat curing of hy-
monomers. Esterification and transesterification droxyfunctional polyester resins. These resins
can be accelerated with metal-based catalysts. are readily available with a low molecular mass
Low molecular mass linear and branched (very good polyester compatibility, but less re-
polyester resins are produced in a one-stage pro- active) or in precondensed form (limited com-
cess at 125–240 ◦ C. The volatile condensation patibility, but very reactive). In order to prevent
products are removed in vacuo (melt conden- premature reaction in the wet paint, the amino
sation process) or by passing a stream of in- resins are blocked by etherification with, for ex-
ert gas through the resin melt (gas stream con- ample, methanol or butanol. Sulfonic acids (e.g.,
densation process). Polycondensation in solu- p-toluenesulfonic acid, dodecylbenzenesulfonic
tion with azeotropic removal of water by solvent acid) have proved suitable for accelerating the
42 Paints and Coatings

deblocking of amino resins during heat curing. or 2-methylimidazole) are used to accelerate the
These acids must also be used in blocked form reaction during heat curing. Triglycidyl isocya-
(ammonium salts, thermolabile adducts). nurate plays a special role as cross-linking agent.
The polyester–amino resin ratio is generally Powder coatings with outstanding weather resis-
in the range 90 : 10 to 70 : 30. High molecular tance and very good mechanical properties are
mass polyester resins can be cross-linked with obtained [95]. Hybrid powder coatings based on
hexamethoxymethylmelamine resins (HMMM) epoxy resins of the bisphenol A type should also
above ca. 190 ◦ C. Amino resins undergo self- be mentioned.
condensation above this temperature [93]. Low
molecular mass linear polyesters react above Radiation Curing. The cross-linking of
160 ◦ C, and branched types above ca. 100 ◦ C. acrylate-modified polyester resins with UV ra-
The latter generally contain acid groups (acid diation or an electron beam is an energy-saving
number 5–25 mg KOH/g) in addition to the hy- alternative to the heat-curing systems. Reactive
droxyl groups to enhance reactivity with amino diluents (e.g., polyfunctional acrylates) are re-
resins. Stoving enamels based on high molecular quired to adjust the viscosity for application;
mass polyester resins and HMMM or benzogua- although they increase reactivity, they reduce
namine resins have excellent flexibility and sur- the flexibility and substrate adhesion of the paint
face hardness as well as outstanding adhesion to film.
metal substrates [99, 100]. Low molecular mass
linear polyesters combined with HMMM resins
have lower flexibility, but have the advantages 2.7.4. Uses
of higher reactivity, better pigmentability, and
higher paint solids content [101, 102]. Low mo- Coil Coating. On account of their outstand-
lecular mass branched resins form particularly ing hardness–elasticity balance, good adhesion
reactive stoving enamels, but the resulting films to metals, good application properties, and fa-
are less flexible and do not adhere as well to vorable cost, paints based on saturated polyester
metal substrates. resins represent the most important system for
coil coating.
Polyisocyanate Resins. Hydroxy-functional On account of their insensitivity to solar radi-
polyester resins play a significant role in two- ation, some polyester resins are particularly suit-
pack polyurethane paints. Combinations with able for weather-resistant topcoats (e.g., facade
nonblocked polyisocyanate resins are discussed claddings, blades of shutters and venetian blinds,
in Section 2.9. vehicle claddings, metal signs). Melamine-
Storage-stable one-pack polyester stoving formulated paints are economic and have a
enamels can be formulated with polyisocyanate well-balanced property profile. Polyurethane-
resins that are thermoreversibly blocked. Tin formulated paints have an even better process-
catalysts (e.g., dibutyl tin dilaurate) are partic- ability and weather resistance (colorfastness,
ularly suitable for accelerating hardening with chalking resistance) [103].
hydroxypolyester resins. Specially adapted polyester resins are avail-
Although linear polyester resins do not read- able for topcoats for interior architectural use
ily undergo heat curing, they form extremely (e.g., underfloor ceilings, light fittings), for ap-
flexible paint films with excellent adhesion pliance claddings (e.g., domestic appliances, hifi
to metal substrates. Polyisocyanate resins are equipment), or for automobile fittings. Hard,
more resistant to hydrolysis than amino resins. high molecular mass copolyesters are suitable
Polyester–polyurethane paints therefore exhibit for primers containing corrosion protection pig-
improved resistance to moisture and weathering ments on account of their low oxygen perme-
but are more expensive. ability and very good adhesion to metals [104].

Epoxy Hardeners. The heat curing of Can Coating. Polyester stoving enamels are
carboxy-functional polyester resins with epoxy widely used for coating can exteriors (metal dec-
resins is mainly used in powder coatings. Cata- orating) but also for protecting can interiors.
lysts (e.g., benzyltrimethylammonium chloride Polyester resins are available that satisfy the
 Paints and Coatings 43

FDA regulations for internal coatings of cans borne polyester paints to control their viscosity
used for food packaging [105]. Polyester coat- and applicability (leveling, substrate wetting).
ings do not affect the taste of the food.
High molecular mass polyester resins, cross- Two-Pack Polyurethane Paints. Polyester–
linked with benzoguanamine and melamine polyurethane paints are described in detail in
resins, are particularly suitable for highly draw- Section 2.9. Polyester polyols for polyurethane
able, sterilization-resistant decorative stamp- systems are generally adjusted to be “softer”
ing enamels [99, 100]. Low molecular mass than those used for stoving enamels. Their hy-
polyester resins also exhibit good processabil- droxyl number and degree of branching are
ity and sterilization resistance in polyurethane adapted to the recommended polyisocyanate
formulations. cross-linking agent.
Polyester resins combined with aliphatic
Automotive Finishes. Important industrial polyisocyanate resins have outstanding weather
automotive topcoats are produced from alkyd resistance, good substrate adhesion, and high
resins. Two-coat metallic finishes consist of an flexibility even under very large temperature
acrylic clearcoat and a metallic basecoat. Sol- changes (aircraft finishes).
ventborne basecoats are generally composed of Polyester–polyurethane paints are particu-
cellulose acetobutyrate and a low molecular larly suitable for coating plastics (maximum dry-
mass, branched polyester resin which exhibits ing temperature generally 80 ◦ C) on account of
high reactivity with precondensed melamine their very high flexibility and good adhesion.
cross-linking resins.
Surfacers are mainly produced from low mo- Powder Coatings. Polyester resins are avail-
lecular mass polyester resins cross-linked with able for two different reactive powder coating
amino resins. Blocked polyisocyanate resins systems:
may also be used for high stone chip resis-
tance. Water-soluble polyester resins are in- 1) Hydroxy-functional resins for combination
creasingly used for water-thinnable stoving sur- with blocked polyisocyanate resins (based on
facers. Spray and dip paints based on polyester isophorone diisocyanate) [107]
resins are used to coat automobile accessories 2) Carboxy-functional (acid) resins for combi-
(e.g., windscreen wipers, axle parts). nation with triglycidyl isocyanurate or epoxy
resins
Industrial Paints. Stoving enamels used to The resulting powder coatings have good
spray or dip-coat machinery, domestic appli- weather resistance as well as excellent impact
ances, vehicles, and office furniture are termed strength and adhesion to metals (even under hu-
industrial paints. On account of their good ad- mid conditions) and are therefore suitable for
hesion and resistance to hydrolysis, polyester– many uses (e.g., in exterior and interior archi-
melamine stoving enamels provide very good tectural applications, for coating machinery, do-
protection of metal surfaces against undercoat mestic appliances, steel furniture, garden tools).
corrosion creep. Polyester resin grades are avail-
able for special mechanical requirements (high Radiation-Curable Polyester Coatings.
impact resistance, hardness, abrasion resistance) Radiation-curable polyester paints (see also Sec-
or for exterior use (weather resistance). tion 3.7) are particularly suitable for coat-
Polyester paints with high solids contents ing flat surfaces (strips, boards, sheets) and
(65–75 wt % at application viscosity) can be for temperature-sensitive substrates (paper, plas-
produced from very low molecular mass resins tics). Acrylate-modified polyester resins are
[106]. Low-pollution paints can also be pro- used for UV printing inks, UV varnishes for pa-
duced from water-soluble polyester resins [96]. per and plastics, as well as for pigmentable, elec-
On account of their good water solubility, tron beam-curable gloss and matt paints [97].
HMMM resins are particularly suitable for Radiation-curable polyester paints are also suit-
cross-linking these resins. Organic cosolvents able for metal coatings with good elasticity.
(mostly glycol ethers) must be added to water-
44 Paints and Coatings

Special Uses. High molecular mass copoly- maric acid and dihydric alcohols, such as ethyl-
ester resins are used in the manufacture of flex- ene glycol and 1,2-propylene glycol. In special
ible packaging. Terephthalate resins are partic- applications, a portion of the α,β-unsaturated
ularly suitable as adhesion promoters for print- dicarboxylic acids can be replaced by phthalic
ing inks, lacquers, and adhesives on poly(ethyl- and/or adipic acid. Unsaturated polycondensa-
ene terephthalate) films. Some polyester print- tion products of maleic acid or maleic anhydride
ing inks adhere directly to these sheets. Lacquers and glycols as well as their copolymerization
that can be heat sealed at relatively low tem- with styrene are described in [111]. The testing
peratures can be produced from high molecu- of UP resins is regulated by DIN 53 184.
lar mass, soft copolyester resins. Special linear Worldwide UP resin production in 1988 in-
copolyester resins are used for magnetic tape cluding captive use amounts was estimated to
coatings [108]. be ca. 200 000 t. Western Europe accounts for
65 000 t, of which ca. two thirds of this is used
for furniture coatings and the rest for filler and
2.8. Unsaturated Polyester Coatings putty production.
Unsaturated polyester coatings are composed
of unsaturated polyester resins (UP resins, Commercial products of UP resins are
→ Polyester Resins, Unsaturated), hardening marketed under the following trade names
(curing) agents, accelerators, promoters, pho- [112]: Alpolit (Hoechst); Crystic (Scott Bader);
toinitiators, stabilizers, covering agents (paraf- Distitron (Alusuisse); Estratil (Rio Rodano);
fin), air release and leveling agents, pigments, Gohselac (Nippon Gohsei); Ludopal (BASF);
and extenders. Most of the coatings also contain Poloral; Verton (Galstaff); Polylite (Reich-
copolymerizable vinyl monomers. hold); Roskydal (Bayer); Silmar (Silmar); Syn-
Although styrene is the most commonly used olite (DSM); Unidic (Dainippon Ink); Vestopal
reactive monomer, esters of acrylic acid have (Hüls); Viapal (Vianova).
also been introduced, particularly for UV cur-
ing applications. Monomer-free UP resins that Paraffin-Containing UP Resins. Since at-
are either dissolved in solvents (e.g., butyl ac- mospheric oxygen inhibits the copolymeriza-
etate) or are water dispersible have also become tion of many types of UP resins with monomers
important [109]. (chain termination), the film surface remains
Unsaturated polyester systems are cured by tacky. This can be prevented by adding a small
free-radical polymerization. Free radicals are amount of paraffin to the coating formulation
generated by use of peroxide (conventional cur- [113]. The paraffin is initially soluble in the UP
ing) or addition of a photoinitiator and exposure coating but its solubility decreases as polymer-
to UV light (UV curing). Conventional curing ization progresses. It accumulates on the film
can be accelerated by use of heat or IR radia- surface to form a layer that prevents access of
tion. oxygen. The paraffin layer also reduces evapo-
Due to the incorporation of reactive ration loss of styrene to < 5 % [114]. This is par-
monomers, the coatings harden to form lay- ticularly important in view of the low maximum
ers of practically unlimited thickness. Styrene workplace concentrations allowed for styrene.
initially acts as a solvent but then copolymer-
izes with the double bonds of the UP resin and Unsaturated Polyester Resins for Fillers
is firmly incorporated into the film. Since only a and Putties. Nontacky film surfaces are also
small proportion of the styrene evaporates, ex- obtained if phthalic anhydride is replaced by
cellent filling properties are obtained with these tetrahydrophthalic anhydride [115]. Use of
virtually “solvent-free” coating materials [110]. endo-methyltetrahydrophthalic anhydride (cy-
cloaddition product of maleic acid and cyclo-
pentadiene) also improves air drying [116]. Both
2.8.1. Unsaturated Polyester Binders classes of products have become important, es-
pecially for the production of fillers and putties
Unsaturated polyester resins are linear, solu- for autobody repair.
ble polycondensation products of maleic or fu-
 Paints and Coatings 45

Air-Drying Unsaturated Polyester Resins. Photoinitiators. In UV curing, benzoin and

Use of UP resins modified with α,β-unsaturated benzil derivatives are added as photoinitiators in
ethers give coatings that surface-harden com- amounts of 1–3 %. These compounds are split
pletely in the presence of atmospheric oxygen into radicals by UV light, which in turn initiate
without the incorporation of paraffin wax [117– polymerization [120–122].
119]. The resulting films therefore have a very
high gloss. Examples of ether reagents are dial- Stabilizers. If stabilization is necessary (e.g.,
lyl ethers of glycerol or trimethylolpropane, as to prolong pot life or increase storage stabil-
well as di- and triallyl ethers of pentaerythritol. ity) 0.01–0.03 % of solid hydroquinone or tert-
Since they are cured to give a high gloss in the butylcatechol as a 1–5 % solution may be added.
presence of oxygen, these materials are referred
to as air-drying or gloss UP resins. Paraffin. The addition of paraffin prevents
inhibition of polymerization by atmospheric
oxygen [123] (see Section 2.8.1). With higher
2.8.2. Other Raw Materials application temperatures (max. 40 ◦ C) higher
melting point paraffins are required (mp 40–
The composition of the coating material should 70 ◦ C). They are usually added at a level of ca.
be adjusted in accordance with the intended ap- 0.1 % with respect to the coating, if possible as a
plication as regards choice of resin, curing sys- 10 % solution in toluene. On cooling, the paraf-
tem, and additives that modify the color, level- fin contained in coating materials and fillers may
ing, mechanical properties, and chemical resis- crystallize out. Paraffin grades that have been ap-
tance. proved for UP resins should be used. The paraf-
fin solution is normally added with the acceler-
Hardeners. Polymerization is initiated by ator (cobalt compound) to the coatings material
peroxide radicals. Typical examples are cyclo- and fillers shortly before application.
hexanone and methyl ethyl ketone peroxides
(hydroperoxides), benzoyl peroxide, perben- Air-Release and Leveling Agents. On ac-
zoates, and peroctoates (acyl peroxides). About count of the many possible formulations and ap-
4 % (relative to amount of resin and styrene) of plications, the type and amount must be matched
a desensitized peroxide (50 % peroxide in plas- to the relevant system. The additive Baysilone
ticizer) is normally used. To avoid potential haz- Paint Additive PL (Bayer) is effective in many
ards manufacturers’ instructions should be care- instances.
fully observed when handling peroxides.
Solvents. Coating compositions based on UP
Accelerators are used to promote peroxide resins are generally solvent-free. When inert or
decomposition at room temperature. Hydroper- other coreacting binders are to be used, low-
oxides are split by heavy metal salts. Normally boiling solvents (e.g., ethyl acetate) are em-
0.02–0.05 % of cobalt as cobalt naphthenate or ployed. With matt coatings containing nitrocel-
cobalt octoate dissolved in aromatic compounds lulose or cellulose acetobutyrate that are applied
is added to the system shortly before application. as thin layers, the solvent content may be as
Acyl peroxides are split by tertiary aromatic high as 75 %. In coatings applied as a thick
amines; manufacturers add up to 2 % amine to layer the content should not exceed 4 %. Unsat-
filler and putty resins (amine-preaccelerated UP urated polyester resins may also be combined
resins). with polyisocyanates to improve adhesion to the
substrate and resistance to chemicals.
Promoters. Substances such as acetylace-
tone, ethyl acetoacetate, or tertiary aromatic Pigments and Extenders. The pigments
amines accelerate the curing reaction initiated and extenders must neither accelerate nor in-
by hydroperoxide and cobalt octoate. The pro- hibit the hardening process. The main function
moter is generally at a level of 1–5 %, relative to of the extenders (talc, barytes, calcite, dolomite)
the as-supplied resin form. is to reduce the 7–10 % shrinkage that occurs on
46 Paints and Coatings

hardening and thus improve adhesion. Ready- primed and sanded. The UV-curable UP primers
formulated filler compositions should have an are based on air-drying UP resins. UV-curable
adequate storage stability. primers can be applied with rollers in amounts
In order to apply paints based on UP resins of 20–40 g/m2 . UV curing is performed at a
in thicker layers to vertical surfaces, the coat- belt speed of 3 m/min. UV-curable solvent-
ing formulation has to be adjusted so as to be containing primers applied by spraying (60–
thixotropic. Thixotropic or standard resins are 70 g/m2 ) have a solids content < 30 %; they are
used for this purpose in combination with thick- then subjected to aeration for 4–5 min at 50 ◦ C
eners (e.g., highly dispersed silicic acid, ben- to remove any remaining solvent, followed by
tonites, and/or hydrogenated castor oil deriva- UV curing at a belt speed of 3 m/min.
tives). For matt coatings, waxes (polyethylene Cobalt–hydroperoxide-containing matt coat-
and polypropylene waxes) and/or silicic acid are ings for topcoats and primers can be left to stand
added in amounts of up to 10 %. for several hours due to their high solvent content
of up to 75 %. This is an important prerequisite
for their application. Solids settling is achieved
2.8.3. Production, Properties, and Uses by adding highly viscous nitrocellulose or cellu-
lose acetobutyrate; it is desirable for economic
Fillers and Putties for Wood. Putties are reasons to obtain special surface effects (open
highly filled (resin to extender ratio 1: 2.5 to pore effect in wood furniture). The coating ma-
1: 3), highly viscous compositions that are used terials are applied in amounts of 20–100 g/m2
to level out unevenness in the substrate (e.g., with a drying time of 6 h at room temperature.
chipboard). Fillers contain less extender (resin After evaporation of the solvent (4–5 min at
to extender ratio 1: 1.5) and are generally used 50 ◦ C), the coating can be cured in 10 min at
as an intermediate layer between the putty and 80 ◦ C in circulating air, in 1–2 min under IR ra-
the topcoat. Fillers and putties are produced with diation, or at a belt speed of 3 m/min under UV
dissolvers, butterfly mixers, or stirrer-type ball radiation. The coatings have a high scratch re-
mills. sistance, good adhesion, and high resistance to
Putties are applied with special roller coaters. household chemicals.
Fillers are applied with reverse rollers (direc-
tion of roller rotation is opposite to that of the Roller, Curtain, and Spray Coatings for
material to be coated), spray guns, or curtain Wood (Thick Layers). Coatings based on
coaters. The amount applied is 50–200 g/m2 de- paraffin-type UP resins are mainly used as clear
pending on the substrate. The high filler con- or pigmented thick coatings for wood, with or
tent of putties prevents inhibition of polymeriza- without matting agents. They are applied by
tion by atmospheric oxygen. The main binders roller, curtain, or spray coating. In special cases
for putties are paraffin-type UP resins that are gloss polyesters are also used. After application
UV cured in a paraffin-free formulation. Air- and standing overnight, the coating is sanded and
drying UP resins in combination with elastify- polished to give a stable high-gloss surface with
ing resins are mainly used for hydroperoxide– excellent holdout and depth. Such systems are
cobalt-hardening fillers. commonly used as substrates for topcoats based
UV curing takes place at belt speeds of on polyurethane or other binders.
ca. 3 m/min with a mercury vapor high-pres- UV-curable UP coatings for both gloss and
sure lamp (80 W/cm). Conventional curing of matt thick-layer varnishes have been used in-
sprayed fillers in circulating air ovens at 80 ◦ C creasingly on account of their rapid drying prop-
requires a hardening time of 10 min. These sys- erties.
tems produce ideal primers for a wide range of Application. The following application
topcoats. methods are used industrially:
Roller Coating. Up to ca. 150 g/m2 of UV-
Roller, Curtain, and Spray Coatings for curable coating materials can be applied with
Veneered Boards and Panels (Thin Lay- reverse roller coating. These materials are pre-
ers). Veneered boards and panels that are to ferred on account of their long application time
be coated in the open-pored form are first
 Paints and Coatings 47

(no pot life). A long application time is advanta- In order to ensure that all pores are filled, a
geous because it allows adjustment of viscosity. spraying filler and a nonsanding sealer must be
Curtain Coating. The main problem in the applied to the putty. The spraying filler (based
application of UP materials is the fact that only on air-drying UP resins with hydroperoxide and
a few minutes elapse between mixing and the cobalt octoate) fills in the ghost lines. The non-
onset of polymerization. This short pot life is sanding sealer (based on polyurethane) prevents
circumvented with curtain coating by separat- bubble formation after topcoat application, par-
ing the cobalt and hydroperoxide used to initiate ticularly in a warm, damp atmosphere. The
cross-linking. For example, in the active prim- spraying filler and nonsanding sealer can be
ing method [124] peroxide-containing nitrocel- coated. Knifing putties and spraying sealers are
lulose lacquers (which may also contain styrene- used in automotive repair finishes and machin-
free UP resins) are first applied with rollers or a ery coatings (on sanded or sandblasted iron).
curtain coater. After evaporation of the solvent, The hardened putties exhibit very good adhe-
a layer of cobalt-containing UP material is ap- sion, complete and even hardening in both thin
plied. Other, less widely used methods include and thick layers, and rapid hardening even at
the double head, sandwich, and reverse methods temperatures as low as 0 ◦ C.
[125]. Since UV coating materials do not have a Special UP resins are used in stone putties
pot-life time (one-component systems) they are and fillers and coatings for marble. The fillers
particularly suitable for curtain coating applica- are pasty to pourable, they are hardened with
tion. benzoyl peroxide and a tertiary aromatic amine.
Spraying. Pot-life-free UV coating materi- The fillers can be sanded and polished after 15–
als can be applied using all spraying equip- 20 min. These hard, reactive coating composi-
ment. Two-component units are used for cobalt– tions harden without discoloration and exhibit
hydroperoxide-containing paints with a short good mechanical properties: spraying or curtain-
pot life. coating topcoats are produced from air-drying
Curing. Paraffin-containing coatings gel af- UP resins. Glossy surfaces are obtained after
ter ca. 10 min at room temperature, are touch- curing with cobalt and hydroperoxide.
free after ca. 30 min, and are stackable after ca.
2 h. Air-drying UP coatings can be cured di-
rectly by heating without pregelling. UV coat- 2.8.4. Transportation and Handling
ings are cured after deaeration for 30 s (curtain
coating) or 5 min (spraying) at a belt speed of Unsaturated polyester resins cannot be stored for
1.25 m/min. Coatings of up to 500 g/m2 can be an unlimited period. If the resins are protected
hardened by conventional curing (cobalt salt and against light and heat, manufacturers generally
hydroperoxide at ambient or elevated tempera- guarantee a shelf life of 6 months (23 ◦ C). Un-
ture) and up to 250 g/m2 by UV curing. saturated polyester resins are delivered in sealed
containers, drums, canisters, and road tankers
Putties and Fillers for Metals and Marble. made of stainless steel, aluminum, tin plate, or
Knifing and spot-repair putties are particularly sheet iron that are sometimes internally coated.
suitable when a high degree of unevenness has The flash point of UP resins is 28–35 ◦ C, de-
to be leveled in a few, rapidly successive op- pending on the styrene content. Appropriate pre-
erations. The putty resins (hard to elastic) are cautions should be observed to prevent electro-
adjusted to a pasty consistency with extenders. static charging.
The curing system consists of benzoyl peroxide The transportation of UP resins is governed
and a tertiary aromatic amine. by the following provisions: GGVSee/IMDG
The putty composition is thoroughly mixed code: class 3.3; UN no.: 1866; Medical First
with the benzoyl peroxide paste required for Aid Guide (MFAG): 310; Emergency Proce-
the hardening (2–3 %) and applied with a putty dures (EmS): 3 05; GGVE/RID: Rn 301 D;
knife. The pot life is generally ca. 5 min; the GGVS/ADR: Rn 2301 D; ADNR: unclassified;
hardening time is ca. 15 min. The dry putty can ICAO/IATA-DGR: 3., 1866 III.
be sanded. Shrinkage of the hardened putty com- The toxicology of styrene (→ Styrene)
position is 1–2 %. should be considered while producing, han-
48 Paints and Coatings

dling, and applying coating compositions con- methylenediphenyl diisocyanate (MDI), and
taining styrene-dissolved UP resins. Respirators 1,1-methylenebis(4-isocyanato)cyclohexane
should be worn to prevent any inhalation of paint (HMDI) are of commercial importance. (For
aerosols during spraying application. a more detailed description of diisocyanates,
see → Isocyanates, Organic.) High molecu-
lar mass polyisocyanates or prepolymers de-
2.9. Polyurethane Coatings [126–129] rived from such products are the basis of most
polyurethane paint formulations. They contain
The term polyurethane paints (coatings) orig- only very small amounts (<0.5 %) of monomers
inally referred to paint systems that utilized that are volatile at room temperature and thus
the high reactivity of isocyanates for chemical permit safe application from the point of view
hardening (curing). However, this term now in- of industrial hygiene.
cludes a large variety of binders. The amount of Polyisocyanates differ as regards their chemi-
polyurethane raw materials processed into coat- cal structure, reactivity, functionality, and isocy-
ings is steadily increasing, and in 1990 was es- anate content. They are the principal curing con-
timated to be ca. 400 000 t worldwide. stituent of two-pack polyurethane paints. Curing
Polyurethane paint films all have a poly- agent solutions have an isocyanate content of 5–
meric structure with urethane, urea, biuret, or 16 wt %. Solvent-free, liquid curing agents may
allophanate coupling groups. Coupling can oc- contain up to 30 wt % isocyanate.
cur during paint hardening (curing) as the re- Aliphatic and cycloaliphatic polyisocyanates
sult of polyaddition of relatively low molecular can be used to produce lightfast, weather-
mass starting products. Alternatively the paints resistant coatings for extremely severe con-
may already contain high molecular mass poly- ditions. Aromatic polyisocyanates are of lim-
mers synthesized by the coupling of appropriate ited suitability for exterior applications and
monomers. High molecular mass adducts with react more quickly than aliphatic polyisocya-
excess isocyanate groups or adducts in which nates. The different reactivities of aromatic and
curing occurs via oxidation of conjugated dou- aliphatic polyisocyanates influence their use be-
ble bonds are also common. cause they affect drying and curing.
Other variants of technical interest include Polyisocyanate types with free, excess isocy-
blocked reactive groups, that can be activated anate groups include adducts of diisocyanates
by heat or atmospheric moisture. Microencap- with polyols, isocyanurates formed by trimer-
sulation of polyisocyanates is also becoming an ization of diisocyanates, and high molecular
important deactivation method. mass products containing biuret or allophanate
Depending on their chemical composition, groups. Monomeric MDI and its mixtures with
polyurethane paints are formulated as twocom- oligomers have a low vapor pressure and can be
ponent (two-pack) or one-component (one- safely handled at room temperature.
pack) mixtures. They are applied from the liquid Blocked polyisocyanates are obtained by
phase, which may be solvent-containing, aque- chemical addition of compounds that contain
ous, or solvent-free, or from the solid phase as acidic or potentially acidic hydrogen atoms (e.g.,
a powder coating. They may be cured under a alcohols). These isocyanates are not reactive at
wide range of conditions: drying above 0 ◦ C to room temperature since they do not contain free
stoving at ca. 200 ◦ C. isocyanate groups. Such polyisocyanates can,
however, be regenerated by heating to eliminate
2.9.1. Raw Materials the blocking agent.
Commercial products include Coronate
See also → Polyurethanes. (Nippoly); Desmodur (Bayer/Mobay); Isocya-
nate (Hüls); Takenate (Takeda); and Tolonate
Polyisocyanates. Numerous diisocyanates (Rhône–Poulenc).
may be considered as a basis for paint
polyisocyanates. However, only toluene di- Polyols. In conventional two-pack poly-
isocyanate (TDI), hexamethylene diisocya- urethane paints, high molecular mass com-
nate (HDI), isophorone diisocyanate (IPDI), pounds containing hydroxyl groups form the
 Paints and Coatings 49

“base” that cross-links and hardens with with isocyanate contents of 5–15 % (based on
polyisocyanates. Polyester polyols, hydroxyl- the solid resin) are commercially available.
containing acrylic copolymers, and polyether Since products that contain free isocyanate
polyols are particularly important. They may be groups react with water, moisture may affect
linear or branched and their hydroxyl group con- storage stability when producing pigmented
tent ranges from 0.5 to 12 %. coatings. This has to be prevented, and use
The structure and content of reactive of water-binding additives has proved effective
groups determine the property profile of the (e.g., special monoisocyanates such as Addi-
polyurethane formed with the polyisocyanate. tive TI (Bayer).
The higher the hydroxyl group content and the
degree of branching, the better the hardness Blocked Polyisocyanate Systems. Type 3 in
and solvent and chemical resistance of the paint Table 5. The isocyanate groups of polyisocy-
films. anates can be “blocked” with agents such as
Commercial products include Desmophen phenol, butanone oxime, -caprolactam, or di-
(Bayer/Mobay); Lumitol (BASF); Macrynal ethyl malonate that are easily eliminated or
(Hoechst); and Phtalon (Galstaff). that rearrange under the action of heat. Mix-
tures of blocked polyisocyanates with polyols
or polyamines are stable, and thus permit the
2.9.2. Polyurethane Systems production of storable one-pack stoving finishes.
Stoving urethane resins containing both reaction
Polyurethane systems for paints and coatings are components are commercially available. The
summarized in Table 5. stoving temperatures vary from 120 to 220 ◦ C
depending on the blocking agent, but can be low-
ered in certain cases by 10–20 ◦ C using catalysts
[Link]. One-Pack Systems (e.g., dibutyl tin dilaurate).
The resulting films have a very high mechan-
Curing with Atmospheric Oxygen. Type 1 ical resistance. They are particularly important
in Table 5. “Urethane oils” are produced by for stone impact protection in automobile fin-
reacting diisocyanates (e.g., TDI or IPDI) ishes, for coating high-quality industrial goods,
with polyol-modified drying or semidrying oils. for electrical insulation, as well as for coil coat-
“Urethane alkyds” correspond in structure to ing applications. Solvent-free products are used
alkyd resins, in which a proportion of the dicar- in liquid form as thick-layer systems or in solid
boxylic acid is replaced by a diisocyanate. Ure- form for powder coatings.
thane oils and alkyds do not contain free iso-
cyanate groups. Drying and film formation oc- Microencapsulated Polyisocyanate Sys-
cur oxidatively, as with alkyd resins (→ Alkyd tems. Type 4 in Table 5. Some powdered diiso-
Resins). Compared to the latter, however, they cyanates or polyisocyanates can be deactivated
generally dry more quickly and the resultant when dispersed in a liquid solvent-free medium
films have better mechanical properties and a and protected by a suitable coating. Diamines
higher solvent resistance. or polyamines can, for example, be added to
produce a stable polyurea layer that requires ca.
Curing with Atmospheric Moisture. 1 % of the isocyanate groups. Since microencap-
Type 2 in Table 5. High molecular mass polyad- sulated polyisocyanates do not cross-link with
dition products of polyols with excess diisocy- reactive groups under normal conditions, they
anate contain reactive isocyanate groups. They form stable one-pack systems at room tempera-
are used to formulate one-pack polyurethane ture. At higher temperature (> 80 ◦ C) the stabi-
paints that cross-link with the formation of lizing coating melts and dissolves, allowing cur-
urea groups under the influence of atmospheric ing to occur. Such systems (e.g., those based on
moisture to produce paint films with excellent dimerized TDI) are used as underbody coatings
resistance to chemical and mechanical attack. in automobile construction.
Solvent-free products and dissolved products
50 Paints and Coatings
Table 5. Polyurethane systems for paints and coatings

Physically Drying Systems. Type 5 in Ta- largely used for industrial applications (e.g.,
ble 5. These systems are based on linear or as glass fiber sizing or as a finish for leather
slightly branched polyurethanes without reac- and leather imitates). Chemical cross-linking is
tive groups that are soluble in organic solvents; achieved by the use of water-soluble melamine
MDI and IPDI are usually used as starting isocy- resins. Stoving temperatures of ca. 140 ◦ C are
anates. On account of their high molecular mass necessary.
these polyurethane resins generally yield highly
viscous solutions with a relatively low solids Systems with Polyisocyanates and Blocked
content. The rapidly drying paints are extremely Reactants. Type 7 in Table 5. Instead of block-
flexible and elastic and have a high resistance to ing the isocyanate groups, they can be combined
mild solvents. Important uses include the coat- with latent reactants (e.g., oxazolidines) to ob-
ing of flexible substrates such as leather imitates tain storage-stable one-pack systems. After ap-
and magnetic tapes. plication, curing is achieved not by heat, but by
atmospheric moisture which induces ring open-
Aqueous Systems. Type 6 in Table 5. Aque- ing and the formation of reactive hydroxyl and
ous dispersions of polyurethanes that are slightly amino groups.
supported by ionic groups also undergo physical
film formation. The binder consists of polymer
chains that are coupled via urethane and urea [Link]. Two-Pack Systems
groups, and contain basic or acid groups. Neu-
tralization by salt formation provides the nec- Polyisocyanate and Polyhydroxyl Systems.
essary hydrophilicity if the “self-emulsifying” Type 8 in Table 5. This is by far the most
properties resulting from incorporation of hy- important system and comprises conventional
drophilic polyether radicals are insufficient. polyurethane paint. The principal binder con-
Anionic dispersions based on IPDI, HMDI, stituents (polyisocyanates and polyhydroxyl
and HDI are particularly important and are compounds) must be kept separate before ap-
 Paints and Coatings 51

plication. In addition to polyols, many other Systems with Polyisocyanates and Blocked
hydroxyl-containing components can be used Reactants. Type 9 in Table 5. In special cases,
for the formulation (e.g., alkyd resins, epoxy compounds with blocked amine groups (e.g.,
resins, castor oil, and cellulose nitrate; see Sec- ketimines) can be used as reaction partners
tion 2.9.1). The mixing ratio of base (hydroxyl for polyisocyanates. The chemical curing of
component) to curing agent (polyisocyanate) these two-pack systems is initiated by humidity
is generally between 1: 1 and 10: 1. The two which causes regeneration of the reactive amine
components are mixed homogeneously immedi- groups.
ately before application. Industrially, mixing can
be performed automatically in two-component
spray equipment. 2.9.3. Properties and Uses
Two-pack polyurethane paints can be applied
by all conventional methods apart from dipping. Polyurethane coatings have three main advan-
Curing takes place at ambient temperature, but tages: high mechanical resistance, outstand-
can be accelerated if necessary by heat. Stoving ing chemical resistance, and (in the case of
is not necessary (energy saving). aliphatic polyisocyanates) excellent lightfast-
The reaction between the isocyanate and the ness and weather resistance. The properties of
hydroxyl groups results in 100 % cross-linking the paint systems which harden at ambient tem-
if the reactants are converted in stoichiometric perature are unsurpassed. They can also be com-
proportions. Optimum paint films are generally bined and formulated in a large number of ways.
formed when NCO : OH equals 1. However, it Specific properties can be optimally adjusted
may be advantageous to deviate from this ra- even for extreme conditions.
tio (under- or over-cross-linking). With aliphatic On account of their broad range of properties,
polyisocyanates, a catalyst (accelerator) is gen- polyurethane paints are used industrially and on
erally necessary. Small amounts (0.05–0.5 %) of a trade scale in virtually all sectors. Practical ap-
tertiary amines or metal-containing compounds plications range from paper coating to the pro-
are normally added to the binder. Amine accel- tection of equipment in industrial plants. Major
erators can also be added to the air stream used areas of use include transportation (large motor
for spraying. Alternatively, the paint films may vehicles, rail vehicles, aircraft, automobile fin-
be cured in an amine-containing atmosphere. ishes and refinishes), the building sector (parquet
Esters, ketones, and ether esters of floor coatings, outdoor coatings, floor coatings,
polyurethane grade (i.e., absence of reactive sealing membranes), the industrial paints sec-
constituents and a maximum water content of tor (equipment, machinery, furniture), as well as
0.05 %) are required for solvent-containing steel structural engineering and hydraulic steel
paints. Aromatic hydrocarbons are suitable structures. Polyurethane paints are particularly
as diluents. High-solids two-pack paints con- important in the surface treatment of plastics.
taining 30–40 wt % of volatile components are
becoming more popular on account of their low
solvent emission. 2.10. Epoxy Coatings
Solvent-free two-pack systems require liquid
reaction components and are normally based on Epoxy resins are generally not used alone but
MDI and its homologues. In contrast to solvent- require a reaction partner in order to be cured
containing paints, pigmented solvent-free two- (hardened). A large number of reaction partners
pack systems require the use of water-binding may be used for curing at elevated or at ambient
agents (e.g., zeolites) to obtain thick, bubble- temperature. The cured films have high adhe-
free coatings. sion, flexibility, hardness, abrasion resistance,
Aqueous two-pack polyurethane paints resistance to chemicals, and corrosion protec-
are obtained by combining, for example, tion. In 1995 ca. 700 000 t of epoxy resins was
hydroxylcontaining polyacrylate dispersions used worldwide by the coating industry (includ-
with water-emulsifiable, low-reactive aliphatic ing civil-engineering applications).
polyisocyanates.
52 Paints and Coatings

2.10.1. Epoxy Resin Types novolacs have a substantially higher functional-

ity than bisphenol A resins, ranging from ca. 2.2
Bisphenol A Resins. Most epoxy resins are (phenol novolacs, e.g., D.E.N. 431, Dow Chem-
condensation products of bisphenol A and ical) to ca. 5.8 (cresol novolacs, e.g., Araldite
epichlorohydrin (→ Epoxy Resins). Depending ECN 1299, Ciba-Geigy). The high functional-
on the ratio of bisphenol A to epichlorohydrin, ity of these resins allows formulation of coat-
resins of varying chain length are obtained, ing systems with a high solvent resistance (high
which differ in molecular mass, melting point, network density). The aromatic structure of the
viscosity, solubility, and content of epoxy and resins is responsible for the high glass transi-
hydroxyl groups. The low molecular mass types tion temperature and good resistance to aqueous
(M r ca. 360–500) are liquid and the medium and acid solutions of the coatings. The chemical
molecular mass types (M r ca. 500–7000) are structure and high functionality lead to coatings
solid at room temperature. Low and medium mo- with limited flexibility and a somewhat lower
lecular mass resins require reaction partners to adhesion to metallic substrates than bisphenol A
give useful coatings. High molecular mass resins epoxy resins.
give useful, physically drying binders, mainly
primers. These resins contain very few epoxy Aliphatic Epoxy Compounds. Epoxidized
groups but many hydroxyl groups. The hydroxyl alcohols are used as reactive diluents for
groups can be reacted at ambient temperature epoxy resins. The reaction products of diols
with polyisocyanates or at elevated tempera- with epichlorohydrin (diglycidyl ethers of bu-
ture (180–300 ◦ C) with amino resins or phenolic tanediol, polypropylene glycol etc., → Epoxy
resins. Resins, Chap. 10) are also used as reactive plas-
ticizers. Polyglycidyl ethers (e.g., of sorbitol
Bisphenol F Resins. Bisphenol F is pro- and pentaerythritol) are commercially avail-
duced by condensing phenol with formalde- able. They have a higher viscosity than the
hyde in an acid medium (→ Epoxy Resins, aliphatic mono- and diglycidyl ethers. They
Chap. 8.1.1). Bisphenol F is a mixture of show good solvent resistance when cured with
isomeric and oligomeric products (novolacs). cycloaliphatic amines. Such resins are also cured
Resins produced by reaction of bisphenol F at elevated temperature with carboxy-functional
with epichlorohydrin have lower viscosities and polyesters, polyacrylates, or polyanhydrides to
a somewhat higher functionality (more epoxy give coatings with good weather resistance.
groups) than the corresponding bisphenol A Aliphatic epoxy resins generally have higher
resins. Like the liquid bisphenol A resins, they color stability and reactivity than aromatic
tend to crystallize. Mixing of bisphenol A and epoxy resins, but their resistance to aqueous acid
F resins prevents or reduces crystallization. On solutions is much lower.
account of their slightly higher epoxy content,
coatings based on bisphenol F resins have a Cycloaliphatic Epoxy Resins. Cycloali-
somewhat higher solvent resistance than sim- phatic epoxy resins are produced by oxidiz-
ilarly formulated bisphenol A resins. Coatings ing olefins with peracids (→ Epoxy Resins,
based on bisphenol F yellow more than those Chap. 11). They are of only minor importance
based on bisphenol A. in surface coatings. They are cured with anhy-
drides, carboxy-functional substances, or Lewis
Epoxy Novolacs. Epoxy novolacs are made acids at 150–200 ◦ C. Ultraviolet curing with tri-
by condensing formaldehyde with phenolic sub- arylsulfonium salts and ferrocenes has become
stances in an acid medium, followed by epox- technically important. Coatings based on cy-
idation (→ Epoxy Resins, Chap. 8.1.2). Only cloaliphatic epoxy resins have a high gloss and
the epoxy phenol novolac and cresol novolac good weather resistance. They adhere to metal-
resins have gained importance in the market. lic substrates better than the acrylate esters nor-
Although bisphenol A novolac resins are also mally used for UV curing but are considerably
available, they have not succeeded in making more expensive.
a commercial breakthrough. All of these epoxy
 Paints and Coatings 53

Glycidyl Esters. Glycidyl ester resins were Therefore, accelerators must be used to cure aro-
originally developed for electrical applica- matic amines with epoxy resins at room temper-
tions. Glycidyl esters of phthalic acid, hexa- ature [137].
hydrophthalic acid, terephthalic acid or trimel-
litic acid (e.g., Araldite PY 284, PT 910) cured Thiols. Thiols have an extremely unpleasant
with carboxy-functional polyesters or polyacry- smell, and are only of industrial importance for
lates at elevated temperatures give coatings with adhesives and joint groutings. They give a high,
both excellent color stability and outdoor resis- permanent flexibility to epoxy resins.
tance.
Isocyanates. Whereas polyamines and thi-
Heterocyclic Epoxy Compounds. The ols cure epoxy compounds via their epoxy
technically most important heterocyclic epoxy groups, isocyanates cross-link high molecular
resin is triglycidyl isocyanurate, obtained by mass epoxy resins via their hydroxyl groups to
reacting cyanuric acid with epichlorohydrin form polyurethanes. The reaction takes place at
(Araldite PT 810, Ciba-Geigy; Tepic, Nissan). ambient temperature. These combinations cure
This trifunctional epoxy resin is combined with more rapidly and at lower temperature than
carboxy-terminated polyesters to give weather- epoxy resins cured with polyamines.
resistant powder coatings [133, 134, 136].
Anhydrides. Polyanhydrides and not
monoanhydrides must be used to cure epoxy sur-
2.10.2. Curing Agents face coatings. They are used in powder form for
powder coatings and in solution for can coatings;
The most important combinations of epoxy both forms are hot curing. The films have a good
resins and curing agents are summarized in acid resistance, and do not impart an undesirable
Table 6. Depending on their molecular mass, taste to foods.
bisphenol A epoxy resins can be cured by
polyaddition via their epoxy or hydroxyl groups. Acids and Carboxy-Functional Polyesters.
Polyamines, polythiols, and polyisocyanates are Curing of epoxy resins with acids and carboxy-
suitable for room temperature cure. Polyan- functional polyesters requires heat. Industrially,
hydrides, polyphenols, acids, and carboxy- these systems are most important in the formu-
functional polyesters are suitable for hot cure. lation of powder coatings: more than 70 % of
Epoxy resins can also be cured by polycondensa- powder coatings are based on epoxy resins and
tion with amino resins or phenolic resins. Epoxy carboxy-functional polyesters (see also Sections
resins can be polymerized with catalysts such 3.4.2 and 3.4.3).
as tertiary amines, boron trifluoride complexes,
ferrocenes, and triarylsulfonium salts.
Polyphenols. Polyphenols react with epoxy
resins on heating, but require an accelerator (e.g.,
Polyamines. Aliphatic polyamines cure
tertiary amines, imidazoles). On account of their
epoxy resins via their epoxy groups at ambient
low color stability, powder coatings based on
temperature. Excess amine is generally prere-
this combination are not used for decorative pur-
acted with the epoxy resin to form a polyamine
poses, but exclusively for functional purposes
adduct. Amines react with monomeric or
where high thermal, mechanical, and chemical
dimeric fatty acids to form polyamidoamines.
resistance is required (e.g., pipe coatings).
Polyamine adduct-cured epoxy resins have
a high chemical resistance. Polyamidoamine-
cured epoxy resins exhibit good adhesion and Amino Resins. Urea, melamine, and ben-
flexibility. zoguanamine resins react with high molecular
Cycloaliphatic polyamines are less reactive mass epoxy resins on heating. Their hydroxy-
than aliphatic amines, and an accelerator must methyl groups react with one another and with
therefore be used for curing at room tempera- the hydroxyl groups of the epoxy resins to form
ture (e.g., salicylic acid). Aromatic polyamines ether bonds. Such systems are used for coating
are even less reactive than cycloaliphatic amines. domestic appliances as well as for packaging.
54 Paints and Coatings
Table 6. The most important epoxy resin–curing agent combinations and their uses

Phenolic Resins. Phenolic resins react with tance, polyols should be added. The films should
high molecular mass epoxy resins on heating. be postcured for 30–120 s at ca. 100 ◦ C [138].
Such systems are used as “gold lacquers” to
line food containers. The similarly synthesized
bisphenol A resols produce colorless coatings 2.10.3. Chemically Modified Epoxy Resins
with a higher chemical resistance, less odor dur-
ing cure, and less alteration of the taste of food in Epoxy Resin Esters. Air- or oven-drying es-
contact with the coating. Flexibility is, however, ters can be produced by esterification of epoxy
lower than with standard phenolic resins. resins (M r 1000–2000) with fatty or oleo-
resinous acids (fatty acids of linseed oil, soybean
Catalytically Curing Compounds. Al- oil, tall oil, coconut oil, or dehydrated castor oil).
though tertiary amines can polymerize epoxides Plasticized epoxy resins can be produced by
even at room temperature, the degree of poly- reacting low molecular mass epoxy resins with
merization is too low to obtain useful coat- dimeric fatty acids. These resins (e.g., Epikote
ings. Boron trifluoride complexes polymerize 872, Shell) generally exhibit better substrate
epoxides on heating. Such combinations are wetting than the unmodified epoxy resins. This
sometimes used in powder coatings if high sol- reaction is, however, associated with the forma-
vent resistance is required. tion of ester bonds, and the resins therefore have
Ultraviolet curing of epoxy resins has be- a poor resistance to alkaline solutions. Instead
come important. Cycloaliphatic epoxy resins are of fatty acids, carboxy-functional polybutadie-
combined with substances that induce polymer- neacrylonitrile elastomers can also be used to
ization under the influence of UV radiation or flexibilize epoxy resins.
an electron beam. Industrially important prod-
ucts include triarylsulfonium salts (UVE 1014, Esters of Epoxy Resins and Acrylic Acid.
1016, General Electric) and arene–ferrocenium If low molecular mass liquid to semisolid epoxy
compounds (CG 24–061, Ciba-Geigy). To en- resins are heated with acrylic acid at ca. 120 ◦ C,
sure good film flexibility and chemical resis- epoxy acrylates are produced. These resins can
 Paints and Coatings 55

be dissolved in low molecular mass acrylate es- Epoxy resin coatings that are cross-linked with
ters and used as raw materials for UV-curable aliphatic amines have the highest solvent resis-
finishes. They are mainly used for paper and tance. Cycloaliphatic amines (Laromin C 252,
cardboard (record sleeves), but also for metals. C 260, BASF; Vestamin IPD, Hüls) have to be
modified and accelerated to permit curing at
Esters of Epoxy Resin and Methacrylic room temperature. These amines give a very at-
Acid. Epoxy resins can also be reacted with tractive appearance to the cured film and are
methacrylic acid on heating. The resulting meth- mainly used for decorative wall and floor fin-
acrylate ester resins are dissolved in polymer- ishes. Aromatic amines (e.g., diaminodiphenyl-
izable solvents and catalyzed with peroxides methane) are solid, but can be used for cold cur-
(e.g., Derakane, Dow Chemical). These cat- ing by adduct formation and acceleration. Films
alyzed resins are applied as thick-layer laminates based on such curing agents (Ancamin LT, An-
in combination with glass fibers, fabrics, or mats. chor; HY 830, HY 850, Ciba-Geigy) have a
The laminates are generally cured at ca. 60 ◦ C glasslike appearance and extremely good resis-
and have extremely good chemical resistance; tance to organic and inorganic acids.
they are therefore used in the chemical indus- Solvent-free epoxy systems must be applied
try for the internal lining of reactors and storage within an extremely short time (30–60 min),
tanks [139–142]. which presents problems, particularly in hot
countries. Such systems are also frequently ap-
plied with heatable two-component spraying
2.10.4. Uses equipment. Ketimines give a longer pot life.
They are produced by condensing ketones and
[Link]. Curing at Ambient Temperature polyamines. When applied as a thin layer, they
react with atmospheric moisture and are con-
Solvent-Free Coatings. Solvent-free appli- verted back into the ketone and polyamine. The
cable binder systems which cure at ambient tem- ketone evaporates from the film and the amine
perature are not only used for coating applica- cross-links the epoxy resin. Ketimines can only
tions. By adding quartz sand to low-viscosity be used if a sufficiently high ambient tempera-
binder systems, floorings can be formulated. De- ture (> 20 ◦ C) and high atmospheric moisture
pending on the chosen filler/binder mixing ra- (> 75 % R. H.) can be guaranteed.
tio, these systems are applied as self-levelling
floorings or as mortar screeds. Adhesives and Solvent-Containing Coatings. Semisolid
joint fillers for concrete applications are for- to solid bisphenol A resins (M r 500–1500)
mulated in a similar way. For all these uses, are used to formulate solvent-containing paints.
only low molecular mass liquid bisphenol A They are sometimes mixed with epoxy novolacs
and bisphenol F epoxy resins (M r 340–400) or to increase the network density and thus the sol-
their mixtures are suitable. While solvent-free vent resistance of the coating. Aromatic hydro-
coatings are applied in film thicknesses bet- carbons, often mixed with alcohols, are gener-
ween 300 and 1000 µm, floorings are applied ally used as solvents. The epoxy resins are cross-
in 2–10 mm layers, depending on the quartz linked with modified aliphatic polyamines, in
sand content and the application method used. the form of in situ amine adducts or as iso-
Reactive diluents (cresyl and isooctyl glycidyl lated amine adducts dissolved in xylene and bu-
ethers, diglycidyl ethers of 1,4-butanediol or tanol. Polyamine adduct–epoxy resin combina-
1,6-hexanediol) are often added in amounts of tions have an extremely good hardness and good
10–20 % to these resins. They react with the resistance to aqueous alkaline solutions and or-
curing agent and lower the viscosity of the ganic solvents.
epoxy resin (1000–3000 mPa · s at 25 ◦ C) to In practice, polyamidoamines are the most
improve processing properties. Polyamines and important curing agents for these types of epoxy
modified polyamines are used as curing agents. resins. Polyamidoamines and polyamidoamine
Aliphatic polyamines are industrially very im- adducts with epoxy resins confer maximum flex-
portant because they are highly reactive and ibility and adhesion to epoxy coatings. Such sys-
can cure epoxy resins at ambient temperature. tems are frequently used as primers on metal-
56 Paints and Coatings

lic and mineral substrates. As topcoats, epoxy ener HZ 340, Ciba) are used as curing agents.
paints are only used for interior applications Such two-component systems are environmen-
since they tend to yellow, become matt, and ex- tally friendly and are mainly used for coat-
hibit chalking under the influence of light and ing concrete and other mineral substrates as
weather. The cured films exhibit good resistance well as pretreated plastics. Up till now more
to aqueous, alkaline, and neutral solutions; their than 80 % of waterborne binder systems are ap-
resistance to organic solvents is limited. plied to these substrates, because waterborne
To reduce the use of organic solvents in epoxy systems adhere well to wet concrete sur-
paints, low-VOC (high-solids) coatings are be- faces and do not attack plastics like solvent-
coming more and more important in both Eu- containg coatings do. Aqueous emulsions based
rope and the USA. The solids content of these on solid resins (M r ca. 1000) containing ca. 10 %
ambient-cured coatings can be increased by the organic solvents are commercially available
partial replacement of the solid epoxy resins (Beckopox EP 384, Vianova; Araldite PZ 3961,
by liquid bisphenol A or bisphenol F epoxy Ciba). These emulsions are less reactive than
resins. Some raw material suppliers offer modi- those based on liquid bisphenol A epoxy resins.
fied bisphenol A resins (e.g., Epikote 874 X 90, Therefore, they can be combined with water-
Shell; Araldite XB 290, Ciba) and curing agents soluble polyamine adducts (e.g., Beckopox
(Witco, various modified polyamidoamine- Hardener EH 623, EH 613, Vianova; Hardener
based hardeners), which allow the formula- HZ 3980, HZ 3981, HZ 3982, Ciba; Hardener
tion of coatings with a low VOC content XE 36, Witco) so that even white coatings with
(< 300 g/L). good chemical resistance properties can be for-
High molecular mass epoxy resins (M r mulated. Due to the higher film-forming temper-
3000–20 000) may be regarded as poly- ature compared to the liquid-resins-based sys-
ols, and are cross-linked with isocyanates to tems, such binder systems should not be used for
form extremely chemically resistant coatings civil-engineering applications. They are mainly
(Desmodur N, L, Bayer; IPDI, Hüls). Epoxy intended for the surface protection of metallic
resin–isocyanate combinations are also used to substrates. Coatings with improved flexibility
formulate rapidly curing shop primers. and adhesion to steel can be obtained by the
use of modified bisphenol A epoxy resin emul-
Solvent-Containing, Air-Drying Epoxy sions (e.g., Beckopox EP 385, Vianova; Araldite
Esters. In order to produce epoxy resin es- PZ 3962, Ciba) which allow the formulation of
ters that can be cured at room tempera- highly filled primers. Their corrosion protection
ture, solid epoxy resins (M r 1500–2000; e.g., properties are similar to primers formulated w
Araldite GT 6084, Ciba-Geigy; Epikote 1004, ith solvent-containing epoxy resins.
Shell) are reacted with air-drying fatty acids
(e.g., linseed oil or soybean oil fatty acid). The
area of application of these resins is very similar [Link]. Curing at Elevated Temperature
to that of air-drying alkyd resins, but they have
a higher chemical resistance and improved flex- Powder Coatings. Powder coatings mainly
ibility. Normal driers (e.g., cobalt octoate) are contain solid bisphenol A resins with M r
used to accelerate drying. between 1000 and 2000 (Araldite GT 6063,
6064, 7004, Ciba-Geigy; DER 662, 663, 664,
Waterborne Coatings. Low molecular Dow Chemical; Epikote 1055, Shell). Carboxy-
mass liquid bisphenol A and bisphenol F epoxy functional polyesters are the most important cur-
resins (M r 340–400) and their mixtures are ing agents (Grilesta, Emser Werke; Grylcoat,
made water emulsifiable by either adding non- UCB; Uralac, DSM). Modified and accelerated
ionic emulsifiers or epoxy-group-containing dicyanodiamides and polyphenols, and in some
emulsifiers which take part in the curing re- cases polyanhydrides may also be used. For a de-
action (Araldite PY 340–2, PY 3960, Ciba; tailed description of powder coatings, see Sec-
Beckopox EP 147w, Vianova). Water-soluble tion 3.4.
polyamidoamines or modified polyimidazolines Powders coatings based on aromatic epoxy
(Casamid 360, 362, Anchor former Akzo; Hard- resins have high chemical and mechanical resis-
 Paints and Coatings 57

tance, but are not resistant to weathering. To ob- The use of carboxy-functional or anhydride-
tain weather-resistant powders, triglycidyl iso- functional low molecular mass polyesters as cur-
cyanurate (Araldite PT 810, Ciba-Geigy; Tepic, ing agents is more recent. They are used to for-
Nissan) must be used as the epoxy component mulate white-pigmented can coatings. Blocked
with carboxy-functional polyesters. isocyanates (Desmodur AP stable, Bayer) cure
Animal studies have shown that trigly- high molecular mass epoxy resins on heating.
cidyl isocyanurate (TGIC) is a severe eye ir- The films have an extremely high hardness, good
ritant, a mild skin and nasal irritant, and can flexibility, and high resistance to chemicals.
cause genetic damage. This has led to concern
over potential reproductive or carcinogenic ef- Hot-Curing Epoxy Resin Esters. Solid
fects and therefore alternative, less-toxic epoxy epoxy resins with a molecular mass of ca. 2000
resins have been introduced. Most similar to can be esterified with semidrying and/or nondry-
the TGIC/carboxy-functional polyester powder ing fatty acids. These resins are used in combina-
coatings in their film properties are those based tion with amino resins for stoving primers, can
on glycidyl esters (e.g., Araldite PT 910, Ciba), coatings, and industrial finishes. The importance
which are also cured with carboxy-functional of epoxy resin esters has, however, decreased in
polyesters. These two systems dominate the ar- recent years.
chitectural and exterior coatings sector since
they combine good weather stability with good Waterborne Paints and Coatings [144,
flexibility and excellent adhesion to steel and 145]. For ecological reasons waterborne indus-
aluminum [134]. Latest developments by DSM trial paints and coatings have become extremely
combine epoxidized linseed oil with carboxy- important. The epoxy or hydroxyl groups of
functional polyesters, so that binder systems are epoxy resins must be chemically modified to
available which do not need to be labelled [135]. make them waterborne. Water-soluble epoxy
paints can be produced by esterifying the resins
Solvent-Containing Paints. Butylated (M r 1000–2000) with a monocarboxylic fatty
urea–formaldehyde resins, butylated or methyl- acid, followed by reaction with an anhydride.
ated melamine–formaldehyde resins, and buty- The resins are then dissolved in a water-
lated benzoguanamine–formaldehyde resins re- soluble solvent (e.g., glycol ether or an alcohol)
act with the hydroxyl groups of epoxy resins (M r and made waterborne by neutralization with a
3000–10 000) at elevated temperature (160– monoamine. Such resins are cured with ami-
200 ◦ C) under elimination of alcohols. Ether no resins (e.g., hexamethoxymethylmelamine)
bonds are formed that are largely responsible at ca. 160 ◦ C. The waterborne epoxy paints that
for the good chemical resistance of such paints. are applied by anodic electrodeposition have a
The coatings have outstanding adhesion, impact similar structure. Cathodically deposited coat-
resistance, good flexibility, and high surface ings (as employed in the automotive industry)
hardness. Epoxy resin–urea resin combinations are generally produced by reacting low molecu-
are mainly used as primers or one-coat systems lar mass epoxy resins (M r ca. 1000) with a sec-
in the packaging sector, whereas combinations ondary amine, followed by neutralization with
with melamine and benzoguanamine resins are an organic acid. Blocked isocyanates are usu-
mostly used as topcoats [143]. ally used for curing.
Phenol–formalydehyde resins (in some cases Waterborne coatings are increasingly used
butylated) and to a small extent bisphenol A– for can coatings. The binders are mainly based
formaldehyde resins have become important as on epoxy resins. High molecular mass epoxy
curing agents for epoxy resins in can coatings. resins (M r 3000–4000) can be made waterborne
Curing occurs primarily via the hydroxyl group by graft polymerization with acrylates, methac-
of the epoxy resin and the etherified methylol rylates, and/or acrylic or methacrylic acid in the
groups of the phenolic resin. The epoxy groups presence of styrene, and subsequent neutraliza-
also react with the phenolic hydroxyl groups of tion with amines. These waterborne polymers
the phenolic resin. The coatings are cured at ca. are normally cured with amino resins. All of the
200 ◦ C and are extremely resistant to foods, cos- coatings exhibit good adhesion and flexibility
metics, and pharmaceuticals. and are mainly used for beverage cans.
58 Paints and Coatings

[Link]. Radiation Curing manufacturing processes, practically all cur-

rently commercially available epoxy resins con-
Cycloaliphatic epoxy resins are normally used tain only the smallest traces of epichlorohydrin
for cationic radiation curing (see also Section [146].
3.8). A strong Lewis or Brønsted acid is formed
after photolysis of the initiator. This acid opens
the epoxide ring, thus initiating the polymeriza- 2.11. Silicone Coatings
tion reaction. The chain length is thereby in-
creased. Aryldiazonium salts are no longer used Polysiloxanes or silicones have been used in sur-
as initiators due to their poor dark storage sta- face coatings since the earliest days of the sili-
bility and unsatisfactory film quality. Diaryl- cone industry [147–149]. They are versatile ma-
halonium salts are only employed to a small terials with an enormous range of properties and
extent. Triarylsulfonium salts are the most im- physical forms [150]. For a detailed description
portant initiators. The special advantages of of silicones, see → Silicones. They have a very
cationic cure are the possibility of coreaction low surface energy, high thermal stability, are
with substances containing reactive hydrogen UV transparent, and have a low glass transition
atoms (e.g., for flexibilization), insensitivity to temperature (T g ). These properties are utilized
oxygen during cure, and low shrinkage. by the paint industry to provide excellent water
The systems are color-stable, weather resis- repellency and resistance to weathering, UV ra-
tant, flexible, and also adhere well to tin-free and diation, and thermal cycling. Silicones used in
low-tin sheet metals, as used in the manufacture paints can be conventiently classified into four
of beverage and aerosol cans. Although arene– types: silicone resins, blending resins, silicone
ferrocenium complexes even allow the cure of organic copolymers, and paint additives.
bisphenol A epoxy resins, provided postcuring
takes place, these systems have not yet become Silicone Resins. Silicone resins used in
important in surface protection applications. The paint applications are usually produced from
reasons for this are inadequate color stability and mixtures of di- and trifunctional organosi-
weather resistance as well as the intense color of lane monomers (e.g., phenyl- and methyltri-
these films. chlorosilane, methylphenyldichlorosilane, and
dimethyldichlorosilane) by controlled hydroly-
sis and condensation. Typically, mixed chlorosi-
[Link]. Occupational Health lanes in xylene are added to water; hydrolysis
produces a layer of concentrated hydrochloric
Liquid unmodified bisphenol A, A/F, and F acid which is then removed. The remaining so-
resins produce little or no irritation of the skin lution of siloxane oligomers (M r 2000–4000)
or mucous membranes; they can, however, act as is neutralized with sodium hydrogencarbonate
sensitizers and cause dermatological allergies. and washed with water. At this stage the low-
Solid epoxy resins based on bisphenol A can viscosity resin contains 3–6 % silanol. Further
be categorized as effectively nontoxic; they are condensation (bodying) and azeotropic distil-
nonirritating and scarcely sensitizing. The same lation of water in the presence of catalysts
is true for the novolac epoxy resins, although such as zinc octanoate reduces the silanol
their liquid forms can have a sensitizing effect. level to 0.5–2 % and yields high-viscosity net-
Reactive diluents and low molecular mass work resins (M r 200 000–500 000). Alterna-
aliphatic epoxy resins of low viscosity show tively, alkoxysilanes (most commonly meth-
a detectable vapor pressure, and have to be oxysilanes) may be used as starting materials
handled with care. These substances produce in which case alcohol, usually methanol, is lib-
medium to strong irritation of the skin and mu- erated during hydrolysis, bodying, and curing.
cous membranes; they are also sensitizers and The final properties of the resin can vary greatly
can cause skin disorders. depending on the nature of the substituents,
Epichlorohydrin, which is used for the syn- the degree of substitution, and the extent of
thesis of epoxy resins, is a suspected carcino- the condensation reaction and hence the con-
gen in animals. Thanks to the well-developed tent of residual reactive groups [148]. Products
 Paints and Coatings 59

vary from hard, brittle monomethyl flake resins unmodified organics, particularly in heat sta-
to soft, flexible phenyl-containing resins dis- bility, chalking resistance, and gloss retention
solved in a solvent. Resins with a higher phenyl [154]. The silicone intermediates are usually low
content are more thermoplastic, have greater molecular mass oligomers that are rich in reac-
heat and oxidation resistance [151], longer shelf tive hydroxyl or alkoxy groups and have a high
life, and tend to be more compatible. A high level of organic substitution. They are copoly-
methyl content confers faster cure rates, flex- merized with polyester, alkyd, and acrylic resins
ibility, hardness, and better retention of prop- containing 80–250 % excess hydroxyl groups,
erties at low temperature. The level and type usually in the presence of titanium catalysts
of substituents selected depend on the applica- [148]. If silanol-functional intermediates are
tion requirements. For example, silicone resins used, the titanium catalysts promote copolymer-
formulated with white or colored pigments can ization via–COH and–SiOH groups, thus elimi-
withstand continuous service temperatures of nating the tendency for homopolymerization via
260–370 ◦ C, whereas aluminum-filled paints SiOH groups. Choice of solvent and catalyst,
made with phenyl-containing silicone resins re- concentration of reactants, and extent of reaction
sist temperatures up to 700 ◦ C by forming pro- play an important role in the final composition
tective ceramic frits [152]. Silicone-resin-based and performance of the copolymer. Methoxy-
paints are used in extreme environments where functional silicone intermediates react with or-
organic paints are ineffective [153], e.g., boiler ganic hydroxyl groups by elimination of metha-
stacks, exhausts, ovens, furnaces, heat exchang- nol. Use of special catalysts, e.g., Al(CH3 COCH
ers, hot plates, grills, air-conditioning units, and COCH3 )3 and Ti[OCH(CH3 )2 ]4 , allows better
jet engines. control of the condensation reaction and lessens
the yellowing caused by many catalyst systems
Silicone Organic Blends. Pure silicone at elevated temperature [155]. Materials made in
resins are too soft and thermoplastic for gen- this way (e.g., silicone polyesters) can contain as
eral paint application but are frequently blended much as 80 % silicone resin. Almost all types of
with traditional organics such as alkyd, acrylic, organic coating have at some time been mod-
epoxy, and phenolic resins. The higher levels ified with silicone resins [156] although com-
of reactive groups in unbodied silicones provide mercial success has been realized mainly with
sites for copolymerization on curing; the low polyesters. A major user of silicone polyester
molecular mass (2000–4000) ensures good com- paints is the coil coating industry where coat-
patibility which is essential for optimum film- ings containing > 50 % silicone have retained
forming properties. The organic component can their gloss and color for more than ten years
improve the hardness and drying properties of [153]. Other applications include appliance fin-
the silicone while the silicone adds gloss and ishes, exterior cookware coatings, and colored
color retention at elevated temperature. These maintenance and architectural paints.
properties are employed in exterior maintenance
paints. Improvement in durability is generally Curing. Curing cycles are primarily deter-
proportional to the silicone content of the blend. mined by the silicone content of the resin [152].
This in turn is determined by performance–cost A typical cure schedule for a 100 % silicone
considerations and usually lies in the range 30– resin is 30 min at 260 ◦ C. For 50–80 % sili-
50 %. cones, satisfactory cures are obtained in 15 min
at 220 ◦ C. For silicone-modified organic coat-
Silicone Organic Copolymer Resins. Sim- ings, complete cure can be achieved using am-
ple blends of organic and silicone resins are bient or low-bake (< 180 ◦ C) cure conditions.
unsuitable for many high-performance appli-
cations where mechanical properties and good Silicone Paint Additives. See also Section
weather resistance are of primary importance. 5.3. Because of their very high surface activity,
They may become incompatible at the required modified silicone fluids and resins are widely
levels and copolymerization is therefore pre- used in paint formulations to achieve special de-
ferred. At levels of 20–60 % the silicone copoly- sirable effects [157, 158]. The only silicone ad-
mers impart considerable improvements over ditive likely to cause surface finish defects is an
60 Paints and Coatings

overdose of polydimethylsiloxane. New silox- in nature and supplied as 100 % solids;

ane organic copolymers are compatible with or- hexakis(methoxymethyl)melamine (HMMM) is
ganics and overcome problems with fish eyes a typical example. Fully alkylated MF resins
(oval surface defects), cratering, and recoata- have gained a major market share in the United
bility. They perform at very low concentrations States accompanied by increasing penetration in
(generally 0.01–0.5 %) and are used to improve Europe and Japan. Replacing a conventional par-
flowout, mar and scuff resistance, adhesion, lev- tially alkylated amino resin with a fully methyl-
eling, and gloss. They can also control foam- ated resin increases the solids content of a paint
ing [159], aid pigment dispersion, and impart by 3–8 %. Reasons for their success include
special textured effects (e.g., hammer finishes). higher application solids, improved hardness–
Silicone additives can be used in most paints in- flexibility relationship, better exterior durability,
cluding solvent-based, waterborne, high-solids, improved reaction with functional groups on the
and powder coatings. backbone polymer, stability in waterborne coat-
ings, reduced emission of formaldehyde, and
high reactivity under controlled conditions. The
2.12. Urea, Benzoguanamine, and incorporation of cross-linking agents of this type
Melamine Resins for Coatings provides the formulator with the capability to
utilize low molecular mass backbone polymers.
Alkylated urea --, benzoguanamine --, and
melamine–formaldehyde resins (→ Amino Properties. Alkylated amino resins can be
Resins) represent a versatile group of cross- classified into two general classes: (1) poly-
linking agents for hydroxy-, amide-, and meric, partially alkylated resins which have
carboxy-functional polymers. They are used a lower solids content and (2) the more
in both waterborne and solventborne coatings, monomeric, fully and partially alkylated prod-
including high-solids industrial coating sys- ucts which have a higher solids content.
tems. These amino resins are almost always Typical polymeric, partially alkylated ami-
employed in combination with other flexibiliz- no resins are butylated or isobutylated conden-
ing functional polymers (backbone polymers) sates with an average degree of polymerization
to form highly cross-linked networks. between 3 and 8 and a combined formaldehyde
The major application for amino resins is content of 1.4–1.8 per amino group [160–162].
in baking systems; there is a small market for The hydroxymethyl (methylol) groups are par-
acid-catalyzed wood coatings that are cured at tially alkylated (degree of alkylation 40 –80 %).
room temperature. Excellent properties can be The final resin has a solids content of ca.
obtained in both the formulated coating and the 50–65 %, and a combination of functional sites
cured film. Advantages include excellent exte- of different reactivity [161]. The solvents most
rior durability, adhesion to metal, gloss and color commonly used are aromatic hydrocarbons and
retention, relatively low cost, and excellent sta- alcohols.
bility. Amino resins have found widespread use The higher reactivity of partially alkylated
in automotive primers and topcoats, appliance amino resins was long attributed to the presence
coatings, metal decorating, and most general in- of free hydroxymethyl groups. Under weakly
dustrial applications. They are usually modified acidic cure conditions, these hydroxymethyl
by etherification with alkyl ether groups; in the groups demethylolate to form alkoxymethyl
paint industry the term alkylated (methylated, groups adjacent to secondary amide groups
butylated etc.) is commonly used for these mod- which respond more favorably to general acid
ified resins. catalysis [162–165].
The first amino resins used in coatings were Since 1970 fully alkylated monomeric
partially butylated, polymeric urea–formalde- melamine resins based on hexakis(methoxy-
hyde (UF) resins introduced in the late 1920s. methyl)melamine (HMMM) and higher-solids
Melamine–formaldehyde (MF) resins followed methylated melamine resins have replaced con-
in 1935. In 1960 a range of fully alkylated, ventional partially butylated amino resins in
predominantly methylated MF resins were in- many applications. They have also made sig-
troduced. These products are more monomeric nificant inroads into the UF and the benzogua-
 Paints and Coatings 61

namine market. Although these resins are des- (e.g., formic, oxalic, or phthalic acid) or weak
ignated monomeric, they are of oligomeric na- inorganic acids (e.g., phosphoric acid). The end
ture, with a degree of polymerization between point of the alkylation reaction can be controlled
1.4 and 3.0. The amount of combined formalde- by compatibility testing of the resin with low-
hyde is about 1.7–1.9 per amino group. The de- polarity solvents. The hydroxymethylation cat-
gree of alkylation for fully alkylated products is alyst remains in the resin either in free form or
90–95 % of all available hydroxymethyl groups. as the salt and may influence the reactivity of the
Fully alkylated amino resins require strong resin.
acid catalysis for fast and/or low-temperature Monomeric partially and fully alkylated ami-
cross-linking. Their catalysis mechanism is dif- no resins are prepared in two separate reaction
ferent from that of partially alkylated resins steps. Hydroxymethylation is carried out under
which respond to weak acid catalysts or general basic conditions to minimize self-condensation
acid catalysis. A fully alkylated melamine resin of the amino resin. The pH is then lowered by
catalyzed by a strong acid catalyst is a faster cur- addition of a mineral acid and alkylation with
ing (cross-linking) agent than a partially buty- methanol is carried out. To obtain monomeric
lated amino resin. amino resins, an excess of formaldehyde has
The catalysts which are predominately used to be used to assure a high level of hydroxy-
are p-toluenesulfonic acid, dodecylbenzenesul- methylation and a low level of residual amide
fonic acid, and dinonylnaphthalenedisulfonic groups that would otherwise lead to polymer
acid, and their amine salts [165]. Compared to formation during the alkylation step. Since wa-
partially alkylated amino resins, fully alkylated ter removal by azeotropic distillation is not pos-
resins have a lower tendency to undergo self- sible with methanol, a large excess of alcohol
condensation and produce films which are hard is required to achieve complete alkylation. Af-
and still more flexible. ter completion of alkylation the resin solution is
neutralized; water, alcohol, and residual formal-
Production. Although the patent literature dehyde are removed by vacuum distillation. The
cites many other amino and amide compounds, salt formed during neutralization is removed by
only urea, melamine, benzoguanamine, acryl- filtration [167].
amide, and glycoluril have found a market po- The fully alkylated amino resin is character-
sition as starting materials for the production of ized by its degree of alkylation and polymeriza-
amino resins. Formaldehyde is the only aldehyde tion, and its residual hydroxymethyl and ami-
used on a commercial scale. Methanol, butanol, no content, all of which can significantly affect
and isobutanol are mainly employed as alkylat- physical and chemical properties.
ing alcohols.
The manufacturing process for partially alky- Environmental Protection. The potential
lated amino formaldehyde resins consist of two release of formaldehyde during application and
consecutive reactions. The first reaction is the cure is a serious problem in the handling of ami-
methylolation (hydroxymethylation) of an ami- no resins. Depending on the structure and the
no compound such as urea, melamine, or ben- conditions of manufacture a resin can contain
zoguanamine with formaldehyde and can be car- 0.25–3 % free formaldehyde. The formaldehyde
ried out under basic or acidic conditions. Hy- liberated from an amino resin may originate
droxymethylation under acidic conditions leads from three sources: unreacted formaldehyde,
to simultaneous alkylation and polymerization formaldehyde bound to the resin in the form of
of the amino resin. The second reaction, alkyl- hydroxymethyl groups, or as a result of hydro-
ation (or etherification), is carried out under lysis of the alkoxymethyl groups during cure
acidic conditions. and subsequent dehydroxymethylation [162].
Conventional low-solids butylated and iso- Fully alkylated MF resins may contain
butylated amino resins are normally prepared in < 0.25 % free formaldehyde. Partially alkylated
this fashion [166]. The reaction water formed resins usually have a higher content (≤ 3 %).
during the hydroxymethylation or alkylation The free formaldehyde content of an amino resin
step can be removed by azeotropic distillation. is largely responsible for the formaldehyde re-
The acids used for catalysis may be organic leased during the application process. This is
62 Paints and Coatings

only a small fraction of the total formaldehyde Storage and Transportation. Amino resins
released. Hydrolysis of the amino resin and should be stored in stainless steel or in lined car-
subsequent dehydroxymethylation during cur- bon steel containers. The lining should be re-
ing account for > 80 % of the total formalde- sistant to degradation or swelling by alcohols.
hyde release (see also page 63). Unlined steel vessels can be used under certain
Although resins with a high amino content circumstances. The unlined vessel should have
have a higher content of free formaldehyde a desiccator on the gas-inlet line to remove wa-
than fully alkylated resins, they release lower ter vapor from the gas that is used to replace the
amounts of formaldehyde during cure. The low- resin as it is pumped out of the tank. Methylated
est amount of formaldehyde during application amino resins are preferably stored in lined drums
and cure is released by alkylated glycoluril– or in fiber pack containers.
formaldehyde resins [168]. Amino resins should be stored at 20–27 ◦ C.
Lower temperatures can cause crystallization
Quality and Specifications. A typical spec- of hexakis(methoxymethyl)melamine and par-
ification for an amino resin contains informa- tially methylated melamine resins. Careful re-
tion on solids, viscosity, color, density, and free heating is then required. Maximum storage tem-
formaldehyde content. perature for fully alkylated melamine resins is
A combination of analytical techniques has 50–65 ◦ C for 14–30 days. Amino resins with a
to be used to fully characterize an amino resin: lower degree of alkylation should not be stored at
molar ratios of amino compound to aldehyde and these temperatures. Fully alkylated amino resins
alcohol, molecular mass, molecular mass distri- are stable at 20–27 ◦ C for more than 24 months.
bution, and functional group content are impor- Butylated and partially methylated amino resins
tant data. should not be stored for more than 6–12 months.
Amino resins are offered at a solids content of Since many amino resins contain solvents,
50–100 %. For solutions a reliable nondestruc- local safety codes regarding flammable liquids
tive drying method is required before analysis should be observed. For bulk storage an inert
[169]. Drying at < 50 ◦ C in a thin film or un- gas atmosphere above the resin should be used
der vacuum gives reproducible results without [175].
loss of resin components or degradation of the
resin. This is especially critical for highly reac- Uses. The use of amino resins in packaging
tive resins. Solids methods which dry the resin at is regulated by the FDA under 21 CFR 175.105,
100–110 ◦ C result in dehydroxymethylation of adhesives; 21 CFR 175.300, resinous polymeric
the resin and reduced solids content particularly coatings; 21 CFR 176.170, paper and paper-
when applied to polymeric butylated types. board in contact with aqueous, fatty, and dry
Total amino resin content can be determined food.
in the solid residue by the Kjeldahl nitrogen Alkylated melamine–, urea–, and benzo-
method or by CHN analysis. In melamine resins guanamine–formaldehyde resins are the princi-
titration of melamine with perchloric acid is pos- pal cross-linking agents in many industrially ap-
sible. The total level of free and combined form- plied baked coatings. They are combined with
aldehyde can be determined by phosphoric acid acrylic, alkyd, epoxy, and polyester resins. The
decomposition and by distillation. amide, hydroxyl, or carboxyl groups of these
Free formaldehyde is readily determined by backbone polymers are used as functional sites
titration in ice water with sodium sulfite solu- for reaction with the amino resin.
tion. Titration at higher temperature results in The choice of amino component depends on
dehydroxymethylation. An indirect method for the end use. Butylated UF resins are princi-
determining the structure of an amino resin con- pally used in low-temperature curing applica-
sists of CHN analysis and 1 H-NMR to deter- tions, such as wood and general industrial coat-
mine the CH2 : alkoxy ratio [170–172]. The hy- ings. Small amounts of these resins are also em-
droxymethyl content of amino resins can also be ployed in container coatings in combination with
determined by reaction with iodine under basic epoxy resins. With the development of high-
conditions or by 13 C-NMR [173, 174]. solids coatings, urea resins have been replaced
in many applications with HMMM-type resins.
 Paints and Coatings 63
Japan
The market for benzoguanamine resins is Mitsui Cyanamid Cymel
small, and is mainly limited to container and Mitsui Toatsu U-Van
appliance coatings because of its superior an- Chemical
ticorrosion properties. Dainippon Ink & Super Beckamine,
Chemicals
The largest market for amino resins is in the Beckamine
automotive topcoat area. Most heat-cured au- Hitachi Melan
tomotive primers, primer surfacers, basecoats, Sanwa Chemical Nickalac
Sumitomo Chemical Suminal
and clearcoats utilize melamine cross-linking Korea
agents. In the United States most of the ami- Monsanto–Kumbo Resimene
no resins used in high-solids automotive top-
coats are monomeric, mixed ether, fully alky-
lated (methylated/butylated) MF resins. Outside Economic Aspects. The growth of the ami-
the United States lower-solids coatings are pre- no resin market is closely related to the overall
dominantly used, which are cross-linked with growth of industrial coatings. The development
conventional low-solids, partially butylated MF of new coating technologies (e.g., powder coat-
resins. The level of cross-linker is ca. 25 % in ings and radiation curing) may depress the fu-
low-solids coatings and 35–40 % in high-solids ture expansion of this market. However, this is
coatings. counteracted to some extent by increased use of
The cure temperature for most amino-resin- melamine resins in high-solids coatings which
based automotive coatings is 120–150 ◦ C. In is greatly influenced by the global trend to less
end-of-line repair applications the same coat- polluting coatings with a lower volatile organic
ings are cured with addition of acid catalyst at content.
80–90 ◦ C. The world market for amino resins used in
Amino resins are also employed in water- coatings in 1990 was estimated to be 200 000–
borne systems used in industrial coatings (e.g., 225 000 t [176]. The U.S. market is about
automotive spray primers and basecoats, can and 50 000 t, with the European market estimated
coil coatings). Stable coatings can be formulated to be of similar size. The Japanese market is ap-
with hexakis(methoxymethyl)melamine or par- proximately 33 000 t. A breakdown of the U.S.
tially methylated melamine resins. market for amino resins used in coating applica-
tions is as follows (103 t):
Commercial products and suppliers of
melamine resins are listed below: Automotive 13.5
General industrial 8.5
Wood 4.5
Paper, film, and foil 5.8
United States Appliances 1.8
American Cyanamid Cymel/Beetle Coil 4.8
Monsanto Resimene Container 4.8
Europe Other 4.0
Vianova Austria Viamine Total 47.7
Krems Austria Sakopal
Hoechst/Casella FRG Maprenal, Resamine
BASF FRG Luwipal, Plastopal
In the United States high-solids amino resins
Hendricks (predominantly methylated resins with a solids
& Sommer FRG Heso Amin content of > 80 %) enjoy a major market posi-
Synthese Netherlands Setamine tion. Both in Europe and Japan methylated resins
DSM Netherlands Uramex
Dyno Cyanamid Norway Dyanomin-Cymel, are used only in applications such as waterborne
UFR coil and metal decorating, where superior per-
Ciba-Geigy Switzerland Cibamine formance is required. Conventional low-solids
Reichhold Switzerland Super Beckamine,
Beckamine
butylated amino resins are still the most impor-
BIP UK Beetle tant products of the industry in these countries.
Monsanto UK Resimene
Toxicology and Occupational Health.
Most of the toxicologial and occupational prob-
lems in handling alkylated MF, UF, and BF
64 Paints and Coatings

resins are caused by formaldehyde release dur- 2.13.1. Resols

ing application and cure [177]. Additionally,
some release of formaldehyde can take place Resols are phenolic aldehyde resins that undergo
from cured objects. self-cross-linking catalyzed with bases or ba-
The amount of formaldehyde released dur- sic salts. Their structure depends on the choice
ing the application process is related to the free and molar ratios of the raw materials (e.g., phe-
formaldehyde content in the coating formula- nols and cresols), the solvents, and the type and
tion. Loss of formaldehyde from hydroxymethyl amount of catalyst used. Resols have free hy-
groups during storage can raise the free formal- droxymethyl groups which can react on heating
dehyde content of a coating formulation. to form homocondensates. Heterocondensation
The release of formaldehyde during the cur- with other reaction partners is also possible.
ing process is predominantly the result of dehy- Phenolic resins are generally pale yellow to
droxymethylation reactions. Some of the hy- dark brown in color, occasionally of high inten-
droxymethyl groups are formed during the cur- sity. In special cases intensely colored resols are
ing process by hydrolysis of alkoxy groups from used as coloring resins to produce defined shades
moisture in the air. For example, HMMM re- in coatings (gold lacquers). The products are
leases about 0.5–0.8 mol of formaldehyde dur- available in solid (solvent-free) and dissolved
ing the cure process at normal humidity levels. form. The choice of solvents is governed by the
High-imino melamine resins exhibit lower emis- intended application; resols are generally dis-
sions of formaldehyde during cure. Formalde- solved in alcohols, glycol ethers, aromatic com-
hyde release during cure can be almost elimi- pounds, or mixtures thereof.
nated with glycoluril–formaldehyde resin [168]. Resols used for coatings generally have a rel-
atively low melting point (ca. 50 ◦ C), with the
result that solid resins may sinter at high ambient
2.13. Phenolic Resins for Coatings temperatures (ca. 30 ◦ C).
[178–180] Resols suitable for use in paints generally
cannot be used as the sole binder because they
Phenolic resins (i.e., condensation products of produce very hard, brittle paint films after stov-
phenols and formaldehyde, → Phenolic Resins) ing. They must therefore be combined with
are among the oldest synthetic binders, and their other paint raw materials [e.g., epoxy resins,
first use in paint technology dates back to the poly(vinyl butyrals)].
early 1920s. Their primary uses have constantly
changed since then, and new classes of synthetic Resols as Sole Binders. Resols are not nor-
binders have become increasingly important. mally used as the sole binder because of their
Initially, phenolic resins attracted a great deal brittleness. There are cases, however, where
of interest because they appeared to be the first flexibility is not important. Uses of phenolic
synthetic products that could be used as a sub- resins as sole binders are restricted to coating
stitute for natural resins (rosin, copal resins, rigid constructions (e.g., pipelines and reaction
shellac). Nowadays attention is mainly focussed vessels). Several coats are often applied to ob-
on performance and technical-economic com- tain the desired layer thicknesses. The first coats
petition between the widely differing groups of are cross-linked at relatively low temperature
resins. (ca. 170 ◦ C) to prevent stress formation within
The main disadvantage of phenolic resins is the film. The overall film structure only under-
their intrinsic yellow to brown color. As a result goes complete cross-linking when stoving the
they cannot be used for colored and white paints. last layer. Relatively high stoving temperatures
They can only be used for decorative coatings in up to 220 ◦ C are required for optimum cross-
a few cases (e.g., gold lacquers). Phenolic resins linking.
have favorable mechanical properties and a high Resols used alone as thermohardening;
chemical resistance. Paint systems that are opti- binders produce coatings with outstanding resis-
mally adjusted to the requirement profile can be tance to chemicals and solvents. Cross-linking
developed by suitable formulations.
 Paints and Coatings 65

takes place primarily via the free hydroxymeth- value (governed by the method of application)
yl groups of the resols. The disadvantage of the with suitable solvents. The paints are generally
low flexibility of these coatings has to be borne provided with flow-improving additives (e.g.,
in mind. melamine resins) and lubricants (e.g., waxes).
Typical application methods for this area of use
Coatings for Sheet-Metal Cans and Con- include roller coating (normal coating, reverse
tainers. By far the most important area of use is roller coating), coil coating, and spray coat-
the coating of sheet-metal containers and cans ing. In order to obtain the required cross-linking
for the storage and preservation of food and densities, the resol–epoxy resin paints must be
other products. Thin sheets of galvanized steel stoved at relatively high temperature, normally
(tin plate), nickel-plated steel (tin-free steel), or > 180 ◦ C. Production demands very short stov-
aluminum alloys are generally used as substrate. ing times, a typical time being 12 min at 200 ◦ C.
Untreated steel sheet may, however, also be used The general trend toward shorter production
(e.g., to produce containers and drums for chem- times and rationalization of the production pro-
icals) and are usually coated with nonpigmented cess is reflected in the “shock drying process”,
paint systems (varnishes). in which the paints are cured within a few sec-
In many cases the metal sheets must be coated onds at up to 300 ◦ C. The thickness of the stoved
before they are formed into containers. This de- film is normally only 2–10 µm; optimum flow
mands extremely high flexibility of the cross- behavior is therefore a prerequisite for a satis-
linked paint system. However, the coating mate- factory pinhole-free film.
rial must also be extremely resistant to the con- Catalysts are used to accelerate hardening
tainer contents, must not discolor, and must, at phosphoric acid and organic phosphates are gen-
least in the food-packaging sector, satisfy rel- erally used in practice. These compounds also
evant legal provisions (Bundesgesundheitsamt improve adhesion of the resol–epoxy resin to
in, FDA in the United States). Depending on the metallic substrate.
the raw material, most as-supplied resols con- Resol–epoxy resin mixtures can also be pre-
tain relatively large amounts of toxic substances condensed by refluxing the prediluted compo-
(phenols, formaldehyde, etc.). They must there- nents under an inert atmosphere for several hours
fore be properly labeled, stored, and handled. As at ca. 100 ◦ C. Although a substantial increase
a result of improvements in production methods in the mean molecular mass is not normally ob-
and the choice of suitable raw materials, usable served, mixtures pretreated in this way exhibit
resols with greatly reduced levels of toxic sub- considerably better flow properties; the suscep-
stance have been developed and made available tibility to external flow interference (craters) is
to the paint industry. also reduced.
Resols are of limited use as sole binders on Waterborne systems based on resol–epoxy
account of their brittleness; they are generally resin precondensates are already at an advanced
used in combination with plasticizing co-resins. development stage. Carboxyl groups are in-
Combinations with Epoxy Resins. When troduced into the preformed resols and made
resols are cross-linked with epoxy resins, the water soluble by salt formation with amines.
latter serve as plasticizing components. The hy- These systems offer a significant saving in sol-
droxymethyl groups of the resols are assumed vent compared with that of conventional high-
to react with the hydroxyl groups of the epoxy solvent, high-viscosity products.
resins to produce flexible coatings. Combinations with Poly(Vinyl Butyrals).
Epoxy resins with an epoxy equivalent Poly(vinyl butyral) resins with a high acetal con-
weight of > 1500, a relatively high molecular tent are used, like epoxy resins, to plasticize
mass (ca. 8000), and a high glass transition tem- resols. The weight ratio of resols to poly(vinyl
perature (ca. 75 ◦ C) are generally employed. butyrals) is generally between 95:5 and 70: 30.
Depending on the required flexibility and resis- The employed application methods and curing
tance properties, the resol–epoxy resin mixing conditions are similar to those used in the resol–
ratio is generally between 15 : 85 and 40 : 60 epoxy resin systems. The resistance of such
(relative to weight of solid resin). The viscos- paint films to organic solvents, amines, and other
ity of the mixture is adjusted to the required chemicals are better than that of the correspond-
66 Paints and Coatings

ing combinations with epoxy resins. In contrast 2.13.2. Novolacs

to the latter, resol–poly(vinyl butyral) combina-
tions are often used as pigmented paints, but If phenols and formaldehyde are reacted in the
heat-resistant inert pigments have to be used. presence of acid catalysts, condensation prod-
Certain shades (e.g., gold lacquers) can often ucts are obtained that do not contain reactive
be obtained more satisfactorily with such com- groups. These products can therefore neither re-
binations on account of the darker intrinsic color act with themselves nor with other compounds
produced on stoving. and are termed novolacs.
Novolacs are solid at normal temperature and
Priming Coats. Resols in combination with generally have a well-defined melting point. The
poly(vinyl butyral) are used for acid-catalyzed largely inert behavior of novolacs means that
priming coats that are cured at room tem- they can only be used for physically drying
perature. These systems produce rapidly dry- paints and coatings. They are extremely solu-
ing corrosion-resistant priming coats for metal- ble in polar solvents such as alcohols, ketones,
lic substrates. The mixing ratio of resol to and esters, but are insoluble in aromatic and
poly(vinyl butyral) is generally 25:75 to 50:50. aliphatic hydrocarbons (e.g., xylene, benzene).
These priming coats (shop primers or wash “Spirit varnishes” are novolacs dissolved in al-
primers) serve as a temporary corrosion pro- cohol that are primarily used as unpigmented
tection in steel construction work. They also varnishes; they have an intrinsic yellow color.
form an excellent adhesive layer for subsequent Their main uses include furniture polishes and
topcoats on substrates that are otherwise dif- rapidly drying coatings (e.g., for wood and toys)
ficult to coat (e.g., aluminum or galvanized in industrial and consumer sectors. Novolacs
steel). A major use is therefore as a prim- have a high dilectric constant which means that
ing coat for rust protection in ships. Phospho- they can also be used as electrical insulation
ric acid is the preferred catalyst and, depend- paints.
ing on the amount used, this coating is formu- The paint solutions dry rapidly and produce
lated as one-pack (acid and paint are premixed) hard coatings that are largely resistant to water
or two-pack (acid and paint are supplied sepa- and hydrocarbons. Novolacs are readily compat-
rately) systems. Corrosion-protection pigments ible with many other binder classes. Addition of
are also employed; for ecological reasons zinc small amounts of alkyd resins or poly(vinyl bu-
phosphates have replaced the previously used tyral) resins improves the flexibility of the coat-
chromate-containing pigments. Highly volatile ings.
alcohols with small amounts of aromatic hydro- Compared with phenolic resol resins, no-
carbons as diluents are used as solvents. volacs are of only minor importance as paint
binders. Novolacs are, however, still very impor-
Electrical Insulation Paints. Resols com- tant as binders for basic dyes in printing inks.
bined with poly(vinyl butyral), oil-free polyester
resins, or poly(vinyl formal) as plasticizing com- Commercial products include Alnovol
ponents are used for this special application. The (Hoechst); Bakelite (Bakelite); Schenectady
presence of small amounts of free phenols can (Schenectady Chemicals).
increase the reactivity of these systems. These
paints are used to coat wires, sheet metal for
transformers and dynamos, as well as to im- 2.13.3. Modified Phenolic Resins
pregnate electric motor windings. The paints are
cross-linked at 100–300 ◦ C. Modified phenolic resins are condensation prod-
ucts of the resol type which contain other start-
Commercial products include Bakelite ing materials besides phenol and formaldehyde
(Bakelite); Phenodur (Hoechst); Schenec- (e.g., acrylic monomers). The phenolic compo-
tady (Schenectady Chemicals); Uravar (DSM nent itself is often modified (alkyl- or arylphe-
Resins); Varcum (Reichhold Chemicals). nols). Modification with rosin is the most im-
portant. The compatibility of phenolic resins
with other binders can be substantially improved
 Paints and Coatings 67

by modification. Rosin-modified phenolic resins Combination of gilsonite with drying veg-

may be combined with linseed oils and alkyd etable oils (e.g., linseed or tung oil) produces
resins. Examples of use include putties, priming high-grade asphalt combination paints, espe-
coats, rust protection paints, and colored top- cially if the two binder components are heated
coats. (cooked) together.
Only a limited amount of resin can be added Asphalt and asphalt combination paints are
to white paints due to its intrinsic color. Addition produced and applied only in dissolved form.
of these hard resins increases the hardness and Aromatic and aliphatic hydrocarbons of the nor-
the gloss of the paint films; accelerates and im- mal boiling point range as common in the paint
proves the drying of oxidatively cross-linking industry are suitable as solvents [e.g., mineral
alkyd resins; and optimizes sanding properties spirit (bp 140–200 ◦ C), light solvent naphtha
and corrosion protection in putties. Modified (bp 155–180 ◦ C)]. Unfilled (unextended) as-
phenolic resins have lost much of their im- phalt or asphalt combination paints are rarely
portance because they have been replaced by used nowadays.
more efficient binder systems (e.g., thermoplas- Finely ground minerals such as talc (10 –
tic cross-linkable acrylic resins, polyurethane 20 wt %) and mica, or aluminum powder (1 –
systems). Rosin-modified phenolic resins are, 5 wt %) are usually incorporated into the asphalt
however, still extremely important in the pro- to improve its film properties, in particular its
duction of printing inks. mechanical, weather, and aging resistance. Anti-
settling agents such as montmorillonite–bentone
Commercial products include Alresen, (0.5–1.5 wt %) also have to be used.
Durophen (Hoechst); Bakelite (Bakelite); Sch- On account of the relatively low inherent
enectady (Schenectady Chemicals); and Super color of gilsonite, asphalt-based paints can be
Beckacite (Reichhold Chemicals). colored with inorganic pigments (e.g., iron ox-
ide, chromium oxide, or aluminum).

2.14. Asphalt, Bitumen, and Pitch Properties and Uses. Asphalt paints have
Coatings [181–184] good resistance to weathering, temperature fluc-
tuation, condensation, aging, and also have good
For a detailed description of asphalt and bitu- anticorrosion properties. They adhere well to
men, see → Asphalt and Bitumen. Pitch is de- metallic substrates, asphalt, and roofing felt.
scribed in → Tar and Pitch. Asphalt paints, particularly those based on
combinations of gilsonite with drying oils, are
used to protect exposed steel structures (e.g.,
2.14.1. Asphalt and Asphalt Combination bridges, lattice towers, penstocks) and are rec-
Coatings ommended for these purposes in DIN 55 928.
Since they are also heat resistant, paints of this
Composition. Only natural asphalts with type are used for protection against corrosion in
small amounts of mineral constituents (as- coking plants and blast furnace plants, as well
phaltites) can be used to produce paints. Of as to protect the reinforcement bars in aerated
the asphaltites, only gilsonite with its mod- concrete. Soft-formulated asphalt paints can be
erately high softening point, particularly low obtained by blending with mineral oils, soft bi-
mineral content (< 1 %), and high solubility tumens, or drying (fatty) oils. These are used to
in hydrocarbons is suitable. This natural prod- protect and seal roofs.
uct is a black, resinous, thermoplastic material
with a relatively high molecular mass; it does
not contain any carcinogenic constituents. Since 2.14.2. Bitumen Coatings
gilsonite is very hard and brittle, it cannot be
used as the sole film-forming substance and must Composition. Bitumen paints contain bitu-
be combined with resins and/or plasticizers. It minous substances as binders. Bitumen is de-
can also be plasticized with softer bitumen or fined in DIN 55 946 as “a low-volatile, darkly-
mineral oils. colored mixture of organic substances obtained
68 Paints and Coatings

in the processing of mineral oils and petroleum, Petroleum fractions and aromatic hydrocar-
whose viscoelastic behavior changes with tem- bons with a boiling point range between ca.
perature. The typical properties of bitumen can 130 and 200 ◦ C are suitable solvents for bitu-
be attributed to a colloidal system in which men solutions. Benzines (mineral spirit) are pre-
the disperse phase (asphaltenes) is stably dis- ferred on account of their less obtrusive smell
tributed in a coherent phase of high-boiling oils and the fact that they are more environmen-
(maltenes).” tally friendly. Use of chlorinated hydrocarbons
Bitumens are thermoplastic, weather resis- should be avoided on account of their toxic prop-
tant, water resistant, absorb very little water, do erties.
not release any toxic substances in water, and Waterborne bitumens may be anionic,
are soluble in hydrocarbons. cationic, or nonionic emulsions, and are pro-
Depending on the application, relatively hard duced with the aid of emulsifiers and, if neces-
distillation bitumen, oxidation bitumen, or high- sary, stabilizers conventionally used in the paint
vacuum bitumen (hard bitumen) are used for industry. The properties of bitumen paint (solu-
physically drying bitumen paints. Waterborne tions and emulsions) (e.g., stability; mechanical,
bitumen paints (bitumen emulsions) are pro- weather, water, and chemical resistance; corro-
duced from moderately hard distillation bitu- sion protection properties) can be substantially
men. improved by incorporating extenders. Suitable
The properties of various types of bitumen extenders include ground slate, ground lime-
should be taken into account when selecting the stone, chalk, talc, and mica (25–45 wt %, de-
most suitable bitumen for a particular applica- pending on extender type and required proper-
tion. Oxidation bitumens have the widest range ties). The use of extenders requires the addition
between the temperature at which they become of antisettling agents. Long-term weather resis-
brittle (fracture point, << 0 ◦ C) and the soft- tance can be considerably improved by incorpo-
ening point. Their plasticity range is between 90 rating soot.
and 130 ◦ C. The relatively hard distillation bitu- Bitumen paints can only be colored to a slight
mens have plasticity ranges of ca. 60–70 ◦ C with extent (e.g., with iron oxide or aluminum pow-
fracture points around 0 ◦ C. The high-vacuum der) on account of their intrinsic color.
bitumens have plasticity ranges of ca. 80 ◦ C
with fracture points above 0 ◦ C. Distillation bi- Properties and Uses. Thoroughly dried
tumens and high-vacuum bitumens (hard bitu- films of bitumen paints are resistant to wa-
mens) are substantially more extensible in the ter, salt solutions, dilute acids, and alkalis. Ex-
plasticity range than oxidation bitumens. tended paints are weather resistant. On account
The distillation and high-vacuum bitumens of the thermoplasticity of bitumen, resistance
have a comparatively limited plasticity range decreases with increasing temperature. Bitumen
and higher fracture point in comparison with the paints are not resistant to organic solvents, fuels,
oxidation bitumens but this is compensated for oils, and greases. Optimally formulated bitumen
by the following advantages. Distillation bitu- paints are nontoxic and may therefore be used
mens and high-vacuum bitumens require less to protect surfaces that come into contact with
solvent (less environmental contamination) to drinking water.
obtain the same paint viscosity and equal hard- On account of their favorable properties and
ness. Their solutions are stable (long shelf life), comparatively low price, bitumen paints have
whereas solutions of oxidation bitumens tend been used to protect concrete structures (founda-
to thicken (gel). Solutions of distillation bitu- tions, bridge abutments), felt roofs, sheet-metal
men and high-vacuum bitumen penetrate porous roofs, drinking water reservoirs, silos, pipes
substrates more readily. After drying, they ad- made from fiber-reinforced cement, concrete,
here better to a wide range of substrates. Their steel and cast iron, and in vehicle construction
weather resistance is better and they absorb less (wagon underframes, car underfloor protection).
water. Since they are more stable to UV radia- Unextended as well as extended bitumen paints
tion than oxidation bitumens, they have a better are listed in DIN 55 928.
aging resistance.
 Paints and Coatings 69

2.14.3. Bitumen Combination Coatings Nevertheless, pitches and pitch-based paints

should not come into contact, even in the com-
The properties of bitumen paints (Section pletely dried state, with drinking water, foods,
2.14.2) can be favorably modified and adjusted or fodder. Pitches with softening points of 50 –
to suit practical requirements by combination 100 ◦ C are normally used for producing solvent-
with other film-forming substances. For exam- containing pitch paints. The content of sparingly
ple, the thermoplasticity can be reduced and/or soluble, high molecular mass constituents (free
mechanical properties (e.g., hardness, extensi- carbon) should be as low as possible to obtain
bility) can be improved by adding polymers such solutions that are free of precipitates.
as polyethylene, polypropylene, polyisobutene, For waterborne coating materials based on
and styrene–butadiene copolymers. The chemi- pitch (DIN 55 946, Part 2, pitch emulsions or
cal resistance can also be improved; high-quality suspensions), the softening point of the pitch
corrosion protection coatings can be obtained by must be below 60 ◦ C. High-boiling coal tar dis-
combination with alkyd resins. tillates, mineral oil extracts rich in aromatics,
Bitumen is permanently compatible with or plasticizing compounds normally used in the
only a few polymers and only when the latter are paint industry (e.g., benzyl phthalate) may be
added in small amounts. Compatibility depends used as plasticizers for hard pitches. Aromatics
largely on the nature and origin of the bitumen. boiling below 200 ◦ C (e.g., xylene, Shellsol) are
Combinations of bitumen with reaction- suitable as solvents. Petroleum spirits as well as
curing paint binders (e.g., epoxy resins and most conventional paint solvents are unsuitable
polyurethanes) are not usually employed in as solvents because they cause precipitation of
solvent-based paints due to their unsatisfactory the relatively sparingly soluble pitches and thus
compatibility. Only with high epoxy resin con- result in segregation. Waterborne pitch-based
tents can a certain compatibility be achieved by paints can be produced using special emulsifiers
addition of solubilizing phenols and aromatic (e.g., bentonite).
oils. Properties such as stability, mechanical and
aging resistance of pitch paints can be improved
by incorporating extenders as are used for bitu-
2.14.4. Pitch Coatings men paints (see Section 2.14.2).
The tar crazing (alligatoring) that occurs dur-
Composition. Special coal tar pitches are ing weathering of nonextended or unsatisfacto-
mainly used to produce one-pack, physically rily extended pitch paints can be prevented by the
drying pitch paints. According to DIN 55 946, optimum use of fillers. On account of the very
these are coal tar pitches whose “physical and dark color of pitch, it is virtually impossible to
chemical properties have been modified by spe- color pitch paints.
cial processes (e.g., polymerization)”. Nonmod-
ified coal tar pitches are no longer used. Other Properties and Uses. Nonextended and ex-
pitches obtained from tar residues occurring in tended solventborne pitch paints can penetrate
various processes (e.g., thermal treatment of py- porous substrates very well and have excellent
rolytic oils, distillation of peat or lignite) are also weather resistance. These paints and the water-
used in pitch paints. borne pitch emulsions provide good corrosion
Both types of pitch consist mainly of polynu- protection properties and are resistant to water,
clear aromatic hydrocarbons. The pitches and salt solutions, dilute acids, alkalis, and micro-
pitch products used in the production of pitch biological degradation. They have only limited
paints are classified as carcinogenic materi- resistance to mineral oils, fuels, and greases. On
als (especially because of their benzo[a]pyrene account of the pronounced thermoplasticity of
content). Relevant regulations should therefore pitch (plasticity range 40–50 ◦ C), the resistance
be observed in their production and use. It of pitch paints decreases significantly with in-
has, however, become possible to reduce the creasing temperature.
benzo[a]pyrene content of some pitches to such On account of their special properties and low
an extent (<0.005 wt %) that the “carcinogenic” cost, pitch paints have been used to protect con-
warning label is no longer needed. crete structures against chemically aggressive
70 Paints and Coatings

water (including effluent and wastewater) and In the cured state, solid epoxy resins (e.g.,
for corrosion protection of steel constructions in bisphenol A resins and polyaminoamides) are
industry, hydraulic steel structures, and under- incompatible with the pitch or “tar”, and
ground pipelines made of steel, cast iron, con- thus produce inhomogeneous films. Mixtures
crete, and fiber-reinforced cement. Pitch paints of pitch-, “tar”-, and anthracene-oil-containing
must not be used on objects that come into con- film-forming substances with epoxy resins and
tact with drinking water, food, and fodder. Both polyisocyanates suffer from limited shelf life be-
nonextended and extended pitch paints are listed cause their constituents react with one another.
in DIN 55 928. This increases viscosity and adversely affects
film curing.
In combinations with epoxy resins, two-pack
2.14.5. Pitch Combination Coatings systems are used: one component contains the
pitch-, “tar”-, or anthracene-oil-containing frac-
Composition. Pitch paints can be combined tion and the curing agent (e.g., polyamine), and
with thermoplastic polymers as well as with the other component contains the epoxy resin.
reaction-curing resins in order to improve their In combinations with polyurethanes, one com-
properties. Pitch paints are mixed with thermo- ponent contains the tar-derived fraction and the
plastic polymers such as poly(vinyl chloride), polyol, while the other component contains the
chlorinated rubber, polychloroprene, polyacry- polyisocyanate.
lonitrile, or polystyrene. The polymer content
is generally low (ca. 4–8 wt %) on account of Properties and Uses. Pitch paints modified
the limited compatibility and the impairment of with thermoplastic polymers have better ther-
paint application properties. Polymer addition mal properties in the dry state (cold and hot be-
reduces the marked thermoplasticity of pitches havior) than conventional pitch paints (Section
in one-pack, physically drying pitch combina- 2.14.4). They also have better cohesion, greater
tion paints. Mechanical properties (e.g., hard- extensibility, and increased chemical resistance.
ness, extensibility, resistance to mineral oils, and On account of these properties, their good wa-
aging resistance) can also be improved. ter resistance, and comparatively low cost these
Extended combinations of pitch paints pitch paint combinations are used to protect con-
(pitch + solvent), “tars” (pitch + high-boiling struction works especially in the sewerage and
tar oils), and anthracene oil (high-boiling tar effluent sector.
oils) with reaction-curing resins (e.g., epoxy Optimally formulated combinations with
resins and polyurethanes) have become ex- reaction-curing resins have excellent water and
tremely important. Combinations not classi- weather resistance as well as a very good per-
fied as carcinogenic can be obtained by using manent resistance to acids, alkalis, mineral oils,
pitches, “tars”, or anthracene oils with very low fuels, and detergents. When cured they are no
benzo[a]pyrene contents. longer thermoplastic and are therefore resistant
Combinations with reaction-curing resins are to heat and hot water, as well as being very abra-
mainly supplied as two-pack paints, whose com- sion resistant.
ponents are mixed together shortly before ap- On account of their outstanding properties
plication. In combinations with polyurethanes, and relatively low cost, such combinations are
one-pack paints that cure by reaction with at- widely used in the following areas: in hydraulic
mospheric moisture are also feasible. steel structures (hydro dams, lock gates, sheet
Low-solvent and solvent-free paints can be pile boards); shipbuilding and harbor construc-
formulated by using liquid film-forming sub- tion (ships’ hulls, quay installations); sewerage
stances (liquid “tars” or anthracene oils, liq- sector (sewers, wastewater treatment plants);
uid resins and curing agents). Very thick coat- and pipeline construction (penstocks). They are
ings [ca. 1 mm dft (dry film thickness) per coat] listed in DIN 55 928.
can be produced with epoxy resin combinations. Due to their smell and taste, all tar combina-
Others can also be applied to moist substrates tion paints are unsuitable for residential build-
and cure under water. ings, stables, and surfaces that come into contact
with drinking water, food, or fodder.
 Paints and Coatings 71

Commercial products include Eurolan

(Deitermann); Inertol (Sika Chemie); and
Prodorit (T.I.B.)
The silica gel and metasilicate gel formed in
2.15. Silicate Coatings these complex reactions contain a large amount
of water, and are then converted into solid, amor-
2.15.1. Water Glass Coatings phous silicate structures with only a low resid-
ual water content by evaporation of water [188].
The expression water glass paints is understood
Extremely finely divided potassium carbonate
to mean coating systems based on the binder
is formed as a hygroscopic byproduct which oc-
water glass (potassium, sodium, or occasionally,
curs as a transparent layer that is slowly dis-
lithium water glass). The general expression sil-
solved by moisture. The sodium carbonate pro-
icate coatings has been adopted for these sys-
duced with sodium water glass leads to the for-
tems and is therefore used throughout Section
mation of saltlike efflorescences. Potassium wa-
2.15.1. For a detailed description of water glass,
ter glass is therefore mainly used for coatings.
see → Silicates.
Coatings formed from silicate paints differ
History. The history of silicate paints be-
from organic coating systems. Chemical bonds
gan with the rediscovery of potassium and
are formed by silicification in the paint layer and
sodium water glass by J. N. von Fuchs around
with the mineral substrate, and adhesion is there-
1818 [185]. The use of these compounds as a
fore not purely physical. The paint layer has a
flame retardant coating was first described in
silicate structure and is thus relatively perme-
1823 [186]. Fuchs, J. Schlotthauer, and W. V.
able with a high degree of hardness. Evaporation
Kaulbach subsequently developed the “stere-
of moisture is not hindered, peeling and flaking
ochromy” process, a new painting technique
are therefore avoided. Since silicate paint layers
in which water glass replaced the previously
have a high gas permeability they do not disturb
used binders lime and casein for mural paint-
the equilibrium with atmospheric carbon diox-
ing. A further significant development was made
ide when applied to a lime plaster or mortar.
by A. W. Keim in 1878 [187], who created the
Since the paint layer and the mineral substrate
two-component technique, still used nowadays,
have a chemically similar structure they both ex-
involving the binder (fixative) and pigments.
hibit the same expansion behavior under the ac-
The modern one-component dispersion silicate
tion of heat and cold; thermal stress between the
paints were developed and introduced to the
paint and substrate is therefore minimized.
market in 1967 (Silin silicate paint, van Baerle
The good resistance of silicate paints to
& Co.; Kieselit, Henkel).
weathering, environmental influences, and tem-
Properties. The special properties of silicate perature is a result of their mineral, chemically
paints are imparted by the binder, generally resistant structure and the almost exclusive use
potassium water glass. The paint coats harden of lightfast inorganic pigments. Silicate paints
physically by evaporation of water, as well as dry to give a matt surface.
chemically by several reactions. These stabi-
lization and consolidation processes are termed Composition, Application, and Uses. Ar-
“silicification” [189]. The water glass reacts as chitectural and exterior coating systems may
follows with atmospheric carbon dioxide: be either one- or two-component (DIN 18 363,
Section 2.4.1). Two-component silicate paints
may consist only of potassium water glass, pig-
ments, and extenders that are resistant to potas-
sium water glass. One-component dispersion
silicate paints may consist of potassium water
Reaction also takes place with the pigments glass, pigments that are resistant to potassium
and extenders of the paint. If the paint is applied
to a mineral substrate, a third reaction occurs,
e.g., with calcium hydroxide:
72 Paints and Coatings

water glass, hydrophobing (waterproofing) ad- rosion protection (see Section 11.1) and flame
ditives, and no more than 5 wt % of organic con- retardant coatings on wood [194, 195].
stituents, relative to the total amount of the coat-
ing material. This total amount is measured by Commercial Products. Commercial one-
the ignition loss (Technischer Arbeitskreis Dis- component products include Calsilit (Kabe Karl
persionsfarben, TAKD, resolution, Feb. 1984) Bubenhofer); Caparol–Sylitol (Deutsche Am-
[190]. phibolin Werke); Color-Silikatfarbe (Sikkens);
In two-component silicate paints, the potas- Granital/Biosil (Keim Farben); Kieselit
sium water glass binder (fixative) and the pow- (Henkel); and Silin (van Baerle). Two-
dered pigments, extenders, and auxiliaries are component products include Purkristallat (Keim
mixed (kneaded) in a 1: 1 ratio by the user and Farben) and Silin (van Baerle).
homogenized after a few hours. The end prod-
uct and reproducibility depend on the knead-
ing time, degree of homogenization, temper- 2.15.2. Alkyl Silicates [196]
ature, and metering accuracy. On account of
the high reactivity the paint should be applied Alkyl silicates may be regarded as esters of the
within a few days of preparation. In contrast, hypothetical silicic acid, which may exist in
one-component silicate paints are formulated monomeric or oligomeric form. They are also
ready for application in the paint factory [191, referred to as silicate esters or alkoxysilanes. See
192]. Depending on the paint manufacturer, wa- also → Silicon Compounds, Organic.
ter or a water–primer (fixative) mixture may Hydrolysis of alkyl silicates produces silicic
be added by the user to optimize adaptation acids with varying degrees of condensation and
to the substrate. The permissible proportion of ultimately silicon dioxide. The reaction time in-
up to 5 wt % of organic constituents does not creases with increasing size of the alkyl group.
affect the advantageous properties of silicate Elevated temperature and high moisture content
paints. Indeed, they stabilize the system and accelerate hydrolysis and condensation.
improve water resistance. Storage stabilities of The resultant silica gel can be used as a binder
more than one year can be obtained and require- for solid particles, i.e., for pigments utilized in
ments with regard to the water uptake coefficient the paint industry. Inorganic coatings with spe-
(DIN 18 558 E) are met [193]. cial properties can be formulated. The silanol
On account of their properties, silicate paints groups formed during hydrolysis make the alkyl
are used as weather-resistant and wash-resistant silicate binders highly reactive in contrast to sil-
coatings on mineral substrates in both exte- ica sols formed from colloidal silicic acid. They
rior and interior applications. Substrates in- differ from water glass paints (Section 2.15.1)
clude lime, lime cement, cement renders (mortar in that alkali is not released during hydrolysis.
groups I, II, and III), concrete, sandy limestone, The properties of the hardened film (high sur-
as well as old silicate or mineral coatings. Old face hardness, temperature resistance, and elec-
lime coats should be removed completely, and trical conductivity) account for their main use as
gypsum substrates should be treated only after binders for corrosion protection coatings con-
special priming. A special water glass priming taining zinc dust (see Section 11.1). Depend-
coat and one or two topcoats are required, de- ing on the temperature sensitivity of the pig-
pending on the substrate. On account of their ment used, they can withstand temperatures up
silicate nature and the fact that they have the to 1000 ◦ C. The absence of organic polymers
same color effect as historical lime paints, sili- makes the paints extremely resistant to organic
cate paints are also used for restoring and main- solvents, and the high degree of hardness confers
taining historical monuments. Their high light- excellent abrasion resistance.
fastness, weather resistance, and water vapor
permeability reduce the danger of coating dam- Composition and Properties. The binders
age even in structures and buildings that do not are produced from orthosilicate esters Si(OR)4
have adequate transverse insulation. Further spe- or industrial mixtures of polysilicate esters. Al-
cial uses of silicate coating systems include cor- though the methyl esters are readily hydrolyzed
and have a very high silicon content (generally
 Paints and Coatings 73

given as SiO2 content), the ethyl esters are nor- value or evaporating the solvent), condensation
mally used for physiological and toxicological commences and the solution solidifies after a
reasons. The less readily hydrolyzable esters of short time. This mechanism is used in two-pack
longer-chain alcohols are employed in special zinc dust paints. In the simplest case the binder
applications. is a hydrolyzate in alcoholic solution. Zinc dust
Various polymeric silica distributions are ob- and, if necessary, extenders, antisettling agents,
tained depending on the production process. colorants, etc. are then added. Addition of zinc
Although this distribution may possibly affect consumes acid and the pH value increases.
hardening behavior, investigations have shown
that this is insignificant in practical applications. Zn+2 HCL→ZnCl2 +H2
The use of alkyl silicates in coatings is based Condensation therefore commences and the
on the following reaction: mixture becomes solid.
Si(OR)4 +2 H2 O→SiO2 +4 ROH where R = alkyl
On application, the paint layer hardens within
a short time due to evaporation of the solvent,
This overall equation can be subdivided into two progressive hydrolysis of ester groups after up-
steps: hydrolysis take of atmospheric moisture, reaction of silanol
groups with the zinc and substrate, and conden-
Si(OR)4 +4 H2 O→Si(OH)4 +4 ROH sation of silanol groups to form sparingly sol-
and condensation uble, cross-linked silica gel [199]. Conditions
are generally chosen such that the film is hard
Si(OH)4 →SiO2 +2 H2 O enough to allow transportation after 4 h and a
topcoat after 24 h. Alkyl silicate zinc dust paints
Both reactions occur in parallel, but their rates
are particularly suitable for applications involv-
can be independently influenced. Condensation
ing high atmospheric humidity and high temper-
can be suppressed by lowering the pH value
ature because these conditions promote harden-
to obtain hydrolyzates that remain stable for
ing. This explains their widespread use for cor-
relatively long periods (6–12 months) without
rosion protection in maritime tropical regions.
gelling.
It has been suggested that this occurs because Historical Development. The importance
protons associate with the silanols which then and advantages of ethyl silicate zinc dust paints
repel one another on account of their positive were recognized and intensively investigated in
charge and thereby oppose condensation. If the the late 1940s [200, 201]. The fundamental work
pH value is raised, these charges are dissipated of Lopata and Keithler [202] on the partial acid
and the silanols can condense [197]. hydrolysis of tetraethyl orthosilicate and the use
The gelling time depends on a range of pa- of the product as a zinc dust paint binder was
rameters [198], the most important being the followed by attempts to improve the application
SiO2 concentration, the degree of hydrolysis, the properties and quality of the coatings (e.g., by
type of solvent, and storage temperature. (The adding poly(vinyl butyral) [203], alkyl titanates
degree of hydrolysis is the degree of conversion, [204], borate esters [205], or trialkyl phosphates
complete conversion to SiO2 and ethanol corre- [206].
sponding to 100 % hydrolysis.) Ethyl silicate was transesterified with higher
In practice the ester is mixed with the required alcohols to produce binders with a higher flash
amount of water and a suitable solvent (e.g., al- point [207, 208].
cohols, esters, ketones). To obtain 100 % hydro- In addition to the general disadvantages as-
lysis of 1 mol of an orthosilicate, 2 mol of wa- sociated with a two-pack system, ethyl silicate
ter must be added. By maintaining a constant hydrolyzate also ages. The condensation reac-
pH (for ethyl silicate ca. 2) the condensation re- tion is merely slowed down and not stopped. As
action can be suppressed to such an extent that a result application properties such as viscosity
hydrolyzates of ethyl silicate containing 20 % and reactivity (and thus the hardening rate), al-
SiO2 and with a degree of hydrolysis of 80– ter during storage. The use of binders of varying
90 % remain stable for about one year. If this ages can lead to considerable practical difficul-
equilibrium is disturbed (e.g., by shifting the pH ties.
74 Paints and Coatings

Continuous efforts have therefore been made The solvents, dilute hydrochloric acid, and
to develop binders for one-pack paints which ethyl silicate are mixed and stirred and the tem-
must be completely compatible with active pig- perature rises; an upper limit of 25–30 ◦ C is of-
ments such as zinc dust. Mixtures of ethyl sili- ten recommended. The second component of the
cate and zinc can be stored for unlimited periods two-pack paint is the pigment–extender mixture.
in the absence of water. If the hydrolysis and The binder can be used after 1–3 d; the storage
condensation reactions caused by atmospheric stability is limited and is generally specified by
moisture can be sufficiently accelerated during the manufacturer. In the above example it is ca.
application of the coating, a one-pack system one year.
can be produced. Binders with a fairly high flash point require
Use of basic catalysts allows formulation of a suitable solvent (e.g., propanol, butanol) and a
such systems because the reaction mechanism silicate base that cannot release any alcohols of
of hydrolysis and condensation proceeds differ- low flash point during partial hydrolysis (e.g.,
ently in the alkaline range [197]; condensation tetrapropyl or tetrabutyl silicate). The slower
occurs more rapidly. evaporation of such alcohols delays the initial
The pronounced settling behavior due to the hardening of these paints.
high density of zinc and the low viscosity of the The amount of water present determines the
alkyl silicate frequently resulted in solid precipi- possible extent of hydrolysis of the Si−OR
tates and caused problems. Nowadays, however, groups (in the above example ca. 82 %) and thus
one-pack zinc dust paints can be used even after storage stability and reactivity. For example, the
several years because they contain special rheo- addition of ten additional parts by weight of wa-
logical additives (e.g., bentonite, pyrogenic sil- ter would reduce the storage time to < 25 % of
ica). The application properties of these paints the original value. Conversely, a lower amount
are similar to those of paint systems based on of water would give a product with a longer
organic polymer binders. In addition to the gen- storage stability which, however, would react
eral advantages associated with a one-pack sys- more slowly possibly resulting in uneconomi-
tem, these alkyl silicate paints do not exhibit age- cally long drying times. Suitable catalysts in-
dependent changes in their application proper- clude hydrochloric acid, other acids, and salts
ties (e.g., viscosity, brushability, and hardening (e.g., zinc chloride or amine hydrochlorides).
behavior) because the degree of condensation Their concentration determines the rate of the
does not alter. hydrolysis, but also affects properties such as
All binders formed from ethyl silicate have a storage stability of the binder, pot life, and paint
relatively low flash point due to the ethanol re- drying.
leased during hydrolysis (flash point of ethanol The production of binders for one-pack zinc
12 ◦ C). The paint may have a somewhat higher dust paints is simple: alkyl silicate, catalyst, and
flash point (15 ◦ C) because its ethanol content solvent are mixed and diluted to the desired con-
is low. The use of higher alkyl groups yields sys- centration. The resulting mixtures are extremely
tems with higher flash points. sensitive to moisture; even small amounts of wa-
ter in the solvents can lead to gelling. Appro-
Production. On account of the many pos- priate equipment and trained personnel are re-
sible variations in batch formulation and pro- quired to avoid mishaps. Interactions between
duction procedure, only a general outline and the constituents can greatly influence applica-
instructions for producing one- and two-pack tion properties and lead to failure. The choice
binders from ethyl silicate can be given here. of an effective antisettling agent is difficult due
The following batch formulation (in parts by to the large difference between the densities of
weight) is typical for a two-pack binder con- zinc powder and alkyl silicate. Most rheologi-
taining 20 wt % SiO2 : ethyl polysilicate 500, cal additives are ineffective in highly polar alkyl
solvents 440, and 1 % hydrochloric acid 60. Al- silicate solutions.
cohols such as ethanol and 2-propanol, often In order to produce ready-for-use zinc dust
mixed with one another and with ketones, ethers, paint, zinc dust is slowly added to the binder in
and esters, are used as solvents. a ratio of 4–4.5: 1 while stirring. Binder addi-
tives (e.g., antisettling agents such as bentonite,
 Paints and Coatings 75

pyrogenic silica) and zinc dust additives (e.g., The zinc oxidation products form a hard ce-
extenders such as mica, talc, kaolin, or colored mentlike layer in the silicic acid film. Resistance
components such as chromium(III) oxide, tita- to diffusion is increased and attack of atmo-
nium dioxide) can be used to adjust the applica- spheric oxygen on the substrate is thus slowed
tion behavior and properties of the paints. down (barrier protection).
Ethyl silicate binders are mainly used in ap-
Commercial products containing ethyl sil- plications involving high temperatures and cor-
icate binders include Dynasil (Hüls); Ethylsili- rosive influences. The principal application of
cate (Union Carbide); Ethylsilikat (Wacker); Sil- ethyl silicate zinc dust coatings is the protection
bond (Akzo); and Silester (Monsanto). of iron and steel against corrosion; it is effec-
Important manufacturers of ethyl silicate tive even at temperatures of up to 400 ◦ C. Ex-
zinc dust paints include Ameron, Carboline, amples include ships, harbor construction work,
Hempel’s Marine Paints, International Paint, Jo- bridges, steel structures exposed to atmospheres
tun, Mobil Chemical, and Sigma Coatings. in industrial areas, tanks, containers, pipelines,
and chimneys.
Transportation and Storage. Containers Ethyl silicate zinc dust paints are applied by
and drums with a polyethylene insert or re- air or airless spraying, often directly after jet
sistant lining are suitable. The binders should cleaning of the substrate. They are seldom ap-
be stored at as low a temperature as possible plied with a brush or roller. Layer thicknesses
and under absolute exclusion of moisture. The range from 15 to 20 µm (shop primers) through
storage time of two-pack systems varies and 50 to 70 µm (primers) to > 100 µm (single
is specified by the manufacturer. Commercial thick-layer application).
products are stable for about 9 months when The contents of two-pack paints must be con-
stored at 20 ◦ C. stantly stirred after mixing to prevent settling.
The pot lives are ca. 8 h. With one-pack paints,
Properties of the Coatings and Uses. Impu- layer thicknesses of up to 200 µm can be ob-
rities in steel (e.g., carbon) can act as local cells tained in a single application. Pot life is unlim-
and cause corrosion. The iron is first oxidized ited provided moisture is excluded.
to divalent ions. A metal with a lower electrode Silicic acid is not attacked by radiation, and
potential (e.g., zinc) is, however, preferentially silicate esters are therefore particularly suitable
oxidized. The electrons that are thereby released binders for coatings in radiation-hazard areas
counteract oxidation of the iron: such as nuclear power stations.
Ethyl silicate zinc dust paints can be covered
Zn0 →Zn2+ +2 e−
with many conventional topcoat systems [209].
This is necessary in an acid or alkaline environ-
2e− +Fe2+ →Fe0
ment to prevent the zinc from being attacked.
Theoretically, oxidation of iron can only begin Ethyl silicate is also suitable as a binder for inor-
when all the metallic zinc has been oxidized. ganic pigments on account of its UV resistance.
This process can occur only if there is suffi-
cient electrical conductivity (i.e., contact) bet-
ween zinc and iron. Thorough cleaning of the 3. Paint Systems
metallic substrate is therefore important to en-
sure the effectiveness of corrosion protection 3.1. Solventborne Paints
coatings.
On account of their higher electrical conduc- 3.1.1. General Information
tivity, silicate esters have clear advantages over
organic polymers as binders. The resistivity of Paints and coating materials normally consist of
a one-pack silicate ester zinc dust paint is ca. a physical mixture of binders, pigments, exten-
1×106 Ω · cm, i.e., two to three orders of mag- ders, additives, and solvents. Depending on the
nitude lower than that of commercially available method of application and area of use, the solids
purely organic systems with a comparable zinc content may reach 80 wt %, the proportion of
content.
76 Paints and Coatings

pigment may reach 60 % of the solids content. ous (i.e., organic) solvent content of less than
The technologically most important component 30 wt %, whereas the Environmental Protec-
is the binder (or binder mixture). Binders may tion Agency (EPA) in the United States de-
be classified as physically or chemically drying fines “high-solids” paints as having volatile or-
according to their film-forming mechanism. ganic contents of < 2.8 pounds/gallon (336 g/L)
Physically drying paints are solutions of ther- [214]. High-solids paints are described in Sec-
moplastic polymers with molecular masses ex- tion 3.2.
ceeding 20 000; on account of their low solubil- Typical examples of low-solids paints (sol-
ity they have a high solvent content (> 60 %) vent content usually > 60 wt %) are:
and a low solids content. Chemically drying
1) Metallic(-effect) base paints for mass pro-
paints have a fairly low solvent content (30–
duction of automobiles and touch-up finishes
60 %) and a high solids content because the poly-
2) Thermoplastic coatings
mer network is formed by cross-linking of the
3) Coatings for the electronics and optoelec-
binder (M r ca. 800–10 000) to form thermo-
tronics industries
setting coatings. Oxidatively drying paints con-
tain allyl groups and reactive double bonds, and Of these three groups metallic basecoats are
cross-link by absorbing oxygen and forming quantitatively the most important. Technical rea-
ether bridges. sons for the high solvent content of these paint
Normally paints are also classified accord- systems include the need for thin layer thick-
ing to the nature of the principal binder and its nesses (e.g., when applying paint with a spin
associated film properties; e.g., alkyd, acrylic, coater). Secondly, binders such as polyimides
polyester, nitrocellulose, epoxy, and oil-based for electrical insulation coatings and thermo-
paints (see Chap. 2). The method of applica- plastic acrylic resins have low solubilities. Fi-
tion, surface properties, and intended use are nally, in some cases (e.g., in metallic basecoats) a
also utilized for classification [210]. Since the high solvent content is needed to optimize rheo-
beginning of the 1980s environmental require- logical behavior [215]. Rheological factors limit
ments have become increasingly important for the reduction of the solvent content, particularly
two main reasons, especially in the case of paints when coating vertical surfaces. Significant im-
with low material transfer (application) efficien- provements can often only be achieved by re-
cies (see Section 3.1.3): placing organic solvents with water. For exam-
ple, the solventborne metal effect paints used in
1) Avoidance of the use of toxic, carcinogenic,
the automobile industry are increasingly being
mutagenic, or teratogenic organic solvents
replaced by waterborne paint systems with a re-
2) Drastic and in some cases legally imposed re-
duction in the solvent content in the paint to ca.
duction of solvent contents (see also Section
10 % based on 25 % solids [216] (see also Sec-
3.1.3)
tion 3.2).
Legal regulations have resulted in a sharp rise
in the solids content and a reduction in the sol-
vent content of the most important paint sys- 3.1.2. Properties and Raw Materials
tems. Among solventborne paints, high-solids
paints have enjoyed the largest growth rate; Solvents. Organic solvents are used to dis-
in the Federal Republic of Germany produc- solve binders (resins) and additives and to dis-
tion of this type of paint rose by 32 % bet- perse pigments and extenders in order to produce
ween 1988 and 1989, whereas the production ready-for-use paints and coatings. For a detailed
of all solventborne paints increased by only 3 % description, see → Solvents. The dissolution be-
[211]. A sharp drop in high-solvent paints is havior (solvency) and interaction of organic sol-
to be expected in the United States and Eu- vents (e.g., ketones, glycol ethers, glycol ether
rope [212, 213]. The definitions of “low-” and esters, alcohols, esters, hydrocarbons, and ter-
“high-solids” paints differ. For example, the penes) with binders have been investigated in
Verband der Deutschen Lackindustrie (Asso- detail [210]. The objectives of such studies are
ciation of the German Paint Industry) defines the optimum adjustment of processability to ob-
“high-solids” paints as paints with a nonaque- tain the appropriate rheological behavior before
 Paints and Coatings 77

and during application, and the maximization of of cross-linking agents are available for a va-
the binder content in the paint formulation. The riety of applications [220]. They include phe-
legally imposed requirement to employ toxico- nolic resins and amino resins. Isocyanates also
logically harmless solvents for the formulation play an important role as cross-linking agents.
of paints has stimulated the development of com- Hydroxyl-containing binders (e.g., polyester
puter programs for optimizing solvent mixtures resins, acrylic resins) that can be cross-linked
based on less harmful or innocuous solvents. with polyfunctional isocyanates have been in-
This required a detailed knowledge of the in- troduced as two-pack paints, particularly in the
teraction between binders and solvents [217]. automobile and plastics industries [224, 225].
Initial programs for calculating optimum sol- Advantages lie in the good weather resistance of
vent mixtures were developed by taking into the urethane groups, the low curing temperature,
account dispersive interactions (C d ), polar in- and the high gloss level of the coating.
teractions (C p ), and interactions resulting from Clear varnishes used in the automobile in-
hydrogen bond formation (C h ) (solubility pa- dustry have to satisfy particularly stringent re-
rameters) [218, 219]. Solvents were chosen in quirements: high gloss, color durability, and
regard to toxicological factors [220] (see also maintenance-free behavior for more than 5 years
Section 3.1.3). Conventional tests for checking [226]. This is expressed in terms of permanently
solubility are still used. high water contact angles (> 90◦ ) and a high
As well as the solubility, the solvent release gloss after several years’ exposure of the paint
during and after application is another impor- in Florida. New acrylic resins have been devel-
tant criterion for solvent selection. Evaporation oped that are copolymerized to about 50 % with
of the solvent mixture from the film is important fluorine-containing monomers such as chlorotri-
not only for a smooth surface, but also for obtain- fluoroethylene [227]. Acrylic resins produced by
ing optimal, reproducible mechanical properties group transfer polymerization represent a new
of the film. The boiling points or vapor pressures class of resins with a narrow molecular mass dis-
of the solvents do not provide sufficient infor- tribution which is advantageous for dissolution
mation for formulating a paint system [221]. A [228].
model for calculating solvent evaporation also New cross-linking reactions for curing paints
includes transport data of the solvents in the film and coatings have been developed, but their tech-
in the form of diffusion parameters [222]. Evap- nical implementation has not been very success-
oration behavior is also determined experimen- ful. The Michael addition of C−H-azide com-
tally (e.g., according to ASTM D 3539.76). pounds to activated unsaturated double bonds
In solventborne paints, small amounts of the is used for automotive repair and touch-up fin-
organic solvents may remain in the resultant film ishes [229]. Esters activated with alkoxy and
after cross-linking. Solvent retention can reduce amide groups have also been described [230].
internal tension, linear shrinkage behavior, and Epoxy–amine, epoxy–carboxy, and epoxy–an-
the glass transition temperature [223]. hydride reactions are gaining importance in
aliphatic epoxy resin cross-linking agents [231,
Film Properties. Physically drying sol- 232]. However, films produced in this way do
ventborne paints contain cellulose esters, not exhibit any major advantages over those pro-
vinyl resins, thermoplastic acrylic resins, duced from polyurethane resins. Much research
polyurethanes, rubber derivatives, and hydro- and development has been devoted to solvent-
carbon resins as principal binders. Chemically borne paints that produce a multilayer system
drying solventborne paints that undergo oxida- after a single application; this leads to consid-
tive drying are based on alkyd resins, epoxy erable savings in material and time. The phase
esters, modified phenolic resins, and urethane behavior of the binder components and solvents
oils. Cross-linkable paints play the most im- plays an important role in these paint systems
portant role. They contain binders with unsat- [233, 234].
urated components (e.g., unsaturated polyester
resins), ethoxy groups (e.g., epoxy resins), and
hydroxyl groups (e.g., alkyd resins, polyesters,
vinyl resins, and acrylic resins). A wide range
78 Paints and Coatings

3.1.3. Environmental Protection and is of paramount importance in automobile fac-

Application Technology tories [236]. Resins, solvents, additives, cross-
linking agents, and other paint components are
The paint transfer efficiency is defined as the subjected to toxicological tests to determine any
amount of paint on the object expressed as a per- possible health-hazard effects before they are
centage of the amount of paint used for applica- used in commercial formulations.
tion. A low theoretical paint transfer efficiency
means high amounts of solvent emission and
waste generation. Special attention must there- 3.2. Solvent-Free and Low-Solvent
fore be given to environmental aspects when us- (High-Solids) Paints
ing conventional spraying methods for produc-
ing smooth, high-quality surfaces (see Table 7). Solvent-free and low-solvent paints are a de-
velopment of conventional high-solvent paints
Table 7. Comparison of theoretical solvent emission data of
various application methods* and are formulated to comply with increas-
ingly stringent environmental requirements. In
this section only those liquid coating materials
are discussed that can be applied by conven-
tional methods (coating, spraying, rolling, dip-
ping, pouring). Solvent-free paints that are ap-
plied with new technologies and methods are
described in Sections 3.4 (powder coatings)
and 3.7 (radiation-curing systems). Waterborne
paints are discussed in Section 3.3.
Low-solvent paints are commonly referred
to as high-solids paints and are defined as sys-
tems with a solids content exceeding 85 wt %.
In practice, however, paints with a solids con-
tent of 60–80 wt % are also termed high-solids
paints, particularly if the corresponding conven-
tional (high-solvent) system normally contains
< 50 wt % nonvolatile components [237].
Low-solvent paints have existed for a long
time in the form of oil-based paints and var-
nishes (Section 2.1). The more recent devel-
opment of high-solvent paints satisfying strict
quality requirements has largely displaced this
type of coating materials. Extensive develop-
The development of electrostatic spraying
ment of high-solids paints occurred only after
(see Section 8.3.2) has led to a sharp rise in paint
regulations governing solvent emissions and air
yield and material transfer efficiency [235]. The
pollution came into force (“Rule 66” in Califor-
use of high-speed rotating atomizers has also
nia, and TA Luft in the Federal Republic of Ger-
contributed to this and allows a very fine droplet
many). There are several reasons for developing
spectrum to be produced. The droplet mist is di-
solvent-free and low-solvent paints:
rected onto the object by a guiding air jet; with
a favorable charge to mass ratio, a high ma- 1) Reduction of atmospheric pollution
terial transfer efficiency (> 75 %) is obtained. 2) Savings in materials and transportation costs
This high efficiency together with the evapo- 3) Savings in energy costs involved in paint pro-
ration losses of the solvent results in a source duction and use
of emission that has led to the development of 4) Time savings due to higher layer thicknesses
solvent and paint recovery units in plants with per application cycle
a particularly high throughput (e.g., in the au- 5) Improvement in safety due to low-solvent
tomobile industry). Successful solvent recovery content
 Paints and Coatings 79

The advantage of high-solids paints compared prevents the paint from sagging on vertical sur-
with more recent technologies lies in the fact faces and accelerates the initial drying. Solvents
that they can be produced and applied with con- also permit the use of high-viscosity binders
ventional equipment and by well-known meth- with high glass transition temperatures which
ods. Consequently potential users are primarily undergo physical drying. These advantages are
small and medium-sized paint shops, the main- largely lost in low-solvent paints, and develop-
tenance and architectural sector, as well as the ment is therefore concentrated on the synthesis
do-it-yourself sector. of special binders with the following features:
1) Reduction of the number-average molecular
mass
3.2.1. Principles
2) Narrow molecular mass distribution (reduc-
One way of lowering the solvent content of a tion of the weight-average molecular mass)
paint is to reduce the viscosity during applica- 3) Chemical modification of the binders
tion by physical or chemical methods. For exam- 4) Use of nonvolatile reactive diluents
ple, dilution of solvent-containing paints can be 5) Use of metal compounds as cross-linking
minimized by hot spraying. The solids content agents
of solvent-containing paints can be increased by In addition to the absence of physical dry-
using solvents with solubility parameters that ing, low-solvent paints require a longer time for
largely correspond to those of the binder, by cross-linking due to the lower velocity of poly-
adding viscosity-reducing cosolvents, or by us- merization of the binder. This has to be compen-
ing additives. For example, the formation of hy- sated by higher unsaturation or a higher propor-
drogen bonds between hydroxyl and carboxyl tion of functional groups in thermosetting paints.
groups increases the viscosity, which however When larger amounts of curing agents are used,
can be overcome by adding small amounts of however, a denser network than in conventional
alcohols. systems may be produced, resulting in better
Solids contents exceeding 70 wt % cannot chemical and weather resistance.
be achieved in this way – modification of the As well as the mean molecular mass and mo-
binder is necessary. Thus, the binders used in lecular mass distribution, the number and na-
high-solids systems have a much lower intrinsic ture of the functional groups as well as the de-
viscosity than conventional high-solvent paints. gree of branching of the polymer molecules are
This is usually achieved by reducing the mean important. Starlike branched polymers exhibit
number-average molecular mass or by using a weaker intermolecular interactions on account
narrow molecular mass distribution (reduction of steric factors. The rigidity of polymers con-
of the weight-average molecular mass). The use taining olefinic double bonds interferes with the
of esterification and transesterification catalysts association of the chains. Both effects lower the
in polycondensation reactions can contribute to viscosity.
a saving in solvents in this manner. Lead and tin The term reactive diluents denotes low mo-
compounds have proved particularly suitable for lecular mass reactants that act as solvents with
this purpose, but are not appropriate for all appli- an extremely low volatility and participate in the
cations on account of their toxicity. Production cross-linking reaction. Reactive diluents have
of the resin in solution followed by concentration become especially important in one-pack sys-
to a higher solids content is a further possibil- tems because they can partially or wholly re-
ity. On account of the low solvent content in the place the solvent in high-solvent paints. Reactive
formulation further measures may, however, be diluents participate in the cross-linking reaction
required because the binder is also responsible because their functional groups are identical or
for flowability, antisagging on vertical surfaces, similar to those of the principal binder. They are
prevention of wrinkle formation, and control- completely incorporated into the polymer net-
ling the drying behavior. In high-solvent paints work during curing. Good compatibility with the
these properties are partially determined by the principal binder in all cross-linking stages is nec-
solvent. Evaporation of the solvent after appli- essary for continuous curing of the paint. If this is
cation produces a sharp rise in viscosity which not the case, component segregation can occur,
80 Paints and Coatings

resulting in hazy films with reduced gloss. Re- Alkyd Resins. The high versatility and
sistance to chemicals and weathering as well as broad range of applications of alkyd resins (Sec-
mechanical strength are also adversely affected. tion 2.6) have benefitted the development of
The most commonly used reactive diluents for high-solids paints. The commonly used one-
oxidatively drying systems are unsaturated com- pack paints contain high-oil, oxidatively dry-
pounds. Polyfunctional methacrylate esters have ing alkyd resins, and have a solids content of
replaced the more volatile monomers. Diacry- 85–90 wt %. They are used as maintenance and
lates or triacrylates of polyalcohols [238], dicy- architectural coatings. Unmodified alkyd resins
clopentenyloxyethyl methacrylate [239, 240], require long drying times, tend to form wrinkles
or their (co)polymers are recommended. Reac- when applied in thick layers, and become yel-
tion products of dicyclopentadiene and butadi- low under the action of heat and in the dark, and
ene also act as reactive diluents [241]. they have therefore been superseded by modified
Low-viscosity metal compounds are also alkyd resins. Low molecular mass alkyd resins
used in cross-linking reactions. For example, al- with a narrow molecular mass distribution are re-
coholates of aluminum, titanium, and zirconium acted with modifiers such as trimethylolpropane
as well as their complexes with volatile ligands diallyl ether to yield low-viscosity alkyd resins
are primarily employed. The reaction involves with improved drying properties [244]. Incorpo-
substitution of the alcohol and formation of a ration of 1,4,5,6,7,7-hexachlorobicyclo[2,2,1]-
coordination compound with the binder [242]. 5-heptene-2,3-dicarboxylic anhydride [115-27-
During evaporation of the solvent, sagging 5] yields low-viscosity, satisfactorily dry-
on vertical surfaces must be prevented by using ing binders that are recommended as flame-
thixotropic paints. These paints can be formu- retardant marine and maintenance coatings.
lated with extenders and additives (e.g., smec- Nondrying alkyd resins cross-linked with
tite, montmorillonite, highly dispersed silica, melamine resins at elevated temperature are
hydrogenated castor oil, polyethylene waxes, used for industrial coatings. Resins containing
and metallic soaps). These paint additives also synthetic fatty acids and resins based on gly-
act as antibleeding and antisettling agents. Mod- cidyl esters of Versatic Acid (Cardura E 10,
ern urethane additives achieve the same effect Shell) are used in combination with low-
without, however, affecting the gloss of the viscosity melamine resins such as hexamethoxy-
paint films [243]. A widely used alternative is methylmelamine. p-Toluenesulfonic acid and its
thixotropic modification of the binder or com- amine salts are used as catalysts. On account of
bination of the binder with highly thixotropic their high storage life, hydrophobic oxime esters
resins (e.g., alkyd resins that have been reacted of sulfonic acids are also employed.
with polyamides).
Polyester Resins. Saturated polyesters (Sec-
tion 2.7) of low molecular mass are formu-
3.2.2. Production and Uses lated with hydroxymethylated, highly etheri-
fied melamine resins or blocked isocyanates to
Low-solvent and solvent-free paints are not as- form one-pack paints, or with polyisocyanates
sociated with specific classes of binders, and to form two-pack paints. 2-Butanone oxime,
may be either one- or two-pack systems. In one- caprolactam, and glycol ethers are used as block-
pack systems, hardening is effected by oxidative ing agents for isocyanates. Aliphatic polyisocya-
cross-linking with the aid of driers (see Section nates are preferred on account of their high resis-
2.6) or by thermoreactive curing agents such as tance to yellowing. Linear or slightly branched
etherified amino resins or “blocked” polyisocy- oligoesters with terminal hydroxyl groups are
anates. Two-pack systems are mixed immedi- usually used as resins. On account of their low
ately prior to application, and curing occurs as molecular mass they require more curing agent
the result of a polyaddition reaction between the than high-solvent binders and more powerful
binder and a curing agent. Such paints can be catalysis for sufficiently rapid cross-linking.
classified according to the nature of the raw ma- Given the possibilities for postcombustion of
terials and binders. the solvent in industrial coating, the trend to-
wards high-solids paints is, however, not so pro-
 Paints and Coatings 81

nounced in this class of binders as it is, for ex- 3.3. Waterborne Paints
ample, in the case of maintenance paints and
architectural coatings. High-quality paints with Waterborne (water-thinnable) paints were devel-
a solids content > 70 wt % are not widely avail- oped in the 1950s with the aim of replacing the
able. Powder coatings are preferred as an alter- common organic paint solvents by water, which
native in the industrial sector. has the obvious advantages of being noncom-
bustible and nontoxic [248].
Polyurethanes. The comments made con- Waterborne paints provided the technologi-
cerning polyester paints also apply to cal basis for electrodeposition paints (Section
polyurethanes (see also Section 2.9). Aliphatic 3.8), in which negatively charged paint particles
isocyanates with a high yellowing resistance (anaphoresis, industrial introduction at the be-
are increasingly used despite their high cost. ginning of the 1960s), or positively charged paint
Polyurethanes have already made large in- particles (cataphoresis, industrial introduction at
roads into all application sectors [245]. Low- the end of the 1970s) are deposited from aqueous
viscosity polyurethane oligomers can be com- solution onto metallic substrates by application
bined with polyester, acrylic, and alkyd resins. of an electrical field [249].
They serve as modifiers for waterborne and low- With the scarcity of raw material resources
solvent binders and improve the hardness and (e.g., petroleum) and the introduction of more
the flexibility of the paint film [246]. Two-pack stringent environmental legislation, waterborne
polyurethane systems may contain as polyhy- paints were developed on a broader basis dur-
droxyl component both low-solvent or solvent- ing the 1970s (e.g., as spraying and dipping
free oligoester diols and oligourethane diols. paints). Among those coating materials that can
Although the latter are more expensive, they are be classed as environmentally friendly, water-
more stable against hydrolysis. borne paints have the widest potential as regards
application, drying methods, and industrial uses.
Acrylic Resins. Low molecular mass acrylic
resins (see also Section 2.5) may be obtained
by using fairly large amounts of chain-transfer 3.3.1. Properties
reagents (e.g., thiols). The resultant problems
of smell have, however, led to the implementa- In the production and application of waterborne
tion of new polymerization techniques, such as paints, water is used as solvent or diluent. The
group-transfer polymerization or dead-end poly- physical properties of water and organic solvents
merization. Bifunctional (telechelic) polymers differ (Table 8); some of these properties have
[247] are obtained and can be used as binders to be taken into account when water is used as a
for low-solvent paints. paint solvent. The water molecules have a high
Epoxy paints (see also Section 2.10) are dipole moment and associate with one another.
usually applied as two-pack systems. Curing This means that water has a high boiling point
with amines is preferred in high-solids systems. and high latent heat of evaporation despite its
Epoxy resins may also be used as coreactants or low molecular mass. This in turn results in fairly
reactive diluents in low-solvent paints based on long evaporation times or in the need to supply
acrylic, polyester, or alkyd resins. energy in the form of heat to evaporate the water
and dry the paint film. The high dipole moment
PVC plastisols, i.e., poly(vinyl chloride) of water is also responsible for its high surface
dispersed in plasticizers, are used in special ap- tension. With substrates having a low critical sur-
plications such as underseals for automobiles or face tension (e.g., plastics or unsatisfactorily de-
as sealing compositions. greased metals) this leads to inadequate wetting,
unsatisfactory edge covering, and crater forma-
Commercial products include Alftalat tion. Critical surface tensions (at 20 ◦ C and in
(Hoechst); Alkydal (Bayer); Beckosol (Re- millinewtons per meter) of water and other sub-
ichhold); Bevibond (Bergvik); Synthalat (Syn- stances follow:
thopol); Vialkyd (Vianova); and Worlekyd (Wor-
lee).
82 Paints and Coatings
Aliphatic hydrocarbons 18.0–28.0
Aromatic hydrocarbons 28.0–30.0
water due to salt formation involving functional
Ketones 22.5–26.6 anionic or cationic groups.
Esters 21.2–28.5 Most water-soluble binders are anionic. They
Alcohols 21.4–35.1 are made water soluble by neutralizing carboxyl
Water 72.5
Poly(vinyl fluoride) 18.5
groups with ammonia or highly volatile (gen-
Oil 28.9 erally secondary or tertiary) amines that evapo-
Polypropylene 29.0 rate during film formation. In cationic binders,
Stainless steel 30.0 salt formation usually occurs between the amine
Steel 55.0
groups of the resin and organic acids (e.g., acetic
or lactic acid). Salt formation with inorganic
The high polarity of water is responsible not acids (e.g., phosphoric acid) is, however, also
only for differences between the application be- used. Typical applications include cationic elec-
havior of waterborne paints and solvent-con- trodeposition paints.
taining paints. It also means that the organic The binder structure must be resistant to
polymers used as binders for waterborne paints hydrolysis in aqueous, alkaline, or acid media.
must have a different structure from those used For alkyd or polyester resins the introduction of
in solventborne paints. the carboxyl groups to be neutralized via full-
ester bonds is advantageous; semi-ester bonds
Table 8. Physical properties of water, butanol, and xylene
tend to undergo hydrolysis. Organic solvents
and organic cross-linking agents (e.g., melamine
resins) also influence viscosity stability on stor-
age [250].
Water-soluble binders generally contain or-
ganic solvent (≤ 10–15 wt %) that originates
from their production via polycondensation or
polymerization reactions in an organic medium.
They can, however, still be dissolved or diluted
with water after neutralization. Anomalous vis-
cosity behavior may, however, arise; it is charac-
terized by a viscosity increase on dilution with
water due to association of the binder molecules
in water (Fig. 3) [251].
Waterborne paints differ according to the na-
ture of their stabilization in water; the polymer
molecules are dissolved in water or dispersed
in water in the form of polymer dispersions or
emulsion polymers. Further developments in-
clude polymer particles formed in organic sol-
vents and then emulsified in water with low or,
more commonly, high molecular mass emulsi-
fiers being used for internal or external emulsifi-
cation. Internal emulsification denotes that part
of the binder molecule functions as an emulsify-
ing moiety, whereas for external emulsification
separate emulsifiers are required.
Figure 3. Viscosity behavior of a short-oil alkyd resin on
Water-Soluble Binders. Water-soluble dilution with water
binders consist of relatively low molecular mass Starting conditions: solids content 71.0 wt %; organic co-
polymers (M r < 10 000) (e.g., alkyds, poly- solvents 24.3 wt %; dimethylethanolamine 4.7 wt %
esters, polyacrylates, epoxides, and epoxy es-
ters) whose individual molecules dissolve in
 Paints and Coatings 83

The organic cosolvents are mainly alcohols, vinyl monomers) and are produced by emul-
glycol ethers, and other oxygen-containing sol- sion polymerization (→ Polymerization Pro-
vents that are soluble or miscible with water. cesses). These waterborne paints also contain
Waterborne paints formed from water- small amounts of organic solvents (< 5 wt %)
soluble binders can undergo different forms of that serve as film-forming (coalescing) agents
film formation and hardening, including drying that evaporate on drying.
at room temperature (e.g., polyacrylates, epoxy The required application viscosity of water-
esters, and alkyds). The rates of initial drying borne emulsion paints is generally obtained by
and through drying are controlled by evaporation adding a small volume of water. The evapora-
of water from the paint film (physical drying). tion behavior of polymer dispersions is similar
Oxidatively drying, water-soluble binders (e.g., to that of conventional, solvent-based paints.
alkyds) also undergo chemical cross-linking that Film formation occurs via evaporation of wa-
can be accelerated with driers. ter from the paint film and coalescence of the
Water-soluble binders (e.g., polyesters, poly- high molecular mass binders; the release of
acrylates) can also be chemically cured with water takes place relatively quickly (physical
cross-linking agents at elevated temperature drying). The minimum film-forming tempera-
(oven drying). These binders can be reacted ture depends on the chemical structure of the
with water-soluble or water-miscible amino polymers. Film formation can be facilitated by
resins (especially fully or partially methylated the addition of organic solvents (e.g., alcohols,
methoxymethylmelamine resins) or with water- butylglycol ethers) or by the action of heat.
soluble or water-miscible blocked polyisocy- Alternatively, chemical cross-linking reac-
anates, which only react after the isocyanate tions can also be used to harden polymer dis-
groups have been unblocked. persions (oxidative drying or oven drying). An
On account of the viscosity anomaly, wa- example is the cross-linking of hydroxyl groups
terborne paints based on water-soluble binders of the polymer dispersions with hexamethoxy-
have a relatively low solids content (ca. 30– methylmelamine resins.
40 wt %) and require relatively large amounts of Characteristic properties of waterborne
organic cosolvents (up to ca. 15 %) to ensure wa- emulsion paints are relatively high solids con-
ter solubility and film formation. They also have tents (50–60 wt %), rapid dilution with water
the advantage of a broad drying spectrum (phys- without any viscosity anomaly, and a low con-
ical, oxidative, oven drying) and a wide range of tent of organic solvents (< 5 %).
application methods (dip coating, flow coating, As a result of the particulate nature of the
spray coating, electrodeposition coating). binders only a low gloss and, in some cases, only
Paint films formed from water-soluble limited corrosion protection can be obtained.
binders tend to be water-sensitive due to their hy- Waterborne paints based on dispersions can be
drophilic, solubilizing groups. They can be for- applied by spraying, however they are of only
mulated to have a high gloss due to good pigment limited use for electrostatic coating and dipping
wetting and stabilization. They can also have a applications due to their rapid drying properties.
high level of corrosion protection which depends
on the corrosion-inhibiting pigments used and Hybrid Systems. Combinations of water-
the chemical nature of the binder. The latter de- soluble and water-dispersed binders may be used
termines adhesion to the substrate and diffusion to achieve synergistic effects (e.g., to control
of water and oxygen through the paint film. the amount of organic solvents or the applica-
tion behavior). Polymer dispersions or powdered
Polymer Dispersions (Emulsion Poly- binders may be used as water-dispersible binders
mers). Waterborne paints based on polymer dis- [252]. The use of polymer dispersions allows the
persions (usually referred to as emulsion paints) solids contents of water-soluble binders to be
are not water soluble. They are water-thinnable increased, the level of organic solvents to be re-
systems composed of dispersions of polymer duced, and the physical drying time to be short-
particles in water (see Section 3.5). The par- ened. The use of water-soluble binders provides
ticles consist of high molecular mass poly- a broad application spectrum and yields paint
mers (e.g., of styrene, butadiene, acrylate, or films with well-balanced properties.
84 Paints and Coatings

Internally and Externally Emulsified sion or dissolved resins, and result in loss of ad-
Binders. In recent developments polyurethane, hesion or blistering during exposure to humidity
polyacrylate, or polyester binders are synthe- and water. Examples are surface-treated organic
sized in an organic medium and partially dis- and inorganic pigments (some phthalocyanine
solved in water by salt-forming groups to form blues, carbon black, transparent iron oxides).
colloidal solutions. This involves internal emul- As a rule, pigments can easily be dispersed in
sification. Alternatively, the polymers are dis- water-soluble binders because the water-soluble
persed and stabilized in the aqueous phase by binder molecules promote wetting and stabiliza-
adding low or high molecular mass emulsifiers tion of the pigments. The dispersion and stabi-
(external emulsification). The disadvantages lization of pigments in polymer dispersions is,
of water-soluble binders as regards low solids however, more difficult because the dispersions
and high organic solvent contents, and polymer form a continuous phase in water and uniform
dispersions as regards film formation can be distribution of the dispersed pigment particles in
compensated in this way. the paint film is hindered by coalescence of the
These binders form the basis for new indus- polymer particles.
trial waterborne paints, an example being aque- Waterborne paints can be applied by a wide
ous metallic base paints for automotive coat- range of methods (e.g., by dipping electrodepo-
ings and finishes. The binders of these paints sition, or spraying) followed by air, forced-air,
are acrylic core–shell polymers [253, 254]. The or oven drying. The influence of climatic con-
core and shell have a different monomer com- ditions (e.g., temperature and atmospheric hu-
position, the shell has anionic groups which in- midity) on sprayability, substrate wetting, pour-
teract with water and stabilize the dispersion. ing and leveling behavior, as well as the rate
The anionic shell allows pseudoplastic flow be- of water evaporation from the wet paint film
havior which ensures parallel orientation of the should, however, be taken into account. For ex-
aluminum pigments in the wet paint film. This ample, the drying of waterborne paints proceeds
orientation and the low solids content are respon- more slowly at low temperature and/or high rela-
sible for the metallic gloss and high color flop tive atmospheric humidity. These disadvantages
(change in color observed on varying the view- can be remedied by suitable formulation of the
ing angle) of the base paints. paints, by heating the intake air to the spray cab-
Generally, the binders have a low content of ins and the ventilation zone, and also by main-
organic solvents (ca. 10 %) and can be applied taining the atmospheric humidity within specific
over a wide temperature and humidity range. limits (e.g., 50–80 %).
Water and organic cosolvents used in clearcoats In order to reduce the tendency to “pinholing”
applied by wet-on-wet coating evaporate rapidly that occurs with higher layer thicknesses, con-
after predrying with convection or IR radiation. trol of application parameters is advantageous.
Examples include using suitable spraying equip-
ment, feeding preheated air to the ventilation
3.3.2. Production and Application zone, using IR drying in the ventilation zone,
and avoiding steep stoving curves.
Most of the pigments used in conventional Corrosion-resistant and wear-resistant mate-
paints and coatings are also suitable for water- rials (e.g., stainless steel and in special cases
borne systems. Some exceptions are lead chro- suitable plastics) have to be used for the equip-
mates and molybdates, manganese lakes (Pig- ment required to produce and apply waterborne
ment Red 48 and 52), some perylenes (Pig- paints. This applies to production vessels, stor-
ment Red 223), benzimidazolone yellow (Pig- age and transportation vessels, to the feed sys-
ment Yellow 151), and isoindolines (Pigment tem used for application (e.g., closed circuit
Yellow 13a) which all have limited alkali resis- tanks, pipelines, and pumps) all of which must
tance. be able to withstand chemical mechanical stress.
Another limitation results from pigments that The use of corrosion-resistant materials for the
contain a high amount of water-soluble compo- spraying equipment is also advantageous.
nents and electrolytes which may reduce storage Waterborne paints should be protected
stability, cause coagulation of the binder emul- against frost during storage. In general, storage
 Paints and Coatings 85

areas do not have to satisfy special fire preven- solvent emission during application to comply
tion regulations. with legal requirements. Savings in organic sol-
vents as diluents, savings in insurance premi-
ums, lower energy consumption in spray cab-
3.3.3. Uses and Environmental Aspects ins, ventilation zones, and drying ovens all con-
tribute to the overall economy of waterborne
Waterborne paints for industrial use only ac- coating materials.
count for a small proportion of the total pro- Thanks to their low organic solvent content,
duction of coatings, paints, and thinners in the the use of waterborne paints substantially re-
Federal Republic of Germany (Table 9) (i.e., duces solvent emission from paint or spray-
for the serial production of industrial and con- ing shops (spray cabin, ventilation zone, drying
sumer goods such as machinery, tools, electrical oven).
equipment). Whereas the proportion of water- Waterborne paints can generally be classed
borne emulsion paints and plaster for decorative as less toxicologically harmful than correspond-
use (architectural paints, see Section 3.5) ac- ing solvent-based paints. Nevertheless, lung-
counted for ca. 45 % of the total production bet- penetrating paint mists (aerosols) of water-based
ween 1979 and 1989, the proportion of water- paints present a health hazard and appropri-
borne paints for industrial use merely doubled ate protective measures (e.g., use of respirators)
from ca. 2 % to almost 4 %. However, indus- must be taken depending on the workplace con-
trial waterborne paints now have a broad appli- centration. Water-based paints are not, however,
cation spectrum based on the development of subject to such stringent regulations concerning
new paint technologies. The most important use hazardous substances as conventional, solvent-
sectors include electrodeposition coating of au- based paints.
tomobile bodies and accessories; spraying and
dipping primers, as well as one-layer coatings
for engines, chassis, axles, and automobile ac- 3.4. Coating Powders
cessories; sprayed fillers for automobile bodies
(first industrial use in Europe 1981); waterborne 3.4.1. Introduction and Economic
paints for automobile bodies (1987); aqueous Importance
protective waxes for preservation of automo-
bile body shells (1989); aqueous primers and Coating of substrates (particularly metallic sub-
one-layer coatings for metal furniture, electrical strates) with particulate plastics is a well-
and electronics equipment, machines, machine established technology. The fluidized-bed pro-
parts, agricultural equipment and machinery, cess was developed in 1952. The electrostatic
construction machinery; and aqueous primers powder coating technique introduced in 1965
and one-layer coatings for plastic parts (e.g., has, however, made a substantially greater im-
radio and television cabinets and office equip- pact [255]. These two processes are discussed in
ment). Section 8.3.5.
Other powder coating processes include
Table 9. Production of paints in the Federal Republic of Germany blowing thermosetting plastics powders onto hot
(Statistisches Bundesamt, BRD) parts for electrical insulation, flocking polyeth-
ylene onto hot pipes to produce an external coat-
ing, and coating small, cold items in electro-
static fluidized beds, followed by thermal cur-
ing. Lances are also used for the internal coat-
ing of preheated vessels and pipes, vibration and
rotation sintering, as well as flame spraying for
repair work and large articles, and the minicoat
and maxicoat processes for coating small items.
The prospects for the increasing use of in- Thermosetting coating powders are applied
dustrial waterborne paints lie in their economic mainly by electrostatic spraying and dominate
advantages and in the possibility of reducing the market. The annual growth rates worldwide
86 Paints and Coatings
Table 10. Production of thermosetting coating powders in 1988 classified according to binder types (as percentages)

* [256]

are ca. 10–20 %. Total world production in 1989, (Table 11). Their production does not show a
including “functional materials”, was 250 000 t comparably significant growth rate.
with a value of ca. $ 1.2×109 . This was sub-
divided according to geographical regions and
countries as follows (103 t): 3.4.2. Production
See also Section 7.2.3.
Europe 140
North America 55
Thermosetting coating powders are produced
Far East 37 exclusively by the extruder process. This method
Rest of the world 18 is employed because it is the cheapest and the
United States 47 most widely applicable and flexible; it allows
Italy 33
Federal Republic of Germany 33
large plants to be supplied with material of con-
United Kingdom 19 sistent quality. Production with extruders in-
France 18 cludes the following steps:
Japan 18
Spain 11 1) Testing of raw materials
2) Weighing of the premixture
In contrast to wet materials, almost no ma- 3) Mixing in the premixer
terial is lost during application of coating pow- 4) Homogenization and dispersion in the ex-
ders (no solvents, no split-off products, powder truder (80–140 ◦ C)
overspray is recovered). These tonnages roughly 5) Cooling the extrudate to room temperature
correspond to three times the amount of ready- 6) Intermediate testing (monitoring the extru-
for-spraying, conventional industrial paint. date)
7) Flaking
Table 11. Estimated production (in 103 t) of thermoplastic coating 8) Fine grinding in an air-classifying mill
powders in 1989 classified according to binder types 9) Screening in a sieve
10) Checking specific properties of the coating
powder
Since modification of the coating powder (e.g.,
tinting) after production) is nearly impossible,
all relevant process parameters (e.g., raw mate-
rials, machine settings) must be kept constant.
This has the advantage for the user that changes
such as thickening, settling, or floating can-
not occur during application and storage. Large
Table 10 summarizes the consumption of
batch sizes are necessary because cleaning of the
thermosetting binders used in various regions.
plant and equipment is time-consuming and ex-
The epoxy–polyester systems predominate over
pensive. An extremely high level of cleanliness
polyester–trisglycidyl isocyanurate and epoxy
must be maintained during production because
systems. The consumption of thermoplastic
different coating powders may be incompatible.
coating powders, particularly those used in the
Thermoplastic coating powders can also be
fluidized-bed and flocking processes, is substan-
produced with extruders. Grinding is partic-
tially lower than that of thermosetting powders
ularly important here and, depending on the
 Paints and Coatings 87

binder and desired particle size distribution, can thermosetting powders to hot substrates by elec-
be carried out at ambient temperature [e.g., some trostatic spray or fluidized-bed processes is re-
polyethylene (PE) powders for the fluidized-bed stricted to EP coating powders.
process] or at low temperature using liquid nitro- Coating powders for exterior use are mainly
gen, etc. [e.g., polyester (SP) electrostatic pow- based on the SP–TGIC system. Of some im-
ders]. Some poly(vinyl chloride) (PVC) pow- portance is the SP–PUR system, i.e., the com-
ders are also produced in this way. The most bination of hydroxy-functional polyester resins
efficient process for producing PVC powders is with caprolactam-blocked isocyanate adducts
to mix the components in a high-speed mixer (primarily based on isophorone diisocyanate).
at 80–110 ◦ C, followed by cooling in a second Acrylic resins are of importance mainly in the
mixer, and screening. United States (AC–PUR) and in Japan (AC–
Polyamide (PA) powders are generally pre- DDA). The AC–PUR system is used for auto-
cipitated from solution. Ethylene–vinyl alcohol motive components and in domestic appliances.
copolymer (EVOH) powders are precipitated by The PUR systems based on uretdione (a dimer-
hydrolyzing ethylene–vinyl acetate copolymer ization product of isocyanates) do not release
solutions. reaction products and may be mentioned as a
specialty.
Typical properties of thermoplastic binders
3.4.3. Properties are summarized in Table 14. Application is
mainly by fluidized bed but includes application
The typical constituents of a coating powder are by flocking. Electrostatic spraying is also used
binders (resins, if necessary hardeners and accel- for finely ground powders. The main uses are in
erators), colorants (mainly pigments), additives, the interior sector. The PA and EVOH powders
and in some cases extenders. are the most widely used thermoplastic binders.

Binders. Thermosetting and thermoplastic Colorants. Coating powder colorants are al-
binders are listed, together with their abbrevi- most exclusively pigments and must satisfy the
ations, in Table 12. A broad range of raw ma- following requirements:
terials is now available and it has become diffi-
cult to systematically classify binder properties. 1) Thermal stability at the curing temperature
Outstanding properties are obtained with suit- 2) Only a slight increase in binder viscosity
ably selected systems and have contributed to 3) No reaction with other constituents of the for-
increased use of coating powders. mulation
The thermosetting binders are the most im- 4) Stability towards shearing forces during ex-
portant. Their properties are summarized in Ta- trusion and grinding
ble 13. The quantitatively predominant EP, EP– Inorganic pigments (e.g., titanium dioxide, iron
SP, and SP–TGIC types cure by polyaddition oxides, and chromium oxides) satisfy these cri-
without release of split-off products. Only SP– teria the best. To obtain maximum durability in
PUR and AC–PUR systems are cured by poly- exterior-grade powder coatings, lead pigments
condensation and release some caprolactam. are sometimes still required. In Europe the use
Thermosetting powders are mainly applied of cadmium pigments is declining. Replacement
to cold workpieces by electrostatic spraying. by organic pigments generally restricts color se-
Materials for interior use are generally pro- lection in the red, orange, and yellow ranges.
duced from epoxy resins based on bisphenol A– Metallic and pearlescent effects are obtained by
epichlorohydrin and are cured with acidic using flakes of aluminum or coated mica.
polyester resins or modified (i.e., substituted
or accelerated) dicyanodiamides. Materials for Other Constituents. The remaining con-
highly reactive systems are cured with phenolic stituents of coating powders impart specific
hardeners (i.e., oligomers with phenolic termi- properties (e.g., additives to adjust flow) and re-
nal groups). Other curing agents include imida- duce cost (extenders such as calcium carbonate
zoline derivatives (for matt coatings), and an- or barium sulfate).
hydrides and their adducts. The application of
88 Paints and Coatings
Table 12. Summary of coating powder binders
Use Thermosets Thermoplasts
Mainly interior EP–SP epoxy resin–COOH polyester resin PE polyethylene LDPE,
EP–DCD epoxy resin–modified dicyanodiamide LLDPE, HDPE
EP epoxy resin–phenolic hardener PA polyamide 11, 12
EP epoxy resin–imidazoline derivative SP polyester
EP expoy resin–anhydride adducts
Interior and SP–TGIC COOH polyester resin–trisglycidyl iso- EVOH ethylene–vinyl
exterior cyanurate alcohol copolymer
SP–PUR OH polyester resin–isocyanate adduct PVC poly(vinyl chloride)
AC–PUR OH acrylic resin–isocyanate adduct
AC–DDA glycidylacrylic resin–dodecanedicarboxylic
acid

a
Table 13. Typical properties of thermosetting powders

c
[257].
d
[258].

3.4.4. Testing To check the film quality of a powder coating,

the same standard methods as for liquid coatings
DIN 55 690 classifies and identifies coating are used. Minimum requirements for powder
powders according to the binder. Standards for coatings have been laid down for certain areas of
testing coating powders in powder form are sum- use in relevant standards (e.g., DIN 30 671 for
marized in Table 15. Relevant European stan- pipes, DIN 30 677 for mountings and fittings,
dards (CEN) have not yet been drafted. Quality BS 6496 for individually coated structural ele-
aspects are described in detail in [259]. ments) or by quality associations (e.g., Qualicoat
or GSB, “Quality Association for Individually
 Paints and Coatings 89
Table 14. Typical properties of thermoplastic powders

Table 15. Standards for testing coating powders in powder form

Coated Building Elements” relating to coating of 3.4.5. Storage and Transportation

aluminum and “Quality Association for Heavy
Corrosion Protection” relating to the coating of Coating powders are shipped in containers of
valves and fittings). varying size. They may, for example, be pack-
90 Paints and Coatings

aged in cardboard boxes each containing one or 2) Higher energy sparks are required to ignite
more polyethylene bags holding 20–25 kg. For powder–air mixtures than solvent–air mix-
larger customer off-takes, reusable metal (e.g., tures
aluminum) containers with capacities for 400– 3) The glow temperature and the minimum ig-
1000 kg are used. Containers may be equipped nition temperature of a powder–air mixture
with built-in fixtures such as a porous layer at are very high (450–600 ◦ C)
the base for aerating and fluidizing the contents. 4) Powders without fines for fluidized-bed ap-
However, containers without such fixtures are plication are extremely difficult to ignite
often preferred because they are easier to clean.
The safe operation of coating powder plants
Thermoplastic powders are often supplied in
and equipment is covered by national provisions
plastic drums or sacks.
and regulations. In the case of Europe, the ten-
Coating powders should be stored in a cool
language brochures “Safe Powder Coating” pub-
dry place. They should not be subjected to ex-
lished by CEPE (the European Committee of
cessive pressure or temperature.
Paint Associations, Brussels) should be men-
tioned.
3.4.6. Environmental Aspects and Safety

Powder coating is the coating method that pro- 3.4.7. Uses

duces the least environmental pollution because
Thermosetting coating powders are
1) the occurrence of paint slurry is avoided, widely used for industrial metal coating and
2) the separation of dust–air mixtures is simple, are distributed among the various markets as
and indicated in Table 16. Uses range from manual
3) the coating powders are solvent-free and gen- application up to fully automatic, large-scale
erally cure by polyaddition. plants with an annual coating powder consump-
Emissions from coating powder spray cab- tion of several hundred tonnes. Job coaters as
ins are generally << 5 mg coating powder per a service industry account for a significant pro-
cubic meter of exhaust air. Emissions from the portion of the coating powder consumption.
driers are generally also extremely low. Other
substances, apart from very small amounts of Table 16. Uses of thermosetting coating powders (1987) expressed
water (≤ 1 %), that are released in the stoving as percentage of production
of coating powders are listed in Tables 13 and
14. On account of these very low emission lev-
els, the use of coating powders is not limited by
environmental protection legislation.
Coating powders that do not contain any haz-
ardous components (e.g., lead pigments) should
generally be regarded as inert dusts and do not
have toxic or fibrogenic effects. As a rule, the
fraction of respirable dust that can penetrate the
lungs is << 10 wt %. Disposal of coating pow-
der waste in landfills does not in general pollute
groundwaters or surface waters.
Coating powders are combustible dusts and * [260]
they can form explosive powder–air mixtures
in certain concentration ranges. However, the The main reasons for the steadily increasing
danger risk is substantially lower than that for use of thermosetting coating powders (see Sec-
solvent-based paints for the following reasons: tion 3.4.1) are as follows:
1) When stored in bulk, coating powders are 1) Economy
difficult to ignite and when heated generally 2) Simple, easily automatable application
only fuse together 3) Ecological advantages
 Paints and Coatings 91

4) Good film properties, wide range of layer plant for powder coating (for coating refriger-
thicknesses ators and deep freezers) came into operation in
5) Improved coating powders and plants 1973. Powder coating has since become wide-
6) New areas of application spread in the household appliances sector.
7) Many years’ experience with all sizes of coat- An extremely wide range of automotive parts
ing plants and components on, in, or underneath automo-
biles are powder coated (e.g., trim, headlights,
The building and construction industry is the
springs, transmission shafts, horns). By coating
main user of coating powders, for both exterior
reflectors, smooth leveling is achieved on the
and interior use. Coating powders have proved
rough, deep-drawn substrate, which eliminates
popular for coloring light metal façades, pan-
the time-consuming, expensive polishing that is
els, and profiles on account of their outstanding
necessary with a liquid paint. Interesting multi-
weather resistance and robust surface. They also
layer coatings that combine powder and/or paint
allow architects complete freedom of expression
layers can be applied to wheels to obtain decora-
and use.
tive effects. In Japan and the United States coat-
In the interior-use sector, a diverse range of
ing powders are used as primers or surfacers on
objects and parts can be powder coated. Exam-
automotive bodies.
ples include partition walls, ceilings, door and
Thermosetting coating powders are also used
window frames, and radiators. The coating of
for storage furniture shelves, shopfitting, and
radiators is particularly interesting because it in-
wire goods. The coating of nonmetallic sub-
volves penetration of the coating powder into
strates (e.g., glass or ceramics) and highly dec-
deep Faraday cages. The excellent impact resis-
orative articles (e.g., spectacles and sanitary fit-
tance of most powder coating films is important
tings) should also be mentioned.
in the building sector because the articles are
Important areas of use of epoxy resin pow-
roughly handled.
ders include the interior and exterior coating of
A further important use is the coating of steel
pipes, fittings, fixtures, filter plates, and steel
and garden furniture, machine parts, and electri-
bars for reinforced concrete, as well as the elec-
cal components such as switch cabinets. Appli-
trical insulation and the encapsulation of elec-
cations in the furniture sector include the coating
tronic components.
of metal rails and fittings.
The coating of steel chairs and garden fur-
Thermoplastic Coating Powders.
niture can be more easily automated with elec-
Polyethylene is mainly used for the exterior
trostatic powder coating than with conventional
coating of pipes. It is also employed for coat-
wet coating. Chairs have an unfavorable shape
ing wire goods, especially in the domestic ap-
and coating with wet paint can only be partially
pliances sector.
automated; generally a final coat is applied man-
Polyamide is extremely resistant to washing
ually. With coating powders, however, coating
lyes and chemicals, provides good corrosion
can be performed fully automatically. The paint
protection, and has a high impact strength and
film has a high scratch resistance which consid-
low degree of abrasion. Areas of use are there-
erably simplifies packaging.
fore very varied, and include wire articles (e.g.,
The coating of cast iron is an important use
dishwasher baskets) and metal furniture (e.g.,
in the engineering sector. Specially formulated
for hospitals).
coating powders are available for porous sub-
Poly(vinyl chloride) is mainly used for wire
strates to prevent bubble formation in the film.
articles (e.g., fences, domestic and household
In the electrical industry, the coating of
appliances). The release of plasticizer during
switchboards with textured powders should be
coating is a disadvantage.
mentioned. Important requirements include sat-
Ethylene–vinyl alcohol copolymer is used
isfactory punching quality, recoatability with al-
particularly for heavy corrosion protection (e.g.,
most all paints, and constant visual properties.
in water treatment and chemical plant construc-
Further important users are the household ap-
tion) but also for wire goods (e.g., household
pliance industry and the automotive parts and
appliances).
manufacturing industry. The first large-scale
92 Paints and Coatings

The main use of thermoplastic polyesters is from + 5 ◦ C (minimum film-forming tempera-

the coating of weld seams in cans. ture, MFT) without producing any permanent
odor. The MFT depends on the auxiliaries and
residual monomers in the plastics dispersions.
3.5. Waterborne Dispersion Paints Emulsion paints are noncombustible in liquid
(Emulsion Paints) [261, 262] form (easy storage and transportation); equip-
ment, hands, and spillages can be washed and
The paints and coatings sector underwent a cleaned with water.
major revolution after World War II. In Ger- According to DIN 55 947, a plastics disper-
many the changeover to synthetic polymers sion consists of polymer particles distributed
[poly(vinyl acetate) and polyacrylates] took in a liquid phase (water in the case of emul-
place during the war due to the lack of natural sion paints). Polymer dispersions may be fine
raw materials (vegetable oils for alkyd resins). (particle diameter 0.1–0.3 µm), medium (par-
Since the postwar demand for synthetic styrene– ticle diameter 0.3–2 µm), or coarse (particle
butadiene rubber fell in the United States, part diameter 2–5 µm). Fine and medium disper-
of the production capacity was converted to sions are mainly used as binders for emulsion
styrene–butadiene latex for paints (latex paints). paints. If a particularly good penetration abil-
Dispersion paints, commonly referred to as ity is required, very fine dispersions with parti-
emulsion paints are now the largest product cle sizes of 0.04–0.1 µm are also used. Poly-
group worldwide in the paint and coating in- mer dispersions of relatively uniform particle
dustry. In the Federal Republic of Germany, size are termed monodisperse, while those with
for example, the total production of paints and a nonuniform or broad particle size distribution
coating materials in 1988 was 1.2×106 t, of are termed heterodisperse or polydisperse. Fine
which interior-use emulsion paints accounted dispersions (0.1–0.3 µm) generally have a fairly
for 226 000 t, exterior-use emulsion paints for high pigment binding capacity (i.e., at equal pig-
120 000 t, emulsion lacquers for 20 000 t, and ment volume concentration (PVC) the pigments
dispersion-bound plasters for 124 000 t. are bound better than with coarser dispersions).
Binders consisting of plastics (polymer) dis- Paints with improved application properties can
persions can be used for matt to gloss coats, be formulated with dispersions in the particle
smooth paint-like products, and plasters (syn- size range > 0.3 µm. Satisfactorily leveling and
thetic resin-bound plasters, DIN 18 550) con- glossy coatings can be produced with fine, het-
taining coarse, structure-imparting aggregates. erodisperse dispersions.
Substrates such as plaster, concrete, cement- Emulsion paints consist of polymer disper-
bonded slabs, gypsum plaster, plaster board, sions as binders, pigments, extenders, and small
wallpaper (wood-chip, glass textile, vinyl wall- amounts of auxiliaries (in some cases < 1 %).
paper, etc.), brickwork and sand–lime bricks, ce- Waterborne polymer dispersions are produced
ment or concrete roofs, floors, sidewalks, wood by emulsion polymerization; monomer droplets
and wood materials (e.g., chipboard and hard- are polymerized in water-containing surfactants
board), and many other substrates can be coated and protective colloids. The size and size dis-
with coating materials based on polymer disper- tribution of the dispersed polymer particles can
sions. Many coating materials containing poly- be controlled by adjusting the stirring rate in the
mer dispersions that form films and dry at el- polymerization reactor and by selecting appro-
evated temperature (>40 ◦ C) are used for the priate protective colloids. For a detailed descrip-
industrial coating of plastic articles (e.g., audio tion of emulsion polymerization, see → Poly-
equipment housings, dashboards and instrument merization Processes.
panels in vehicles), metals, window frames, etc.
The advantage of waterborne coatings con- Polymers. The nature and amount of the em-
taining polymer dispersions is that they can be ployed dispersion greatly influences the quality
applied without stringent safety measures be- of an emulsion paint. The nature of the plastics
cause water is their principal liquid component. dispersion is governed by the monomers used
Most of them dry physically, by evaporation of for emulsion polymerization. The most impor-
water, under ambient conditions and generally tant polymers for emulsion paints are listed be-
 Paints and Coatings 93

low in order of increasing resistance to alkali ide, and nitrogen oxides. Inorganic extenders
(which may be of importance for use on exterior are obtained from natural minerals by crushing,
mineral substrates): grinding, elutriation, and drying. The most im-
Vinyl acetate copolymers are used world- portant extenders are calcite, chalk, dolomite,
wide in polymer dispersions. Copolymers with kaolin, quartz, talc, mica, diatomaceous earth,
dibutyl maleate are particularly elastic, while and barytes. Synthetic inorganic extenders are
copolymers with vinyl esters of Versatic Acid produced from inorganic products by diges-
have particularly good weather resistance for tion, precipitation, or annealing. The most im-
shade formulations. Copolymers with acrylate portant synthetic extenders are precipitated cal-
esters and vinyl acetate–ethylene–vinyl chloride cium carbonate, barytes (blanc fixe), and sili-
terpolymers with a good cost–performance ratio cates (Aerosil). Synthetic organic extenders in-
are also important. clude polymer fibers, as well as the more re-
Vinyl propionate copolymers (e.g., with cently introduced hollow polymer spheres which
acrylate esters) are used in the same way as can be used to formulate paints with a particu-
vinyl acetate copolymers. larly low density.
Acrylate–methacrylate copolymers (pure
acrylates) are used in particular for house paints Auxiliaries.
and other emulsion paints with high weather re- Dispersants ensure that the individual parti-
sistance and for waterborne industrial paints. cles in the emulsion paint do not combine to form
Styrene–acrylate copolymers are widely agglomerates. Protective colloids and emulsi-
used as binders for interior-use paints, plasters, fiers are used during emulsion polymerization to
and exterior-use paints with a relatively high ensure that small polymer spheres are formed in
PVC. Water absorption and elasticity decrease the aqueous phase but do not fuse together. They
with increasing styrene content. influence film formation of the emulsion paint
Styrene–butadiene polymers have a very low and can cause foaming. Protective colloids in-
water uptake but tend to undergo chalking and clude poly(vinyl alcohols) and cellulose ethers.
are therefore used for formulating interior-use Emulsifiers include anionic and nonionic surfac-
(latex) paints that can withstand repeated clean- tants.
ing. Wetting agents are used to disperse the ex-
tenders and pigments. They include sodium
Commercial Products. Examples of com- polyphosphates, and sodium and ammonium
mercial products are Acronal, Propiofane salts of low molecular mass poly(acrylic acids).
(BASF); Lipaton (Hüls); Mowilith (Hoechst); Polyphosphates tend to undergo secondary reac-
Plextol (Röhm); Primal (Rohm & Haas); tions; polyacrylates are therefore preferred from
Rhodopas (Rhône-Poulenc); and Vinnapas the point of view of storage stability, gloss, etc.
(Wacker). An excess of dispersion auxiliaries increases
the water sensitivity of the coating films and
Pigments. Many colored pigments are used thus reduces washfastness and weather resis-
in emulsion paints. Titanium dioxide is responsi- tance. The optimum amount and composition of
ble for the hiding power, whiteness and, depend- dispersants is of decisive importance as regards
ing on the type of TiO2 used (rutile or anatase), the quality of each formulation.
the chalking resistance of paints. Surface-treated During the production and transportation of
rutile should be used for chalking-resistant emulsion paints the dispersants and emulsifiers
paints because anatase reacts photocatalytically cause foaming which leads to the undesirable
with oxygen and moisture resulting in radical re- formation of craters and pores in the coating
actions, decomposition of the binder at the TiO2 film. Defoamers reduce the surface tension of
interface, and chalking. the liquid to such an extent that the air bubbles
in the foam collapse. They include silicone oils,
Extenders are used to adjust the properties waxes, fatty acids, if necessary on a solid carrier,
of a coating (e.g., layer thickness and structure). e.g., on silicates. The defoamers are formulated
They influence water uptake and permeability in an auxiliary liquid (e.g., mineral oil, silicone
to water vapor, carbon dioxide, sulfur diox- oil, or glycol).
94 Paints and Coatings

Preservatives prevent microbial growth in ticles approach one another until they come
emulsion paints stored in drums or cans. Fungi into contact. On further evaporation of water,
and bacteria are present in the raw materials (es- capillary pressure is generated in the water-
pecially water) and also pass during the produc- filled interstices between the polymer spheres,
tion process into the emulsion paints. The most as well as between the polymer spheres and other
commonly used preservatives include formalde- solids (extenders, pigments). The polymer par-
hyde-releasing agents, chloroacetamide, isoth- ticles thus coalesce to produce a coating film.
iazolinone, and heterocyclic nitrogen–sulfur A precondition for this film formation is that
compounds. For health reasons mercury com- the minimum film-forming temperature (MFT)
pounds and organic tin compounds should not is reached or exceeded during drying. Below the
be used. At higher concentrations, preservatives MFT an emulsion paint forms a noncoherent,
have a fungicidal action and prevent fungal in- fissured, mechanically unstable film. The MFT
festation of the coating and coated substrate. depends on the structure of the polymer binder,
Coatings may also contain algicides. its glass transition temperature, and on the nature
Thickeners are used to modify the rheolog- and amount of film-forming auxiliaries and other
ical properties of emulsion paints. Rheological additives in the formulation. The MFT range
properties include viscosity, consistency, appli- may extend from −5 to +50 ◦ C; in the case of
cation behavior, coating resistance, splashing house paints and wall paints the range is + 5 to
during roller application, leveling, covering of + 10 ◦ C.
butt surfaces and edges, pouring resistance, set-
tling behavior, and storage stability (postthick- Production. Emulsion paints are produced
ening). in paddle mixers, of which high-speed dispersers
Similar to all other auxiliaries, thickeners are by far the most widely used and effective.
influence the water retention and open time, High shear forces are produced in these dis-
water resistance, washfastness, abrasion re- persers which account for their good dispers-
sistance, weather resistance, and gloss. The ing action. With some viscous, coarsely filled
most important thickeners are methyl cellu- emulsion paints, however, the shear forces can
lose and hydroxyethyl cellulose. The viscos- destroy the dispersion; beam agitators are more
ity rises with increasing polymerization of the suitable in this case.
cellulose ether. Synthetic thickeners based on
poly(meth)acrylates, polyvinylpyrrolidone, and Properties. The most important properties of
polyurethanes are also important. Inorganic emulsion paints are their rheology (which af-
thickeners include layer silicates of the montmo- fects the application properties); hiding power
rillonite type (e.g., aluminum silicate and mag- (extinction); pigment volume concentration (in-
nesium silicate). They confer a better washfast- fluences stress, water uptake, water vapor per-
ness and abrasion resistance than the cellulose meability, weather resistance); water vapor and
ethers and polyacrylates. However, they develop water permeability (influences the moisture bal-
a lower water retention capacity (open time). ance of the substrate and thus the durability and
Film-forming auxiliaries are high-boiling protection of the substrate against weathering);
solvents that promote film formation and re- adhesion to the substrate (particularly with alter-
duce the minimum film-forming temperature. nating moist–dry, moist–hot, and moist–frosty
They act as temporary plasticizers until the end conditions); and the elasticity (in the case of
of film formation and then evaporate during the crack-covering coatings and wood coatings).
drying phase. Film-forming auxiliaries include
butyl diglycol acetate, butyl diglycol, glycol Application. Emulsion paints can be applied
ether, and glycol ether esters, which in some by brush, roller, dipping, inundation, and spray-
cases are also termed plasticizers. An example ing. A wide range of qualities of emulsion paints
of one of the most important types is dibutyl with tailor-made properties can be produced
phthalate. from the available binders, thickeners, and aux-
Film formation is the physical “solidifica- iliaries.
tion” of an emulsion paint. Water evaporates
from the wet coating film and the polymer par-
 Paints and Coatings 95

Types of Emulsion Paints. The most im- 1950s of the technique known as dispersion
portant types of emulsion paints are the follow- polymerization [263]. This process provides a
ing: means of preparing nonaqueous polymer dis-
Emulsion lacquers have a pigment volume persions in a controlled manner. A wide range
concentration of 15–20 % and contain almost ex- of such dispersions have been made, mainly by
clusively TiO2 and finely particulate inorganic free-radical addition polymerization.
and organic colored pigments with which satis- As with many technological advances, how-
factorily leveling paints with a uniformly high ever, the development of stable, nonaqueous col-
surface gloss can be formulated. Emulsion lac- loidal dispersions posed theoretical problems in-
quers are produced mainly with fine, pure acry- cluding the mechanism responsible for their sta-
late dispersions. Lacquers used for industrial bilization. Electrostatic stabilization, operative
coatings are also emulsion lacquers. in many aqueous systems, could not account for
Exterior-use paints have a pigment volume the stability of dispersions in low dielectric me-
concentration of 30–55 %. They may be for- dia and the concept of steric stabilization was
mulated with all of the aforementioned disper- proposed [264].
sions. Properties are adapted as appropriate to
the substrates, climatic conditions, market cir- Steric Stabilization. Steric stabilization in-
cumstances, etc. The most important properties volves interactions between polymer chains lo-
of exterior-use paints are their water and water cated on the surface of particles [265–268]. Sta-
vapor permeability (moisture balance), chalking bilizing repulsive forces are generated by the in-
resistance, and adhesion to the substrate. Spe- teraction of polymer chains located on approach-
cial requirements apply in certain areas of appli- ing particles. These forces are related to the free
cation (e.g., CO2 protection on reinforced con- energy changes accompanying the increase in
crete, fungal and algal resistance in moist sur- the concentration of polymer segments during
roundings, crack bridging on cracked substrates, interpenetration or compression of the polymer
and alkali resistance on new mineral substrates). chains. For practical purposes, sterically stabi-
Interior-use paints have a pigment volume lized dispersions are achieved if:
concentration of up to 80 % depending on the re- 1) Every particle in the dispersion carries a com-
quired surface effects. The gloss, cleaning abil- plete sheath of solvated polymer chains, each
ity, mechanical strength, washfastness, and abra- chain being anchored at one or a few points
sion resistance decrease with increasing pigment to the particle surface. Solvated denotes that
volume concentration. the liquid phase of the dispersion would be a
Tinting paints are used to tint and shade good solvent for the polymer chains if they
emulsion paints. They contain colored pigments were not anchored to the particle surface.
and wetting agents to ensure good color devel- 2) The chains are so strongly anchored to the
opment in white emulsion paints. particle surface that the sheath remains in-
Synthetic resin-bound plasters contain, in ad- tact during encounters with other particles.
dition to the components of an emulsion paint, 3) The sheath of polymer chains is thick enough
coarse aggregates (sand, marble chippings, col- to render the van der Waals attraction bet-
ored stones) to produce decorative effects. ween the particles insignificant at their point
of closest approach. In general, all polymer
chains are long enough to provide such a
3.6. Nonaqueous Dispersion Paints sheath [264].
The term nonaqueous dispersions can be ap- Simple homopolymers or random copoly-
plied to all particulate dispersions in any liquid mers that are solvated by the dispersion medium
medium other than water. It has, however, come are only weakly adsorbed to the surface of
to have a more restricted meaning, namely, par- the polymer particles and cannot therefore pro-
ticulate dispersions of organic polymers in or- vide the strongly anchored sheath of solvated
ganic liquids. polymer chains necessary for steric stabiliza-
The upsurge of interest in this type of col- tion [269]. Block and graft copolymers play a
loidal system followed the development in the key role in the steric stabilization of nonaqueous
96 Paints and Coatings

dispersions. Block and graft copolymers contain In dispersion polymerization, sufficient graft
long runs of identical monomers in the polymer copolymer must be present to satisfy the increase
chain (block) or in side chains (graft): in particle surface area as polymerization pro-
ceeds. The graft copolymer can be either made
in situ as a side reaction during dispersion poly-
merization, or it may be premade and added as
required. The side reaction for the formation of
the graft copolymer occurs in two ways:
1) Hydrogen abstraction grafting to a simple
polymer dissolved in the diluent for the dis-
persion [271]
To provide strong adsorption (i.e., anchor- 2) Copolymerization with a dissolved polymer
ing of a solvated polymer sheath) to the surface carrying a copolymerizable residue (stabi-
of the particle, at least one component of the lizer precursor) [272]
block or graft copolymer must be solvated by In hydrogen abstraction grafting, the initia-
the medium and at least one component must be tor abstracts a hydrogen atom from the main
insoluble in the medium and preferably compat- dissolved polymer. The graft copolymer is then
ible with, or identical to, the polymer particle to formed by free-radical copolymerization of an
be dispersed. appropriate monomer:

Block and Graft Copolymer Stabilizers

in Dispersion Polymerization. A sterically-
stabilized, nonaqueous, polymer dispersion is
made simply by heating a solution of a free radi-
cal initiator (e.g., azobisisobutyronitrile), an ap-
propriate monomer, and a suitable block or graft
copolymer in an organic liquid which is a non- For optimization of the hydrogen abstraction
solvent for the polymer product and acts as a grafting process, the soluble polymer must be
diluent for the dispersion. The block or graft carefully chosen and should be used with an
copolymer acts as a stabilizer for the dispersed initiator that generates very reactive free radi-
polymer obtained by free radical polymerization cals (e.g., benzoyl peroxide). Adventitious hy-
of the monomer. Although both block and graft drogen abstraction and grafting can also occur.
polymers can act as stabilizers, graft polymers Many dispersions, in which steric stabilization
are normally used because they are more easily is claimed to arise from the adsorption of simple
synthesized. soluble polymers, may thus actually be stabi-
Although dispersion polymerization is simi- lized by graft copolymers formed in situ during
lar to conventional aqueous emulsion polymer- the preparation of the dispersions [273].
ization, there are some crucial differences. In Although the hydrogen abstraction process is
dispersion polymerization, the monomer is usu- a useful technique for many practical purposes,
ally soluble in the organic liquid in which the it is not easy to control. Control is considerably
polymer dispersion is to be made; a surfactant is improved when a diluent-soluble polymer carry-
therefore not necessary to maintain the monomer ing one or a few copolymerizable groups, often
in emulsion form. Since the monomer is in solu- known as a stabilizer precursor, is used under
tion, agitation of the polymerizing system is of conditions that minimize hydrogen abstraction
secondary importance. Furthermore, in contrast grafting (e.g., use of initiators such as azobi-
to emulsion polymerization, the initiator frag- sisobutyronitrile that produce moderately reac-
ments do not stabilize the resulting dispersion. tive free radicals).
The initiator to monomer ratio can therefore be Stabilizer precursors can be made by copoly-
used to control the molecular mass of the poly- merization of a monomer that contains a con-
mer without affecting the particle size of the dis- densable group. The copolymer is then reacted
persion [270]. with a monomer containing a complementary
 Paints and Coatings 97

group. For example, lauryl methacrylate may and technological applications, block copoly-
be copolymerized with hydroxyethyl methacry- mers ionic initiation and “living polymer” tech-
late. The resulting copolymer contains hydroxyl niques have been used [277, 278]. The growing
groups that can be esterified with methacrylic polymer chains remain active until they are de-
acid, thereby introducing copolymerizable vinyl liberately quenched. These processes yield poly-
groups: mers that are monodisperse with respect to mo-
lecular mass. Measurements made on disper-
sions, sterically-stabilized with almost monodis-
perse block copolymers, yield results which are
more readily interpreted.
Stabilizer precursors can be used in con-
ventional dispersion polymerization only be-
A more convenient way is to use the addi-
cause the starting reaction mixture is homoge-
tion reaction of a carboxylic acid and a polymer
neous. Some nonaqueous dispersions, however,
containing an epoxide group [272]:
are made by processes in which one or more of
the reactants is/are insoluble in the liquid diluent
(e.g., polycondensation) [279]. In these cases,
preformed graft copolymers must be used be-
cause they function not only as stabilizers for
the final dispersion, but also as dispersants or
emulsifiers for the starting materials.
An alternative type of stabilizer precursor can In order to maintain stability, the solvated
be made by polymerizing a monomer with an sheath must remain anchored to the particle sur-
initiator (e.g., azobiscyanovaleric acid) in the face. In some circumstances (e.g., exposure to
presence of a transfer agent (e.g., thioglycolic strong solvents which tends to swell the par-
acid); both initiator and transfer agent have the ticles), anchoring can fail during preparation
same condensable group (in the above case a and use of the resulting dispersion. This can be
carboxylic acid group) [274, 275]. Under suit- avoided by including in the anchor component
able conditions, > 95 % of the resulting poly- of the block or graft copolymer a group which
mer chains carry a single terminal condens- is capable of coreacting with the polymer being
able group. When the polymer is reacted with a formed in the polymerization or condensation
monomer containing an appropriate group (e.g., process as the particles are being made [280].
a carboxyl-terminated polymer with glycidyl The solvated sheath on the particles can then
methacrylate), a monofunctional stabilizer pre- only be removed by totally disrupting the parti-
cursor is produced (i.e., it has a single terminal cles.
copolymerizable group).
The development of monofunctional precur- Characterization. The solvated sheath
sors led to the production of graft copolymers which provides the steric stabilization of non-
that were fairly pure, in that they were relatively aqueous dispersions has been extensively stud-
free from ungrafted polymer. Monofunctional ied. Hydrodynamic techniques have been used to
precursors can also be made by condensation measure the thickness of the sheath [281, 282],
[275]. Indeed, graft copolymers made by the co- low angle neutron scattering to measure the
polymerization of monomers with the reaction polymer segment distribution within the sheath
product of glycidyl methacrylate and the self- [283], and compression experiments to mea-
condensate of 12-hydroxystearic acid [276] have sure the strength of the sheath–sheath interac-
been used extensively in dispersion polymeriza- tion [266, 284]. The importance of the solvation
tions, not only for technological applications, power of the medium for steric stabilization has
but also to study the mechanisms of dispersion been demonstrated by flocculation experiments
polymerization and steric stabilization. [285]. Flocculation is observed as the solvent ap-
The emphasis so far has been placed on pro- proaches the “theta” condition for the unattached
cesses which, by their random nature, lead to polymer chains, both by using solvent mixtures
polydispersity. For some fundamental studies and by change of temperature. The theta con-
98 Paints and Coatings

dition is the state at which the configurational fore only has a significant effect on the effective
entropy losses caused by constraints on the poly- volume fraction, and hence the rheology of the
mer molecule are balanced by an increase in en- dispersions, when the dispersed particle size is
ergy associated with polymer segment associa- very small and/or the volume fraction of the dis-
tion. persion is very high. Dispersions of high molec-
Flocculation has also been observed when the ular mass polymers have a much lower viscosity
diluent of the dispersion is a good solvent for than their solutions at the same temperature.
the chains constituting the steric barrier. This Dispersions with uniform particle size have
is observed when free polymer, even when it is been used to model the rheological behavior
identical to that constituting the steric barrier, is of dispersions of noninteracting hard spheres
dissolved in the diluent of the dispersion [286]. [295]. Liquid dispersions with the appropriate
The magnitude of flocculation is a function of particle size distribution have been made with a
both the molecular mass and the concentration very high volume fraction [296].
of the added polymer. The depletion flocculation
theory suggests that this phenomenon is related Uses. Nonaqueous polymer dispersions have
primarily to the perturbation of the free poly- been used as the main film former in thermoplas-
mer chains in solution rather than those in the tic and, more sucessfully, in thermosetting au-
solvated sheath [287]. tomotive coating compositions [297]. The sys-
The anchoring of the solvated sheath to the tems have the advantage of a higher solids con-
surface of the polymer particles has received rel- tent at application and hence lower emission of
atively little attention. At least one component volatile organic solvents. Cross-linked particles
of a graft or block copolymer must be insoluble when swollen with solvent have been used as
in the diluent for the dispersion. Preferably, the rheological control agents to improve the ap-
anchor component should be identical to or com- plication of spray coatings in which the main
patible with the polymer constituting the parti- film former is solventborne [298–300]. Discrete
cles. There is some evidence that anchor poly- polymer particles in a continuous matrix have
mer segments which are incompatible with par- also been used to improve the properties of the
ticle polymers tend to clump at the surface of the final paint films [301, 302]. Nonaqueous disper-
particles [288, 289]. sions have proved convenient for the production
Similarly, the structure of polymer particles of polymer in a form suitable for powder coating
produced by dispersion polymerization has not applications [303].
been extensively studied. The kinetics of clas- More generally, nonaqueous dispersions
sic dispersion polymerization imply that particle have been used as components of polishes [304],
nucleation is followed by gel-phase polymeriza- adhesives [305, 306], fiber coatings [307], textile
tion within the particles. This suggests that the impregnating agents [308], printing inks [309,
resulting particles should have a fairly homo- 310], and electrophotographic toners [311, 312].
geneous structure [290, 291]. There is evidence, Finally, the preparation of nonaqueous poly-
however, that in some circumstances (e.g., when mer dispersions has been used as a technique for
the monomer is not a good solvent for the result- polymer production. Process advantages such
ing polymer), polymerization occurs predomi- as the use of lower temperatures for polyamide
nantly in solution. The polymer then precipi- and polyester synthesis can be obtained [279].
tates out and is swept onto the surface of ex- Products such as synthetic elastomers can be ob-
isting particles leading to a more heterogeneous tained in powder form [313]. The fine particu-
structure [292]. Fluorescence quenching studies late form of dispersions of water-soluble poly-
on dispersions made from labeled reactants have mers (e.g., polyacrylamide) offers a convenient
confirmed the heterogenicity of particles made route to aqueous solutions of polymeric floccu-
by some dispersion polymerization procedures lants and thickeners [314].
[293, 294].

Properties of Nonaqueous Dispersions.

The stabilizing solvated sheath of nonaqueous
dispersions is of limited dimensions. It there-
 Paints and Coatings 99

3.7. Radiation-Curing Systems used in metal finishing and can coatings mainly
because of their high adhesion.
3.7.1. Introduction Prepolymers and monomers bearing acrylic
functionalities still dominate the radiation cur-
Radiation curing is a relatively new technology ing market and are discussed in more detail here.
which uses electromagnetic (mainly UV) or ion-
izing (mainly accelerated electrons) radiation to
initiate a chain reaction in which mixtures of 3.7.2. Radiation-Curable Systems Based on
polyfunctional compounds are transformed into Acrylates
a cross-linked polymer network.
A UV-curable acrylate system usually con-
Resin Systems. Radiation-curable resin sys- tains four main components: prepolymer(s),
tems can be classified as follows: monomer(s), photoinitiator(s), and additives.
A fully formulated EB-curable system is not
1) Polyester–styrene mixtures
merely a UV system without photoinitiator but
2) Products with methacrylic groups
the same principles apply and the same raw ma-
3) Thiol–thiene mixtures
terials are used.
4) Prepolymers and monomers with acrylic
functionalities
Prepolymers. A broad range of acrylated
5) Epoxy resins
resins (oligomers) are commercially available.
The polymerization of all these systems can be The film-forming properties depend on the
divided into initiation, propagation, and termi- oligomer system. One of the most common
nation steps. The initiation step involves gener- is the acrylated epoxy system. In acrylated
ation of a reactive species (free radical or acid). urethanes, an isocyanate-functional prepolymer
During irradiation with UV light, the reactive with a polyol backbone can be reacted with
species are formed by chemical decomposition a hydroxy-functional monomer (e.g., hydroxy-
of a photoinitiator. In electron-beam (EB) cur- ethyl or hydroxypropyl acrylate). Many different
ing, reactive species (radicals) are generated by resins can be synthesized by varying the polyol
interaction of accelerated electrons with organic backbone, the isocyanate type, and the hydroxy-
compounds. functional monomer. Polyester acrylates are an-
In systems 1–4 radical polymerization takes other example of commercially important pre-
place. Decomposition of the photoinitiator (e.g., polymers. Acrylated acrylics have an acrylic
benzoin and its derivatives) leads to formation backbone with pendant acrylate functionality.
of free radicals which react with the carbon– Selection of the prepolymer is guided by the
carbon double bonds. In system 5 acidic reac- desired film-forming properties. For example,
tive species are formed which react with cy- acrylated epoxy resins typically provide hard,
cloaliphatic epoxy compounds and vinyl ethers solvent-resistant films with fast cure at relatively
to form a cross-linked network. Diazonium, sul- low cost. Acrylated urethanes may be chosen
fonium, and iodonium salts are used to initiate for their excellent film flexibility and tough-
this cationic polymerization, a typical example ness. Aliphatic urethanes are used in prefer-
is Ph3 S+ PF−6. ence to aromatic urethanes for stringent exte-
Polyester–styrene resins have a low raw ma- rior weatherability requirements. The acrylated
terial price and are used in wood finishing. Dis- acrylics offer excellent nonyellowing properties
advantages are the presence of volatile styrene when a soft film can be used.
and the low cure speed. Products with methac- Polyester acrylates are used in a wide range
rylic groups are used where line (cure) speed is of applications from overprinting varnishes to
less important, mainly in combination with acry- lithographic (offset) inks.
lates in special end uses (e.g., in the electronics
industry) to improve adhesion or to obtain spe- Monomers. In radiation-curable systems,
cific physical properties. Thiol–thiene mixtures the solvent is replaced by reactive diluents
can lead to very flexible cured films but their (monomers) which are incorporated in the net-
odor seriously limits their use. Epoxy resins are work during cross-linking. These monomers
100 Paints and Coatings

have two important functions: they reduce the manipulations and installation are easy, and only
viscosity of the mixture and they strongly in- minimal floor space and manpower are needed.
fluence the physical and chemical properties of A further advantage is that the finished products
the final coating. Monomers can be divided into are of high quality.
three groups:
Disadvantages. Raw material costs are high
1) Monofunctional monomers: improve the
but taking into account solvent recovery costs for
flexibility of the end product (e.g., isobornyl
solvent-based systems this is changing in favor
acrylate, N-vinylpyrrolidone).
of radiation curing. The products used are po-
2) Difunctional monomers: e.g., hexanediol di-
tentially hazardous (irritant) and special precau-
acrylate (HDDA), tripropylene glycol di-
tions must be taken for safe handling. Because of
acrylate (TPGDA).
the extremely high reactivity and fast cure, there
3) Tri- or tetrafunctional monomers: increase
is a tendency for shrinkage leading to adhesion
the cross-linking density of the final coat-
problems on certain substrates.
ing. Examples include trimethylolpropane
triacrylate (TMPTA), pentaerythritol tri- or
tetraacrylate (PETA). 3.7.3. Equipment

Additives can be extremely important in Radiation curing requires only a fraction of a

high-performance radiation-curable formula- second exposure to the UV or EB source.
tions. Pigments for inks or coatings, fillers for
cost control or viscosity control, defoamers and UV Curing. The UV lamps are usually
wetting agents, flatting agents and slip aids can medium-pressure mercury lamps or electrode-
all play essential roles in UV/EB inks and coat- less gas-filled lamps. Cooling is necessary to
ings. Reactive additives such as surfactants or avoid overheating of the lamp which would lead
slip aids to avoid migration in the final coating. to decreased lifetime and changes in the spectral
output.
Photoinitiators are essential for UV-curable Semielliptical reflectors are commonly used
systems and can be classified into two groups: to concentrate the light and cure coatings applied
to a moving flat substrate. Parabolic reflectors
1) Photoinitiators that produce radicals by provide a parallel beam of light and are mainly
intermolecular abstraction of hydrogen (e.g., used to cure coatings on uneven substrates.
benzophenone, thioxanthone). These prod-
ucts require a co-initiator (e.g., tertiary EB Curing. Electron-beam accelerators
amines, acrylated amines). (150–300 kV) used in finishing plants are of two
2) Photoinitiators that produce radicals by types:
intramolecular photocleavage (e.g., benzoin
ethers). 1) Scanner type: electrons are generated from
a point cathode in high vacuum. They are
Radical polymerization is inhibited by oxy- then focused, accelerated, and scanned along
gen, leading to tacky surfaces. This can be over- the scan horn whose length is adjusted to the
come in UV-curable formulations through the coating width.
use of amines (co-initiator) and in EB formula- 2) Linear cathode type: electrons are emitted
tions by working under an inert atmosphere. from suspended wire cathode(s). Contrary to
the scanner-type accelerators, electrons are
Advantages. An important ecological ad- not focussed but are emitted over the total
vantage is that only reactive products are used; length of the wire(s).
this means that there is no solvent recovery prob-
lem and no pollution. Energy consumption is
low. Curing is performed at room temperature 3.7.4. Fields of Application
so heat-sensitive substrates can be used.
Perhaps the most important advantage is the Radiation curing is used for protective coatings,
economic aspect. Curing is done at high speed, inks, adhesives, and in other minor areas.
 Paints and Coatings 101

Coatings are either clear or pigmented. dimensional modeling (stereolithography) in

Coatings for paper include clearcoats for lam- which a solid part is made from a vat of UV-
inated paper on pressboard (wood-grain pa- curable liquor by the use of UV lasers controlled
pers to simulate natural wood). Inks and over- by computers using CAD/CAM software.
print varnishes for the graphic art industry are Release coatings (casting paper, caul sheet,
a large, rapidly growing segment. High-gloss labels) are manufactured by EB curing. Other
overprint varnishes for magazine covers, record new applications of radiation curing include
jackets, and other consumer items are also often binders for magnetic media, leather coatings,
radiation-cured. and paper upgrading.
Plastic coatings for interior and exterior ap-
plications are also an important use segment. Im-
portant factors are cost, adhesion, weatherabil- 3.8. Electrodeposition Paints
ity, and availability of raw materials.
The coating of wood is an important use of ra- Electrodeposition (electrophoretic) coating was
diation curing. Three-dimensional curing is very developed in the 1960s as a method of prim-
difficult and requires spray application, good ing electrically conducting bulk articles for in-
control of film thickness, and well-engineered dustrial use [315]. A high application efficiency
curing lines to assure complete cure of coated (> 95 %) can be achieved by using ultrafiltra-
objects (e.g., chairs). UV-curable coatings are tion techniques [316] and has promoted the use
also used for cork in Spain and Portugal. of electrodeposition. In 1989 ca. 90 % of all auto-
Adhesion to metal is sometimes difficult to mobiles and many industrial goods were primed
achieve. However, due to the development of by electrodeposition. The market volume for
adhesion promoters industrial applications on electrodeposition paints in Europe in 1988 was
metal exist. Electronics applications are impor- estimated to be ca. 90 000 t/a, corresponding to
tant; photoresists (both wet and dry film), solder a turnover of ca. 470×106 DM. The increase
masks, potting compounds, and conformal coat- in sales in the Federal Republic of Germany in
ings are products based on UV-curable materi- 1989 was ca. 8 % [317].
als.
Optical fibers have been coated with a pro- Properties. Electrodeposition paints are
tective layer of UV-curable materials for a long aqueous dispersions of organic polymers which
time. are used to apply organic coatings to electrically
conducting substrates by passage of direct cur-
Inks. Radiation-curable inks are applied to rent [318–320]. When direct current flows bet-
metal, paper, wood, and plastics (→ Printing ween two electrodes, charged dispersion parti-
Inks). Lithographic (offset) and screen print- cles are deposited on one of the electrodes in
ing inks are the most important printing inks. a diffusion-controlled boundary layer after an
Flexographic inks are known but it is difficult induction time t i . Coagulation of the particles
to achieve the low viscosity required for this occurs as a result of the change in pH value
printing technique while maintaining the good caused by the electrolysis of water [321]. If the
cured ink requirements. Intaglio inks (special surface charge of the dispersion particles is pos-
inks used to avoid counterfeiting of items such as itive, coagulation occurs at the cathode [322]; if
bank notes) are also employed and ink-jet print- the charge is negative, coagulation occurs at the
ing with UV-curable materials is starting. anode [323]. The deposited polymer particles
consolidate due to electroosmosis and rapidly
Adhesives are well established, mostly produce a high electrical resistance that slows
in lamination. Some UV-curable pressure- down deposition [324]. This behavior results in a
sensitive adhesives are used in the automotive uniform coating, even of parts with complicated
industry. shapes (e.g., automobile bodies). The surfaces to
be coated are pretreated with inorganic conver-
Other uses include the production of flex- sion layers (usually zinc phosphate) to improve
ographic printing plates from UV-curable ma- adhesion of the electrocoat and corrosion pro-
terials. An interesting application is three- tection [325].
102 Paints and Coatings

The compositions of cathodic and anodic trodes with the help of ion-exchange membranes
electrodeposition baths are given in Table 17. [327].
The main components are resins, pigments, ex-
tenders, some solvent, and neutralization agents. Binders. The first important anodic elec-
The latter are used to neutralize the charge on the trodeposition paints were formulated with un-
resins so that they become water dispersible. The saturated oils that were functionalized with
application data affect the plant and equipment maleic anhydride. Reaction with maleic an-
technology (e.g., choice of construction mate- hydride was followed by semiesterification of
rials, energy consumption, and rectifier design) the succinic anhydride derivatives [328]. These
[318, 326]. resins are cross-linked by oxidative radical poly-
merization via their residual double bonds.
Table 17. Typical bath and application data of electrodeposition Specially developed polybutadiene oils sub-
paints
sequently replaced natural oils as raw mate-
rials. Unsaturated polyesters, saturated poly-
esters, and alkyd resins can be dispersed in water
at an acid index of 40–80 mg KOH/100 g solids
after neutralization with amines, and can be
used as anodic electrodeposition paints. Acrylic
copolymers form an important class of binders
for one-coat, weather-resistant coatings. These
electrodeposition paint binders can easily be
synthesized by copolymerizing acrylic acid with
unsaturated carboxylate esters and/or vinylo-
gous compounds.
Cathodic electrodeposition paints important
Electrodeposition tanks range in size from for corrosion-resistant priming coats are based
0.2 to 400 m3 depending on the objects being on modified epoxy resins that contain amino
coated and the throughput rate. Tanks may be groups. Dispersion is obtained by neutraliz-
operated batchwise or continuously. The former ing the amino groups with organic acids [329,
are mainly used for truck bodies and small mass- 330]. Acrylic resins modified with amino groups
produced parts, the latter for high throughputs as can also be used for cathodic one-coat paints.
in car body priming. In addition to the coating Polybutadienes can be modified for cathodic de-
tank, the most important parts of the unit are the position (e.g., by amidation with diamines after
counter electrodes, rectifier, circulating pumps, reaction with maleic anhydride). Blocked iso-
heat exchanger, filters, rinsing zones, and ultra- cyanates are mainly used as cross-linking agents
filtration units (see Section 8.3.3) [318]. [331, 332]. The properties of cathodic electrode-
The non-water-soluble resins are converted posited coatings are listed in Table 18.
into a soluble (i.e., ionized) state by using
neutralizing agents (e.g., acetic acid). In or- Table 18. Properties of cathodic electrodeposited coatings [333]

der to maintain constant bath composition and

thus constant coating quality, two compensation
methods are used for feeding the baths. In the
first method the neutralizing agent released dur-
ing the deposition period is used to disperse un-
derneutralized, often one-pack feed material in
the bath. The solids content of the bath is, how-
ever, usually kept constant by using fully neu-
tralized, uniformly predispersed material. Ex-
cess neutralizing agent must then be removed
through a circulation system at the counter elec- Conventional paint additives (e.g., cross-
linking catalysts, corrosion inhibitors, and sur-
 Paints and Coatings 103

factants) are used to complete the formula- corrosion protection) on a surface coating. For
tion of commercially employed electrodeposi- optimization of these effects the colorants must
tion paints. Dispersion mixtures for modifying be mixed in a suitable manner and in appropriate
film properties have also been described [333]. amounts with the relevant binder. The distribu-
tion of the primary pigment particles in the poly-
Environmental Protection. On account of mer matrix should be as uniform as possible.
the high paint transfer efficiency and low sol-
vent content, environmental pollution in elec-
trodeposition coating is much lower than with 4.1. Inorganic Pigments [339–347]
spray coating. The solvent contents of electrode-
position paints relative to the solids content are In this section the emphasis is on inorganic pig-
5–10 % in comparison with solventborne spray ments for topcoats and finishing coats. Func-
paints with a solvent content of 50–100 %. The tional pigments (e.g., for corrosion protection)
most important sources of emission are the elec- are discussed to some extent in more detail in
trodeposition tank, the rinsing zone, the stoving Section 11.1. The particle size of inorganic pig-
oven, and the drain of the ultrafiltrate [334]. De- ments used in paints is 0.05–10 µm, that of
velopments in new electrodeposition paints aim transparent pigments 0.01–0.05 µm. The pig-
to reduce the organic volatile solvent content, to ment volume concentration in gloss paints is
have fewer condensation products in the stoving 10–35 % but may reach >80 % in matt emul-
ovens, and to have lead-free formulations [335]. sion paints. For a detailed discussion of inor-
ganic pigments, see → Pigments, Inorganic.
Uses. Electrodeposition coatings are used
primarily for corrosion protection of steel (e.g., White Pigments. The most important white
in automobiles, agricultural machinery, steel fur- pigment for surface coatings is titanium diox-
niture, and appliances). New areas of application ide [13463-67-7] with a worldwide consump-
include coil coating primers [336], beverage can tion in 1989 of ca. 1.8×106 t (60 % of total con-
coatings [337], and photocurable electrodeposi- sumption). World wide consumption in 1995 is
tion paints as photoresists [338]. ca. 3.1 x 106 t [588]. Of the three known crystal
modifications, only rutile and anatase are pro-
duced synthetically and utilized on a commer-
4. Pigments and Extenders cial scale. The brookite modification has no eco-
nomic importance. The light scattering capac-
Pigments, dyes, and extenders are defined ity of titanium dioxide is superior to all other
in DIN 55 943 under the heading “colorants” white pigments due to its high refractive in-
(coloring materials). Further standards are dex; pigmented coatings therefore have an ex-
DIN 55 944 and 55 949. Similar definitions tremely good hiding power. When combined
are given in ASTM D 16–84, ISO 4617, and with colored pigments, titanium dioxide exhibits
ISO 4618. A pigment is defined as a substance the highest brightening power of all industrially
that is insoluble in the application medium (e.g., produced white pigments. On account of these
a paint) and is used as a colorant or on account of unique optical properties, its toxicological in-
its corrosion-inhibiting or magnetic properties. nocuousness, and its chemical resistance, tita-
A dye is defined as a colorant that is soluble in nium dioxide has largely replaced all other white
the application medium. pigments.
Extenders are sometimes difficult to distin- Doping the crystal lattice and coating the sur-
guish from pigments; they are defined as sub- face with metal oxides or hydroxides has re-
stances that are insoluble in the application duced the photocatalytic polymer decomposi-
medium and are used to increase the volume, ob- tion caused by titanium dioxide to such an extent
tain certain technical properties, and/or improve that all stability requirements can be met. Since
optical properties (see also Section 4.3.1). anatase is generally more photoactive than ru-
Pigments, dyes, and extenders are incorpo- tile, aftertreated and/or lattice-stabilized rutile
rated in binders to obtain decorative effects (e.g., pigments are preferred for exterior applications
color, gloss, dulling) or functional effects (e.g., (exposure to sunlight).
104 Paints and Coatings

Commercial products include Bayertitan be used in paints because they have better disper-
(Bayer); Finntitan (Kemira Oy, Vuorikemia); sion properties. Pigments surface-coated with
Hombitan (Sachtleben); Kronos (Kronos Titan); metal oxides (e.g., Al2 O3 ) frequently exhibit
Tibras (Titanio do Brasil); Tiofine (TDF Tiofine good flocculation stability.
BV); Tiona (SCM Chem.); Tioxide (Tioxide Commercial products include Bayferrox
Group); Tipaque (Ishihara S.K.); Tripure (Du (Bayer) and Deanox (Deanshanger Oxide
Port); Titafrance (Thann et Mulhouse); and Works). Other manufacturers include S.I.L.O.,
Tronox (Kerr McGee). Columbian Chemical Company, and Mobay.
White pigments of historic importance or less
economic importance than titanium dioxide in- Chromium Oxide Pigments are composed
clude zinc sulfide, lithopone (mixtures of ZnS of chromium(III) oxide [1308-38-9], Cr2 O3 ,
and BaSO4 ), zinc oxide/zinc white (ZnO pro- crystallized in a corundum lattice. This crystal
duced from metallic zinc by oxidation of metal structure impact has a certain degree of hard-
vapors), and white lead (basic lead carbonate, ness and abrasivensss. On account of their ex-
2 PbCO3 ·Pb(OH)2 ). On account of their specail cellent colorfastness and insolubility in solvents,
properties these pigments have been able to com- acid, and alkali, chromium oxide pigments have
pete against titanium dioxide in some applica- successfully competed against more brilliant or-
tions. Special properties of zinc sulfide and litho- ganic green pigments. Hydrated chromium ox-
pone are their low absorption in the near UV ide pigments are less important. Pure chromi-
range; they can therefore be used to color UV- um oxide pigments are not toxic. About half of
curable paints. Lithopone-pigmented putties can the consumption of chromium oxide pigments in
easily be sanded and have favorable rheological the Western World (total production, 48 000 t in
properties. The luster of lithopone is used to ad- 1995) was used for coating materials.
vantage in wallpaper coatings. Zinc sulfide and Manufacturers include Bayer (green chro-
white lead are sometimes used in coating mate- mium oxide) and British Chrome and Chemicals
rials because of their fungicidal properties and and Nikon Kagagu (chromium oxide).
to neutralize acid to protect against corrosion.
Also, the lower abrasivity in comparison to TiO2 Mixed Metal Oxide Pigments. This term
pigments can be of importance. usually refers to metal oxide pigments that are
derived from spinel (MgAl2 O4 ), rutile (TiO2 ),
Iron Oxide Pigments. Iron oxide pigments hematite (α-Fe2 O3 ), or bixbyite (α-Mn2 O3 )
may be natural or synthetic, the synthetic oxides structures. Substitution of metal ions in the host
have a wider color range and more uniform qual- lattice by other chromophoric metal ions opens
ity. Worldwide consumption of synthetic iron up a broad color spectrum. The oxidic mixed-
oxides in 1989 was 500 000 t, coating materi- phase pigments generally exhibit outstanding
als accounted for about 185 000 t. The color lightfastness and resistance to weathering, heat,
range includes the basic colors red (α-Fe2 O3 , and chemicals. Heavy-metal ions can only exect
hematite), black (Fe3 O4 , magnetite), yellow (α- their toxic effects in dissolved form. Since these
FeOOH, goethite), and orange (γ-FeOOH, lep- pigments are sparingly soluble, they may be
idocrocite). Mixtures of these colors are used classified as toxicologically innocuous. Around
as brown pigments; the γ-Fe2 O3 (maghemite) half the production capacity of ca. 11 000 t
normally used for magnetic recording purposes (1988) was processed into coating materials.
can, however, also be used to impart brown col- Commercial products include Heucodur
oration. Manganese- and chromium-containing (Dr. H. Heubach); Irgacolor (Ciba-Geigy);
iron oxide phases are important as heat-stable Kerafast (Blythe Colours); lightfast pigments
brown pigments (e.g., for stoving enamels). (Bayer); mixed-phase pigments (Degussa,
Iron oxide pigments are extremely important Ferro B. V., Ferro Corporation, Shephard
in coating materials due to their outstanding hid- Chemical Corporation); and Sicopal; Sicotan
ing power, excellent lightfastness and weather (BASF Lacke und Farben).
resistance, insolubility in water and organic sol-
vents, resistance to alkalis, and their toxicologi- Cadmium pigments may be regarded as
cal inertness. Only micronized pigments should mixed-phase pigments, and are derived from the
 Paints and Coatings 105

wurtzite lattice of cadmium sulfide (cadmium (130 000 t in 1988) is used in coating materi-
yellow). Partial substitution of cadmium by zinc als.
shifts the color of cadmium yellow to greenish Commercial products include Heucotron
shades. Replacement of the sulfide ions with se- (Dr. H. Heubach) and Sicomin (BASF Lacke
lenium yields orange to dark red pigments (cad- und Farben). Other manufacturers include Bur-
mium red). Of all inorganic pigments, cadmium rell Colours, Ciba-Geigy, Ten Horn B.V., ETS,
pigments exhibit the most brilliant shades; they and Capelle Frères).
have excellent hiding power and also a much
higher heat stability than organic pigments and Ultramarine pigments are sodium
are completely stable against bleeding. Public aluminum silicates of the composi-
discussion concerning environmental problems tion Na8 Al6 Si6 O24 ·Sx (Na-rich) or
has lead to a sharp fall in the consumption of Na8−y Al6−y Si6+y O ·Sx (Si-rich). Small sulfur-
cadmium pigments in paints. In the Federal Re- containing anions (e.g., S− −
3 and/or S2 ) are bound
public of Germany, only ca. 22 t of cadmium as chromophores in the interstices of the crys-
pigments were used in paints in 1986. tal lattice to equalize the charge. Depending on
Commercial products include Langue- composition, blue, red, green, or violet pigments
domer (Société Languedocienne de Micron can be obtained. Ultramarine pigments have a
Couleur); and Sicotherm (BASF Lacke und high heat resistance but their universal use in
Farben). Other manufacturers include Blythe paint systems is limited on account of their poor
Colours, Brown, Degussa, Ferro Corporation, hiding power and limited weather resistance.
Harshaw Chemical Company, and Reckitts Special types coated with silica must be used
Colours. In 1987 Bayer stopped production and when resistance to acids is required. Ultramarine
marketing of their Cadmopur pigments. pigments are regarded as being physiologically
innocuous. The worldwide ultramarine produc-
Bismuth pigments are based on bismuth or- tion capacity is ca. 30 000 t.
thovanadate [14059-33-7], BiVO4 or produced Manufacturers in Western Europe include
as the two-phase system BiVO4 –Bi2 MoO6 to Reckitts Colours, UK.
improve their colorfastness. The colors of this
group of pigments are similar to that of cadmium Blue iron pigments have the general com-
yellow. position M(I)Fe(III) (CN)6 ·H2 O, where M(I) is
Commercial products include Sicopal Yel- Na, K, or NH4 . These pigments have a very
low (BASF Lacke und Farben). high tinctorial strength, but are difficult to dis-
perse on account of their fine state of division
Chromate and molybdate pigments are and tendency to agglomerate. Micronized types
generally mixed-phase pigments from the sys- behave more favorably on dispersion. Thermal
tem Pb(Cr, S, Mo)O4 . They include chromium resistance (up to ca. 180 ◦ C) is generally suffi-
yellow (molybdenum-free) and molybdate or- cient for stoving lacquers. Stability to dilute acid
ange and red. Variations in shades are possi- is good, although there are problems in the al-
ble by adjusting the crystal modification (or- kaline pH range. These pigments can be used in
thorhombic or monoclinic) or proportion of free coatings for exterior use due to their lightfastness
lead sulfate. Pigments from the system PbCrO4 · and weather resistance. Their main area of appli-
PbO should also be classified in this group (chro- cation is, however, the printing ink sector. Blue
mium orange and chromium red). The chro- iron pigments are toxicologically innocuous. To-
mate and molybdate pigments have a high tinc- tal world production of blue iron pigments was
torial strength combined with good hiding power ca. 50 000 t in 1988, a considerable proportion
and brilliance. Depending on the nature and de- of which was used in paints and, in particular,
gree of stabilization, products are classified as printing inks.
standard, lightfast, or SO2 -resistant. Chromate Commercial products include Milori-
and molybdate pigments are classed as harm- blau (ETS, Capelle Frères) and Vossenblau
ful to health and must be identified. A consider- (L. Vossen und Co., Degussa).
able proportion (>60 %) of the total world pro-
duction of chromate and molybdate pigments
106 Paints and Coatings

Nacreous (pearlescent) pigments and in- tive sector has risen sharply in recent years (e.g.,
terference pigments generally consist of in the automobile topcoat and finish sector).
platelets with a high refractive index (at least Manufacturers in Western Europe include
in some regions in pigments with a layer struc- Eckart-Werke (Fürth, FRG) and Silberline Ltd.
ture) and a high transparency. The first such pig- (UK).
ments were based on natural products such as
fish silver, as well as synthetic products such as Transparent Pigments. Transparent coat-
bismuth oxychloride, BiOCl, and basic lead car- ings are obtained when there are slight differ-
bonate, Pb(OH)2 ·2 PbCO3 . Layered pigment ences between the refractive indices of the pig-
structures (especially coated mica particles) now ment and binder. Pigment particle sizes that
dominate, however. The mica surface is coated are substantially smaller than the wavelength
with a titanium dioxide layer of defined thick- of light must be used. Light scattering under
ness. The photoactivity of the titanium dioxide these conditions is very low and light absorp-
for exterior applications can be lowered by suit- tion predominates. Many transparent shades can
able aftertreatment (see page 103). Variations in be produced from colored inorganic pigments;
the layer thickness produce a range of interfer- examples include α- and γ-FeOOH (yellow), α-
ence colors. Lowering the titanium dioxide con- Fe2 O3 (red), α-CrOOH (green), and CoAl2 O4
tent or additional coating with Fe2 O3 or Cr2 O3 (blue).
(if necessary without a TiO2 layer) results in fur- On account of their fine state of division,
ther interesting color effects based on combina- transparent pigments may cause dispersion and
tion of interference and selective light absorp- flocculation problems. They are used not only
tion. These pigments can also exhibit metallic for their decorative effects – their high UV ab-
effects. Other layer structures (e.g., alternating sorption and lightfastness are also exploited to
coatings of mica with TiO2 and Fe2 O3 ) also pro- protect the binder matrix and substrate (e.g.,
duce metallic effects. Inorganic pigments based wood).
on mixed phases of platelets with the compo- Manufacturers in Western Europe include
sition Alx Mny Fe2−(x +y) O3 (x = 0–0.2, y = 0– BASF Lacke und Farben (Stuttgart, FRG).
0.06) also create metallic or interference effects
in coatings.
Special effect pigments based on mica are re- 4.2. Organic Pigments
garded as toxicologically harmless. Their eco-
nomic importance has arisen steadily; produc- Organic pigments are used to color and/or cover
tion capacities amounted to several thousand a substrate. They have gained importance be-
tonnes in 1989. cause the use of some inorganic pigments con-
Commercial products include Iriodin taining heavy metals has been legally restricted.
(E. Merck); Merlin (Mearl Corporation); and Organic pigments have a high light absorp-
Paliochrome (BASF Lacke und Farben). tion and a low scattering power, whereas inor-
ganic pigments have a low light absorption and
Metallic effect pigments consist of highly high scattering power. Combinations of organic
lustrous flakes of nonferrous metals (e.g., alu- and inorganic pigments are therefore often ad-
minum, copper) or alloys (e.g., brass). Leafing vantageous. Organic pigments are therefore of-
types undergo special organic surface treatment ten advantageous. Organic pigments also have
with fatty acids and collect at the surface of the a lower density and higher surface area than in-
coating film. Nonleafing types are coated with organic pigments; their color purity and tinting
alkylamines and are uniformly distributed in the strength are often higher. Organic pigments tend
solid paint film. When the pigments are dis- to dissolve at high temperature and in binders
persed in aqueous media, care must be taken to and solvents (migration).
prevent reaction with water on freshly created Organic pigments may be transparent or
metal surfaces because this leads to graying; for opaque. Transparent pigments are used in glazes
the same reason care should also be taken when and in combination with inorganic pigments in-
using chlorine-containing solvents. The impor- cluding special-effect pigments.
tance of metallic effect pigments in the decora-
 Paints and Coatings 107

The most important class of organic pigments etry. A change in the cross-linking density can
in terms of production are the azo pigments. affect the properties of the coating.
Other important pigment classes include metal-
complex pigments (e.g., copper phthalocyanine) Uses in Paints. Most organic pigments on
and higher polycyclic compounds (e.g., anthra- the market are suitable for use in paint systems.
quinone, quinacridone, isoindolinone, and pery- Apart from the properties mentioned above, the
lene). For a detailed description of these pig- rheological character of the pigment is impor-
ments, see → Pigments, Organic. tant because it affects both dispersion and the
Organic pigments are synthesized and then paint. Rheological behavior during dispersion
dried to form powders. The powder consists of determines how much pigment can be dispersed
agglomerates of pigment particles. Breaking up per batch. Favorable rheology (i.e., low viscos-
and incorporation of the agglomerate in the paint ity) allows higher pigment and binder concen-
(dispersion) are very important because they de- trations at equal application viscosity. “High-
termine the appearance and film properties of the solids” coatings have a low solvent content and
pigmented paint layer. These steps are described are therefore more environmentally acceptable.
in detail in Chapter 7. Pigment dispersions for Pigments can also influence other coating
paint formulation are also commercially avail- properties (e.g., film gloss) as a result of com-
able. plex interactions between the pigment, binder,
and solvent, and the method of application.
Properties. Lightfastness and weather re- The choice of pigment depends on the re-
sistance are the most important properties of quired color, binder, and fastness. Pigment
paint pigments. The organic pigments should be manufacturers have therefore produced pattern
colorfast and stable towards radiation, heat, and cards and information describing their prop-
atmospheric substances. Pigments may also be erties and areas of application. The pigment
partially responsible for photochemical or ther- should, however, be tested in the binder to be
mal degradation of the binder which leads to de- used and for the particular application.
terioration of optical film properties (e.g., gloss). Commercial products include Cinqua-
Migration should not occur when organic sia, Cromophtal, Irgalith, Irgazin, Monastral
pigments are used in paints that are applied in (USA only) (Ciba-Geigy); Cromofine (Dainichi
differently colored layers on top of each other. Seika); Graphtol, Sandorin (Sandoz); Hansa,
Resistance to migration depends on the pigment, Hostaperm, Novoperm, Permanent (Hoechst);
binder, and solvent. Helioecht, Indofast, Palomar, Perrindo, Quindo
The pigment should be heat stable because it (Bayer, Mobay); Heliogen, Paliogen, Paliotol,
may be subject to increasing temperature during Sico (BASF); Monastral, Monolite (ICI); and
dispersion, stoving, or use. Rubicron (Toyo Soda).
Chemical resistance is required for various Commercially available pigment prepara-
areas of use (e.g., in automotive finsihes to re- tions containing dispersion resins or a disper-
sist car washes and battery acids and in wash- sant are used when pigments are difficult to
ing machine coatings to resist detergent solu- disperse in a given binder or if the dispersion
tions). Chemical resistance is also of importance stage of production is to be omitted. The pig-
in paint formulation if acids or bases are em- ment preparation is then simply stirred into the
ployed as catalysts or if an aqueous basic or paint. The compatability of the dispersion resin
acidic binder is used. Since coatings are perme- or dispersant with the other paint components
able to industrial gases (e.g., SO2 and NOx ), the determines the area of application. Some prepa-
pigments must be resistant to these gases that can rations can be used for a wide variety of uses
affect the colorfastness of the pigment. such as solventborne or waterborne systems.
The pigment must also be compatible with Others have very restricted application areas
the paint binder. In chemically drying paints, the and can only be used with a few binders and
pigment may react with the reactive components solvents. Trade names and manufacturers in-
of the paint system. This can lead to changes in clude Colanyl, Flexonyl, Hostatint (Hoechst);
the pigment or in the cross-linking stoichiom- Encelac, Luconyl, Sicoflush, Sicomix (BASF);
and Mikrolith, Unispers (Ciba-Geigy).
108 Paints and Coatings

Solventborne Systems. The trend towards tically insoluble in the application medium and
high solids in solventborne paint systems has are used to modify the volume, achieve or im-
made rheology an important factor. Viscosity prove technical properties, and/or change optical
is affected by the binder, solvent, and pigment. properties. DIN 55 945 states furthermore that
The effect of the pigment on viscosity is reduced in white extenders, the refractive index is gener-
by optimization of the particle size and by suit- ally below 1.7; in certain media an extender may
able surface treatment. This is particularly im- also be a colorant (pigment).
portant for organic pigments which tend to have Since the refractive indices of most binders
a higher viscosity than inorganic pigments be- are also < 1.7, extenders do not contribute sig-
cause of their smaller particle size. nificantly to the hiding power when they are used
The pigment is dispersed in the binder and in an amount below the critical pigment volume
solvent which wet and stabilize the pigment. concentration (CPVC). The hiding power of a
Destabilization of the pigment (e.g., reagglom- dry film depends mainly on the amount of ti-
eration, flocculation, and flotation) must not oc- tanium dioxide present, a white pigment which
cur when the other paint components are added. has a high hiding power due to its high refractive
Aqueous Systems. Dispersion of organic pig- index.
ments in an aqueous phase is difficult because Above the CPVC, however, dry hiding be-
of their hydrophobic character. Surfactants are comes apparent. Air inclusions are formed in the
therefore often used to reduce the surface ten- micropores of the dry film, and consequently the
sion of the water and thereby improve wetting. hiding power depends on both the amount of ti-
Suitable treatment of the surface of the pigments tanium dioxide and the amount of trapped air.
can also facilitate wetting. In addition to clas- If the refractive index of an extender is greater
sical steric stabilization of the pigment, electro- than 1.7 (e.g., zinc oxide), it can also be termed
static stabilization is also possible due to the high a pigment, though the transition is not clear-cut.
dielectric constant of water. Special dispersion The refractive indices of some important exten-
resins or surfactants are used to aid dispersion; ders and white pigments are as follows:
they must be compatible with the binders and Water 1.33 Mica 1.58
must not alter the paint properties. Commercial Chalk 1.55 → Polymer Barytes 1.64
pigment preparations are also marketed which 1.5–1.6 Zinc oxide 2.06
contain appropriate dispersion resins and sur- Kaolin 1.56 Zinc sulfide 2.37
Talc 1.57 Anatase (TiO2 ) 2.55
factants. Siliceous 1.55 Rutile (TiO2 ) 2.75
Powder Coatings. Powder coatings do not earth
contain solvents or water, they consist solely of
binder and pigment. The pigment is incorporated Classification. Extenders are mainly nat-
into the reactive resin (e.g., with an extruder). ural minerals that are converted into a us-
The particle size required for the application is able form by working natural deposits, sepa-
then obtained by grinding and sieving. Cross- rating secondary constituents, and comminu-
linking of the paints is carried out at high tem- tion (micronization). Synthetic products such
perature (> 150 ◦ C), hence the heat stability of as precipitated carbonates [e.g., calcium car-
the organic pigments is very important. bonicum praecipitatum (ccp), precipitated sul-
Coil Coatings. Only a few high-grade or- fates (e.g., blanc fixe), precipitated and pyro-
ganic pigments are suitable for use in coil coat- genic silica, and silicates are used for optical
ings since they must be stable to storing temper- brightening. Synthetic fibers (generally organic)
atures > 250 ◦ C. are used for reinforcement. The classification of
extenders used in surface coatings is summa-
rized in Table 19. They are discussed in detail
4.3. Extenders elsewhere (→ Aluminum Oxide, → Calcium
Sulfate, → Magnesium Compounds, → Mica,
4.3.1. Introduction → Silica, → Silicates, → Talc).

Definitions. According to DIN 55 943 ex- Economic Aspects. The calcium car-
tenders are powdered substances that are prac- bonates (calcites, chalks, limestone powders,
 Paints and Coatings 109
Table 19. Classification of extenders used in coatings

dolomites, precipitated calcium carbonates, and 4.3.2. Properties

surface-treated carbonates) account for 80–
90 % of the extenders used in Western Europe. Extenders were originally employed for increas-
In the Federal Republic of Germany calcium car- ing volume (i.e., filling) to reduce the cost of
bonates are more predominant than in the re- the end product. Sophisticated and modified pro-
mainder of Western Europe (ca. 90 %); calcites cessing techniques (e.g., micronization, surface
with a high degree of whiteness and a mean par- treatment, and precipitation) have been used to
ticle size of 2–5 µm are most widely used. Next modify and improve the extenders and have led
follow talc, kaolins (with calcined kaolins), sil- to the discovery of other important properties
ica, barytes, and mica. (see Table 20).
Extenders included in Table 20 as well as
Occupational Health. Some mineral ex- their physical characteristic data are described in
tenders with extremely fine particles (dusts) are [350]. Measurement of these properties allows
governed by special legal provisions. The most definition and comparison of the extenders. Such
important regulations in Germany, for example, properties include:
are [348]:
chemical composition
1) Safety precautions (Unfallverhütungsvorschriften,
particle shape and size distribution
UVV 26), “Protection against Noxious Min-
density
eral Dust” (VBG 119)
tamped density and tamped volume
2) Technical rules for dangerous substances
specific surface area
(Technische Regeln für Gefahrstoffe,
brightness (whiteness)
TRGS), TRGA 508, (siliceous dust)
abrasion
3) MAK values, TRGS 900, maximum work-
pH
place concentrations and biological tolerance
wettability, dispersibility
values
oil absorption
Reference should also be made to the use of
paints and coating materials for food containers
and packaging [349].
110 Paints and Coatings
Table 20. Properties of extenders
Filler Chemical Occurrence Particle shape Density, Oil number, Brightness Specific pH Particle size
composition g/cm3 g linseed surface area, distribution, µm c

oil/100 g m2 /g
extender
Calcium CaCO3 natural rhombohedral 2.7 14–21 75–95 0.5–3 9.0 ± 0.5 0.5–100 (300)
carbonate (calcitic)
natural microcrystalline2.7 18–22 70–90 0.5–3 9.0 ± 0.5 0.5–100 (300)
synthetic aragonite 2.9 25–35 >95 7–10 9.5 ± 0.5 fiber length 1–3
fiber diameter
0.2–0.5
synthetic rhombohedral 2.7 35 >95 7–10 9.5 ± 0.5 fiber length
0.3–0.8
(calcitic) fiber diameter 0.2
Dolomite CaCO3 /MgCOnatural
3 rhombohedral 2.8 16–25 85–92 0.5–3 9.8 0.5–100 (300)
Talc Mg natural platelet-like 2.7–2.8 30–55 75−>90 3–12 9.5 ± 0.2 0.2–80
hydrosilicate
China clay Al silicate natural platelet-like 2.6 35–65 79–92 8–20 5 (natural) 0.2–40
7.5–9
(primary
dispersion)
China clay Al silicate synthetic amorphous 2.6 ca. 50 88–90 8–10 6.5 ± 0.5 0.2–40
calcined platelets
Siliceous Al natural platelet-like 2.6 ca. 45 81–90 10–15 7–8 0.1–20
earth silicate/quartz
corpuscular
Wollastonite CaSiO3 natural fibrous 2.8–2.9 25–30 85–88 2–5 9–11 3–100
Pyrogenic SiO2 synthetic amorphous 2.2 280 a >90 100–400 4 ± 0.5 0.008–0.04
silica
(average particle
size)
Quartz SiO2 natural trigonal 2.6 13–27 75–88 1–18 (90) 7–8 2.5–100 (250)
Cristobalite SiO2 synthetic tetragonal 2.4 23–25 85–90 ca. 2 8–9 2.5–100 (250)
calcined
Mica Al silicate natural platelet-like 2.7–2.9 35–75 60–85 3–12 7.5–9.5 1–100
Barytes BaSO4 natural rhombic 4.0 8–10 60–90 1–3 8–9 0.8–50
Barytes BaSO4 synthetic rhombic 4.0–4.2 13–20 92–95 1–4 6–7 0.3–10
Aluminum Al(OH)3 synthetic platelet-like 2.4 20–40 95–97 2–10 9±1 0.05–100 (250)
hydroxide
Gypsum CaSO4 natural platelet-like 2.4–2.6 17–20 83–87 5000–6000 b
7 ± 0.5 2–40
Slate AlH(SiO3 )2 natural platelet-like 2.7 30–35 28 8000 b 9 ± 0.5 30–200
Plastorite Mg, Al, K natural platelet-like 2.75 23–33 81–85 6000– 7.5 ± 0.5 5–250
silicate 14 000 b
Glass fibers C-, E-Glass synthetic fibrous 2.5 fiber length
0.5–10 mm
fiber thickness 9–12
Glass beads A-Glass synthetic solid, spherical2.5 16 0.4–1.5 0–50
Glass beads A-Glass synthetic hollow, 0.2–0.4 16 0.4–1.5 0–50
spherical
a
Oil adsorption (lubrication point according to ASTM D 281).
b
According to Blaine, cm2 /g.
c
This particle size is mostly used in paints, other particle sizes are also possible.

Chemical Composition (DIN 51 070 and Since these components mainly occur as
ISO 787, Parts 3, 8, 13, 14, 19). The extenders water-soluble salts, they lead to problems in
should be chemically inert in the paint. Sec- the paint film; for example, the paint film ef-
ondary constituents (e.g., iron ions) may pro- floresces under the influence of humidity. This
duce color changes. Sulfates, sulfides, alkali, is important in exterior-use paints because it af-
alkaline-earth, and heavy-metal ions may cause fects weather and corrosion resistance.
problems due to their chemical reactivity and The extender should be acid-resistant (e.g.,
toxicity, and also affect abrasion and weather barytes, talc, mica, china clay, silica, silicates).
resistance. Minerals with a platelet (lamellar) structure
 Paints and Coatings 111

(e.g., talc, mica, and china clay) are particu- Lamellar extenders improve coating proper-
larly suitable for corrosion protection systems ties, e.g., rheology (in particular thixotropy by
since they cover the surface better than parti- talc and kaolin), matting (talc), dry hiding (talc,
cles of other shapes. Better covering makes the kaolin), and adhesion (talc, kaolin).
paint film less permeable to water vapor, thereby
reducing bubble formation and improving film Density (ISO R 787, Part 10). The densities
adhesion. New developments have shown that of all mineral extenders lie in a relatively nar-
special sorts of calcites result in a remarkable row range (ca. 2.5–2.8 g/cm3 ). The exception is
corrosion resistance; this can be explained by the barytes with a density of ca. 4.0 g/cm3 .
buffering effect when the paint film is exposed to Extenders with a lower density (< 2 g/cm3 )
harmful acid atmospheres [351]. Platelet-shaped aroused interest for volume packaging (i.e.,
extenders should not, however, be “contami- packaging based on volume rather than weight)
nated” with differently shaped particles (e.g., in the emulsion paint sector. However, paints
talc with carbonates). produced with low-density extenders had com-
pletely different application properties. Further
Particle Shape and Size Distribution developments have therefore been aimed at
(DIN 66 111, 66 115–66 120, 66 141, 66 143– modifying emulsion paints to allow the use of
66 145, 66 165, ISO 25 591). Particles may more platelet-like extenders (e.g., talc or kaolin)
have the following shapes (figures denote the in combination with the commonly used carbon-
aspect ratio) [352]: ates.

Spheres 1/1 Tamped Density and Tamped Volume

Cubes 1/1 (ISO 787, Part II). The tamped density is the
Parallelepiped (1–4)/(1–< 1) ratio of mass to volume, while the tamped vol-
Platelets 1/(1/4–1/100)
(lamellae) ume is the ratio of volume to mass after tamping
Fibers 1/< 1/10 under specified conditions. These quantities pro-
vide information about the volume requirements
Extender producers try to retain the origi- of the products.
nal particle shape during processing because the
paint producer does not want to have the platelet Specific Surface Area (DIN 66 131, BET
shape of kaolin, talc, etc. destroyed during mi- method). The activity of extenders (i.e., their in-
cronization. fluence on the properties of the end product) de-
Particle size and size distribution are impor- pends on their surface area and their interaction
tant factors in determining the usability of the with, for example, the polymer matrix.
extender. The particle size spectrum produced The specific surface area is measured by ab-
by micronization corresponds to a Gaussian dis- sorption methods. The BET (Brunauer, Emmet,
tribution. The size spectrum is numerically char- and Teller) method is widely used for light-
acterized by the mean particle size (d 50 ), the colored extenders.
fines, an upper limit, and by the screen oversize Extenders can be classified as follows (BET
(→ Particle Size Analysis and Characterization surface area in m2 /g):
of a Classification Process).
A spectrum of particle sizes ensures opti- Inactive < 10
mum packing density. Interstices between indi- Semiactive 10–50
vidual particles can be filled with finer particles Active 50–100
Highly active > 100
that prevent the penetration of binder. Both the
manufacturer and user try to ensure that a spec-
ified product always has the same particle size Brightness and Yellowness (DIN 5033,
distribution. 53 163). Extenders should be chromatically
If, however, a certain extender grade does not neutral and should not cause discoloration or
have optimum packing density, it can be com- fading in the paint. Color, brightness, and yel-
bined with fine extenders or extenders with dif- lowness are determined quantitatively (see Sec-
ferent particle shapes. tion 9.2.2).
112 Paints and Coatings

Measurement is carried out by directing light The rate of color development and the de-
on the surface of the test sample. The pro- crease in granularity may serve as a measure of
portion of light reflected by the sample is de- the dispersibility.
termined with a spectrophotometer and com- Dispersion is defined as the formation of
pared with that reflected by a standard sur- smaller particles from powder agglomerates in
face (usually barium sulfate). The brightness a medium and the simultaneous wetting of the
is the reflectance obtained with a R 457 filter particles by the medium. In a fully dispersed ma-
(λ = 457 nm). The yellowness is obtained by terial there is a statistically uniform distribution
subtracting the brightness from the reflectance of the particles throughout the entire medium.
measured with a R 57 filter (λ = 570 nm). Gen- Grinding produces crystal fracture surfaces
erally, measurement methods must be specified and increases the surface activity of extenders.
by the manufacturer to allow comparison. Since the surface also bears hydroxyl groups, the
ground extenders are generally hydrophilic.
Abrasion. The abrasion of extenders de- Such extenders are consequently not wetted,
pends on their hardness and particle size. A or if so only poorly, by aliphatic hydrocarbon
high degree of abrasion is undesirable because solvents. However, the binder takes over this
it causes wear in machinery and contamination function to some extent because it contains sur-
of the blended material with abrasion products. factants and wetting agents added by the formu-
Contamination produces surface defects in the lator [353].
film. Einlehner’s method is often used to inves- In nonaqueous systems the disadvantages of
tigate the influence of the extender on abrasion extender hydrophilicity can be overcome by sur-
in machinery. An aqueous slurry of the exten- face treatment (stearic acid and stearates for car-
der is stirred for 1 h in a special apparatus. A bonates, silanes for silicates). Such treatment is
metal sieve is placed in this slurry throughout not necessary for aqueous systems and may even
this period and the weight loss of the sieve is be damaging.
then measured and converted to a specific sur- Wetting and micronization of the agglomer-
face area. ates play important roles in the dispersion pro-
The abrasion of a mineral decreases with the cess. The resultant dispersion should remain sta-
particle size. Abrasion is low if a mineral does ble over a prolonged period, flocculation is unde-
not contain any secondary abrasive constituents. sirable. For a more detailed discussion of disper-
Thus, for example, the abrasion of talc increases sion, see → Disperse Systems and Dispersants.
with the content of secondary constituents such
as quartz and calcium carbonate. Abrasion can Oil Absorption (DIN 53 199, DIN
also be reduced by subjecting the material to ISO 787, Part 5). The oil number is the amount
surface treatment, normally with stearic acid or of linseed oil that is absorbed by a pigment
stearates. or extender sample under defined conditions.
The oil number depends on the nature of the
pH Value (DIN 53 200; DIN ISO 787, extender, its particle size distribution, packing
Part 9). The pH value of an extender refers to density, and specific surface area.
the pH value of an aqueous suspension of the Heterodisperse extenders have a smaller
relevant extender. It is very important for paint binder requirement than homodisperse exten-
manufacturers to know whether an extender con- ders because their interstices can be filled with
tains acidic or alkaline constituents to predict its fine particles. In homodisperse systems the
behavior in an existing formulation. binder penetrates the interstices.
The wet point in waterborne paints is anal-
Wettability, Dispersibility (DIN 53 328; ogous to the oil number in solventborne paints.
ISO 8780, 8781). The dispersibility of a pow- It represents the number of milliliters of water
der is defined as its capacity for being dispersed. (containing 2 % wetting agent) that are required
Dispersibility depends on the wettability of the to convert 100 g of extender to a compact mass.
substance and on the number and strength of the
binding sites between the agglomerates.
 Paints and Coatings 113

4.3.3. Modification of Extenders they form an essential constituent of the coating.

In view of the increasingly stringent quality and
Precipitated Extenders. Precipitated ex- environmental requirements for the production
tenders such as calcium carbonate (calcium car- and use of coatings, high-quality paint systems
bonicum praecipitatum), barium sulfate (blanc are almost always formulated with additives.
fixe), and silica have been known for a fairly long Many effects can be achieved with additives,
time. When natural minerals are micronized, and not all of their, in some cases, very specific
a minimum particle size limit is encountered. uses can be discussed here. Information on paint
Lower particle sizes (< 1 µm) can only be ob- additives and their mode of performance is given
tained with considerable technical effort and ex- in the literature and company brochures. There is
pense. Extenders with finer particle sizes are pro- very little comprehensive literature on additives
duced synthetically by precipitation. The struc- [354–357]. The physical and chemical princi-
ture of one and the same extender can be modi- ples of paint production and application are help-
fied by controlling the precipitation conditions. ful in understanding their mode of action [358–
Particularly pure and thus bright extenders can 360]. A large number of paint additives are listed
be produced by a suitable choice of starting sub- according to areas of use in special tables [361,
stances [350]. 362]. Today the Internet is a very helpful tool
Surface-Treated Extenders. Some exten- for collecting information and this holds also for
ders tend to form agglomerates during storage, additives. All major additive suppliers maintain
or absorb moisture or additives from the paint websites where detailed information about their
mixture. This can be prevented by surface treat- products can be found. Additionally, these web-
ment. Stearic acid and its salts are used in large sites often contain background information and
amounts to coat calcium carbonates. guidelines for additive selection.
In subsequent developments the aim was to Additives may be classified in the following
chemically bond the extender and substrate, with groups:
the surface-treatment agent acting as a bridging 1) Defoamers
element. Silanes have proved particularly out- 2) Wetting and dispersing additives
standing in this respect and a large number of 3) Surface additives
products with widely varying organic groups 4) Rheology additives
(e.g., amino, mercapto, vinyl, and methacry- 5) Driers and catalysts
lic groups) are available for this purpose. Such 6) Preservatives
products are usually used to treat kaolins and 7) Light stabilizers
other silicates.
This subdivision is by no means exhaustive but
includes the major additive groups. Individual
5. Paint Additives products cannot always be assigned to one of
these groups because one additive may simulta-
In addition to resins, solvents, and pigments, neously influence a combination of paint prop-
paints also contain additives. The additive con- erties. Additionally it is sometimes difficult to
tent is typically between 0.01 and 1 %. Paint ad- draw the line between additives and other paint
ditives are used to prevent defects in the coating ingredients (e.g., resins, pigments, extenders,
(e.g., foam bubbles, poor leveling, flocculation, and solvents) when these materials are used in
sedimentation) or to impart specific properties an additive-like manner.
to the paint (e.g., better surface slip, flame retar-
dance, UV stability) that are otherwise difficult
to achieve. 5.1. Defoamers
Such products were formerly termed “aux-
iliaries” and were often only used to correct a Although foam may occur as an interfering fac-
paint batch that did not comply with the required tor already during paint production, most prob-
specifications and showed some defects. Nowa- lems arise when it causes surface defects during
days additives are already taken into consider- the application process.
ation when a new paint formulation is created;
114 Paints and Coatings

Liquid foams are a fine distribution of a gas a polysiloxane is sometimes included to inten-
(normally air) in a liquid. Thin films of liquid sify the defoaming action. For high-quality wa-
(the lamellae) separate the gas bubbles from terborne coatings in industrial applications, de-
one another and the gas–liquid interfacial area foamers are used that contain hydrophobic sili-
is quite high. For a detailed description, see cone oils (modified polysiloxanes) as the prin-
→ Foams and Foam Control. cipal defoaming component instead of mineral
Defoamers (antifoaming additives) are liq- oils (in combination with hydrophobic particles
uids with a low surface tension which have to or without). They have a better defoaming ef-
satisfy three conditions [363–365]: fect, but are more expensive. In most cases sili-
cone defoamers do not cause the gloss reduction
1) They must be virtually insoluble in the
that is often observed with mineral oil products.
medium to be defoamed
More recently silicone-free defoamers that make
2) They must have a positive penetration coef-
use of other foam-destroying polymeric struc-
ficient E
tures have also come to the market.
3) They must have a positive spreading coeffi-
Silicones are also the predominant defoamer
cient S
components in solventborne coatings. Products
with a correct balance of compatibility and in-
E = σL −σD +σL/D >0 compatibility can be synthesized by selectively
modifying the silicone backbone with polyether
S = σL −σD −σL/D >0 and/or alkyl chains.

σL = surface tension of the liquid phase

σ D = surface tension of the defoamer
σ L/D = interfacial tension between the liquid
and the defoamer
If both E and S are positive, the defoamer pen-
etrates into the foam lamella and spreads across
the surface. This creates interfacial tension dif-
ferences that destabilize the lamellae and cause Silicone-free defoamers based on other in-
the foam to collapse. In simple terms it can be compatible polymers (e.g., acrylates and acrylic
said that defoamers act because of their con- copolymers) are also commercially available.
trolled incompatibility with the paint system. If
a defoamer is too compatible its defoaming ef-
fect is not sufficient, if it is too incompatible
5.2. Wetting and Dispersing Additives
film defects occur (e.g., gloss reduction, forma-
tion of craters). Defoamer action is often very In the production of pigmented paints, the pig-
system specific and slight changes in a coating ment particles must be distributed as uniformly
composition may already require a different de- and as finely as possible in the liquid phase
foamer. As foam mostly occurs during the appli- (see Section 7.2.2). The pigment agglomerates
cation process, also application parameters and must first be wetted by the binder solution. This
substrate properties (e.g., porosity) can influence fairly complex process (described in detail in
foam behavior. [366]) mainly depends on the chemical nature of
For waterborne paint systems (especially the pigments, solvents, and binders and loosely
emulsions used for decorative purposes) de- packed agglomerates and low viscosity of the
foamers based on mineral oils are often used penetrating binder solution are helpful for fast
(→ Foams and Foam Control, Chap. 5.5). In ad- agglomerate wetting. Surface tension of the liq-
dition to the mineral oil as carrier, these prod- uid phase and the contact angle between the liq-
ucts contain finely dispersed hydrophobic par- uid and the pigment surface also strongly control
ticles (e.g., silica, metal stearates, polyureas) the wetting speed, and this is where the wetting
as defoaming components. A small amount of additives exert their influence: Wetting additives
 Paints and Coatings 115

Figure 4. Stabilization of pigment dispersions

A) Electrostatic charge repulsion induced by polyelectrolytes; B) Steric hindrance through low molecular mass dispersing
additives; C) Steric hindrance through polymeric dispersing additives
a) Pigment particle; b) Polyelectrolyte; c) Molecular structure causing steric hindrance; d) Pigment-affinic group

are materials of low molecular mass with a typi- The first mechanism is prevalent in waterborne
cal polar–nonpolar surfactant structure. They re- emulsion systems and makes use of polyelec-
duce the surface tension of the binder solution trolyte structures to create electrical charges on
to such an extent that the contact angle becomes the pigment particles. The latter predominates in
zero, which is the requirement for good wetting. solventborne paints, and additive molecules can
Further reduction of the surface tension should have relatively simple fatty acid based chemistry
be avoided as it can reduce wetting speed. or more complex polymeric structures. In coat-
After the agglomerates have been broken ings with water-soluble resins both mechanisms
down into smaller particles by impact and shear can be employed, but in practice steric stabiliza-
forces (grinding, milling), the pigment disper- tion is often preferred, especially in high-quality
sion must be stabilized to avoid reformation of coating formulations.
larger pigment clusters by flocculation. Floccu- Good adsorption of the additive to the pig-
lation is due to the van der Waals forces between ment surface is necessary for efficient stabiliza-
the particles, which are attractive in nature. They tion. Problems may arise in this respect with
are effective only over very short distances, but many organic pigments because of their highly
the Brownian motion of the pigment particles in nonpolar surface. This is where polymeric dis-
the liquid causes particle collisions and thus floc- persing additives have an advantage in compari-
culation. To avoid flocculation it is necessary to son to the low molecular mass structures. These
build up an energy barrier between the particles polymeric wetting and dispersing additives can
that keeps them well separated. If this barrier is better stabilize such difficult pigments by virtue
higher than the thermal energy (kT ) of the parti- of their macromolecular structure and the large
cles, flocculation can be effectively minimized. number of pigment-affinic groups (Fig. 4 C).
Dispersing additives are stabilizing substances Wetting and dispersing additives can also
that are adsorbed onto the pigment surface via solve flooding and floating problems. Since most
pigment-affinic groups (anchor groups with a paints contain more than one pigment, the pig-
high affinity for the pigment surface) and es- ments often segregate in the paint film during
tablish repulsive forces between individual pig- drying. Nonuniform pigment distribution within
ment particles. Stabilization is achieved either the film surface is termed floating [formation of
via electrostatic charge repulsion (Fig. 4 A) or Bénard cells (Fig. 5 A) and streaks]. In flooding
via steric hindrance due to molecular structures the surface is uniformly colored, concentration
that project from the pigment surface into the and thus shade differences occur only perpen-
binder solution (Fig. 4 B and C) [359, 367, 368]. dicular to the surface; this phenomenon only be-
116 Paints and Coatings

comes evident in the rub-out test (Fig. 5 B). In tives (Fig. 6). They form bridges between pig-
this test, after a short drying period part of the ment particles and thus build up flocculates. Size
wet paint film is rubbed with the finger until al- and stability of the flocculates are controlled by
most dry (i.e., until it starts to become tacky). the additive. This method is, however, not ideal
This treatment distributes the pigments evenly for high-quality topcoats because flocculation
in the paint film and segregation is not possible. may reduce gloss and impair other paint prop-
A color difference detected between the rubbed erties (e.g., hiding power, color strength, trans-
section and the untouched area indicates flood- parency). Controlled flocculation also changes
ing. the rheology of the paint system (see Section
5.6). Wetting and dispersing additives with such
properties are often used in combination with
other rheological additives. They enhance the
action of the rheological additives, often syn-
ergistically, and problems such as sagging and
settling can be overcome. In the case of settling,
the presence of an additive layer on the pigment
surface prevents the formation of hard sediment
which would be difficult to stir in again. Instead
any settled material formed is soft and easy to
incorporate again. Antisettling additives gener-
ally increase the low shear viscosity to improve
suspension of the pigment particles and avoid
the formation of hard sediments.

Figure 6. Controlled flocculation

Figure 5. Uneven pigment distribution (color differences)

due to flooding and floating
A) Bénard cells; B) Rub-out test 5.3. Surface Additives
During and directly after application of a coat-
Flooding and floating are caused by local ed- ing several defects can develop in the coating
dies in the drying paint film. The pigment par- surface. Many of these defects can be explained
ticles undergo eddy motion and if they differ in by differences in interfacial tension. Poor sub-
mobility, they can become separated from one strate wetting, for example, must be expected
another. The mobility of the pigments depends if the paint has a higher surface tension than
on density, size, and the strength of their interac- the substrate to be coated. When spray dust or
tions with the binder molecules. Additives can solid dust particles fall onto a freshly coated sur-
minimize mobility differences between different face, craters are formed if the deposited droplets
pigments by controlling these pigment–binder or particles have a lower surface tension than
interactions and thereby prevent flooding and the surrounding paint material. Craters are also
floating. formed if the surface to be coated is locally con-
Another way of avoiding flooding and float- taminated with substances having a very low sur-
ing is to prevent the separation of the pigments face tension (e.g., oils) and the surface tension
by coflocculation. Additives that work in this of the paint is too high to wet these contaminated
way are known as controlled flocculating addi- areas.
 Paints and Coatings 117

Surface tension differences may also develop but do not lower the surface tension as strongly
within the paint itself: during drying the sol- as silicones.
vent evaporates and this change in composition Leveling also depends highly on paint rhe-
also alters the surface tension. Even slight sur- ology which can be modified by using special
face tension differences lead to the formation of solvent blends. Finally, wetting and dispersing
Bénard cells which may result in visible surface additives can also alter the rheology and thus
defects such as orange peel and air draught sen- influence leveling.
sitivity. Besides modified polysiloxanes and acrylate
In general, surface tension differences lead copolymers also fluorinated structures and addi-
to material transport in the liquid paint film tives based on acetylene diols are used in prac-
from the region of lower surface tension to tice to counteract surface defects.
that of higher surface tension. This movement
is responsible for the above-mentioned defects.
Other phenomena such as fat edges, picture 5.4. Driers and Catalysts
framing, and ghosting can be explained in a sim-
ilar way. Driers (siccatives) are used in paint systems that
Silicone additives (mainly organically mod- dry at ambient temperature by oxidation pro-
ified methylalkyl polysiloxanes) lower the sur- cesses. They accelerate the drying process by
face tension of coatings and minimize surface catalyzing the autoxidation of the resin. Dri-
tension differences. ers are in general organometallic compounds
(metallic soaps of monocarboxylic acids with
8–11 carbon atoms, mainly naphthenates and
octanoates), the metal being the active part.
Cobalt, manganese, and lead (primary or ac-
tive driers), calcium, zinc, zirconium, and bar-
ium (secondary or auxiliary driers) are mainly
They are therefore ideal for solving the prob-
used (→ Metallic Soaps). In practive, mixtures
lems described above. Organic modification of
of metallic soaps are commonly used to obtain
the silicone (polyether and polyester chains, aro-
the optimum ratio of auxiliary to active drying.
matic groups) serves to adjust the compatibility
Co–Pb–Ca is a typical combination that has been
with the paint system. The alkyl groups have a
widely used in the past. Due to increasing envi-
strong influence on the surface tension: methyl
ronmental awareness, lead as a drier metal was
groups give very low surface tension, longer
banned for most applications, and lead-free drier
alkyl chains give higher values.
systems use zirconium instead. More recently
Silicone additives also improve the slip prop-
the use of cobalt, which is the most important
erties of the dried coating (reduced coefficient of
drier metal today, has come under discussion be-
friction), which then exhibits improved blocking
cause of its toxicological potential. Replacing it
and scratch resistances. Similar effects can be
by precomplexed manganese driers in which or-
achieved with wax additives (wax emulsions and
ganic compounds such as 2,2 -bipyridyl are used
dispersions in water or organic solvents and mi-
as ligands may be the solution in future.
cronized waxes), which can have an additional
Auxiliary driers cannot be used on their own,
flattening effect and also improve surface pro-
they always have to be combined with active dri-
tection.
ers.
Poor leveling is also considered a surface de-
The driers mentioned above can also be used
fect. The leveling properties of a coating depend
in waterborne formulations, but it was found that
on many factors. Silicones influence the surface
they show reduced effectivity in such systems.
structure by suppressing eddy motion during
One reason is that the metal ions are easily com-
drying. Acrylate copolymers are also used for
plexed with water molecules. A possible way
the same purpose. They are incompatible with
around this problem is to use precomplexed dri-
the paint system and accumulate at the surface.
ers.
They also have a stabilizing effect on the surface
Driers can cause skin formation during paint
storage, particularly if the can or container has
118 Paints and Coatings

been opened. Oximes or alkylphenols are added Preservative measures are governed by the
as antiskinning additives. They block the action intended use of the coating. There are no uni-
of the driers in the can, but at the correct dosage versal additives on account of the large num-
do not prolong the drying time of the applied ber of possible types of damage; combination
paint film due to their volatility. products containing several active ingredients
The curing of coatings that are cross-linked are available and often used. Organomercury
by other chemical reactions can be accelerated compounds, chlorinated phenols, and organotin
with catalysts. Acid catalysts are the most im- compounds were often used, but these environ-
portant and are used for a large number of stov- mentally harmful products are now being re-
ing enamels and force-dried, acid-curing wood placed more and more by metal-free organic
paints. They are mostly sulfonic acids of widely substances, mainly nitrogen-containing hetero-
varying structure, often blocked with amines to cycles.
allow formulation of storage-stable paints. The In-can preservatives, besides being effective
use of a catalyst can lower the stoving time against a wide range of microorganisms and hav-
and/or stoving temperature to save energy or to ing low toxicity for humans and animals, must
permit the coating of temperature-sensitive sub- have good water solubility and good compatibil-
strates. ity with the coating system. Dry-film preserva-
Catalysts also include accelerators for two- tives must have low water solubility and volatil-
pack polyurethane paints (e.g., tin and zinc com- ity so that they stay in the coatings film as long
pounds, tertiary amines), initiators for unsatu- as possible.
rated polyester resins that act as radical-forming
agents, and photoinitiators for UV curing sys-
tems. 5.6. Rheology Additives
The flow properties of paints can be modified
5.5. Preservatives with rheology additives. This is important for
obtaining optimum application behavior of the
Waterborne coatings systems are easily attacked paint material, i.e., good leveling and no sagging
by microorganisms. The biodegradable paint at the desired film thickness. Paint rheology also
material detoriates and, as a result, bad smell, plays a role in storage stability (settling, see Sec-
discoloration, and growth of mildew can be ob- tion 5.2).
served. Solventborne coatings are not prone to Thickeners, mainly cellulose derivatives
this kind of attack because of their content of (e.g., methyl cellulose, ethylhydroxypropyl cel-
organic solvents, but the dry paint film can also lulose) or polyacrylates, are generally used in
be attacked by microorganisms. In this case, it emulsion paints. Polyurethane thickeners (asso-
does not matter whether the coating was sol- ciative thickeners) with more favorable leveling
ventborne or waterborne, and under humid con- properties are also increasingly used.
ditions algae and fungi can grow on the coating A large number of rheological additives for
surface. In both cases, preservatives (biocides) solventborne systems are commercially avail-
are used to protect the coating. In-can preserva- able. Hydrogenated castor oils, pyrogenic sil-
tives protect waterborne paint systems against ica, modified ureas, and modified montmoril-
contamination by microorganisms during pro- lonite clays (organoclays, e.g., bentonite) are
duction, transportation, and storage. Dry-film preferred.
preservation is aimed at preventing the growth The rheological action of the above addi-
of bacteria, fungi, and algae on the applied paint tives is based on the fact that they form three-
film. A special area of use is the protection dimensional network structures via hydrogen
of wood against biodegradation by putrefactive bonds in the paint. These lattice structures are
fungi and insects. Antifouling additives for un- destroyed by shear forces but are restored when
derwater coatings that are intended to prevent the forces are removed. This recovery is not,
marine growth are also included in this category however, immediate. The rising viscosity ini-
(see also Section 11.4). tially allows leveling of the surface but subse-
quently prevents sagging. This time-dependent
 Paints and Coatings 119

change in viscosity is known as thixotropy cal decomposition (which leads to delamination)

(Fig. 7). In paints thixotropy is more desirable by the filter effect of the UV absorber that is
than purely pseudoplastic flow behavior because added to the clearcoat; UV absorbers cannot trap
it allows a compromise between sagging and lev- radicals. Hindered amine light stabilizers do not
eling. absorb in the UV region, but trap radicals already
formed, and are mainly responsible for the gloss
retention and prevention of crack formation in
paints. Optimum protection against decomposi-
tion phenomena in the coating is achieved by
using a combination of both stabilization meth-
ods.

UV Absorbers. Four different classes of

UV absorbers are shown below:

Figure 7. Thixotropy: viscosity is shear-force-dependent

and time-dependent

5.7. Light Stabilizers

High-quality industrial coatings, especially au-
tomotive finishes, are subjected to severe weath-
ering in exterior applications. In two-coat metal-
lic coatings, exposure to UV light, oxygen, mois-
ture, and atmospheric pollution causes decom- The hydroxyphenylbenzotriazoles are the
position of the polymer material in the automo- most important. They absorb the damaging UV
tive finishes. This decomposition results in loss light and rapidly convert it into harmless heat
of gloss, crack formation, color changes, and de- (keto–enol tautomerism) [372].
lamination phenomena [369]. The action of all UV absorbers depends on
High-energy UV light is particularly detri- the Lambert–Beer law, and the absorption prop-
mental because each polymer material can be erties of the UV absorber. The further the ab-
damaged particularly easily at one or more sorption edge extends into the near UV region,
wavelengths in the UV range. Light stabiliza- the more UV light can be filtered out. Of the four
tion is therefore essential [370]. UV absorber classes shown above, the hydroxy-
phenylbenzotriazoles have the broadest absorp-
Methods of Stabilization. Two stabiliza- tion band [369, 373]. In addition to thermal
tion methods have been adopted industrially stability [373] and stability to extraction with
[371, 372]: water or organic solvents, photochemical sta-
bility is important [374–376]. Ultraviolet re-
1) Competitive UV absorption by UV absorbers
flection spectroscopy can be used to establish
in the wavelength range 290–350 nm.
whether the employed UV absorber is still ef-
2) Trapping of the radicals formed during poly-
fective, even after several years’ external weath-
mer degradation by radical scavengers (hin-
ering [377]. The hydroxyphenylbenzotriazoles
dered amine light stabilizers, HALS).
have a much higher photochemical resistance
In two-coat metallic paints, the basecoat is than oxalic anilides and hydroxybenzophenones
protected against color change and photochemi- [369, 373, 378].
120 Paints and Coatings
a
Table 21. Outdoor exposure of a two-coat metallic coating
Light stabilizer 20◦ gloss after n years Florida

n=0 n=2 n=4 n=6 n=8

Unstabilized b 93 45
1 % Benzotriazole I c 94 71 58
1 % Benzotriazole I and 1 % HALS I 94 70 67 56 50
a
Clearcoat, acrylic–melamine; basecoat, polyester–cellulose, acetobutyrate–melamine, silver metallic; bake: 130 ◦ C, 30 min; exposure:
Florida, 5◦ South, black box unheated; percentage of light stabilizer relative to binder solids; benzotriazole I,
2-(2 H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [70321-86-7].
b
Cracking after 2.25 years.
c
Cracking after 5.5 years.

Radical Scavengers (Sterically Hindered The formation of nitroxyl radicals NO·· is

Amines). Two typical sterically hindered essential for stabilization since the concentra-
amines (HALS = Hindered Amine Light Stabi- tion of harmful peroxy radicals falls sharply in
lizer) follow: their presence [380].
Light stabilizers are tested under artificial
weathering conditions (accelerated weathering)
and under outdoor weathering (Florida, 5◦
South, black box, not heated) [378]. Figure 8
and Table 21 illustrate the influence of light pro-
tection agents on gloss retention and crack for-
mation in two-coat metallic coatings.
The tetramethylpiperidine group is respon-
sible for the stabilizing action. Different sub-
stituents on the nitrogen atom result in differ-
ent pK b values, which are important in the area
of use of the products. HALS I, bis(1,2,2,6,6-
pentamethyl-4-piperidinyl) ester of decane-
dioic acid [41556-26-7], is used in systems
that are not catalyzed by strong acids (in-
teraction of the acid with the basic nitro-
gen atom). HALS II, bis(2,2,6,6-tetramethyl-1-
isooctyloxy-4-piperidinyl) ester of decanedioic
acid [122586-52-1], was developed for acid-
catalyzed systems because it does not undergo
undesirable interactions with acid catalysts.
The mode of action (Densiov cycle) of HALS Figure 8. Accelerated weathering of an acid-catalyzed
(as deduced from investigations on polyolefins) two-coat metallic coating in an UVCON apparatus (Atlas
follows (P = polymer) [372, 379]: Corp.)
Clearcoat: high-solids acrylic–melamine; Basecoat: high-
solids acrylic–melamine, silver metallic; Bake: 120 ◦ C,
30 min; Benzotriazole II: 3-(2 H-benzotriazole-2-yl)-5-
(1,1-dimethylethyl)-4-hydroxyoctyl benzenepropanoate
[84268-23-5]
a) Unstabilized; b) 2.5 % Benzotriazole II; c) 1.5 %
Benzotriazole II and 1 % HALS II (percentage relative to
binder solids)
 Paints and Coatings 121
Company Products
5.8. Commercial Products
[Link]/
Kusumoto Wetting and dispersing additives,
The number of additives available on the mar- defoamers, surface additives,
ket is quite large and picking some of these and waxes, rheology additives,
preservatives
mentioning them as examples is not very help- [Link]/
ful, because their use is often system specific. Lanxess Wetting and dispersing additives,
In addition, new additives are constantly being defoamers, surface additives,
catalysts, driers, antiskinning
developed to meet market requirements. There- additives
fore, it seems more useful to give a list of the [Link]/
main additive suppliers, and further up-to-date [Link]/
Micro Powders Waxes
information can be obtained from these sources. [Link]/
This following list contains the main compa- Münzing Chemie Wetting and dispersing additives,
nies worldwide that manufacture additives for defoamers, surface additives,
rheology additives
coatings. However, such a list can never be ex-
haustive and there are many other companies ac- [Link]/
tive in the same market. The information given Noveon Wetting and dispersing additives,
defoamers, surface additives,
here may change without notice due to mergers waxes, rheology additives
and acquisitions and other circumstances. [Link]/
Troy Wetting and dispersing additives,
defoamers, surface additives,
Company Products rheology additives, driers,
preservatives
Air Products Wetting and dispersing additives,
defoamers, surface additives [Link]/
[Link]/ Worlée-Chemie Wetting and dispersing additives,
defoamers, surface additives,
BYK-Chemie Wetting and dispersing additives,
rheology additives
defoamers, surface additives,
waxes, rheology additives [Link]/
[Link]/
Ciba Wetting and dispersing additives,
defoamers, surface additives,
waxes, preservatives, UV
stabilizers, photoinitiators 5.9. Use and Testing of Additives
[Link]/
Cognis Wetting and dispersing additives, Additives are generally used in very small
defoamers, surface additives,
rheology additives, corrosion amounts (≤1 % of total formulation) and cor-
inhibitors, plasticizers, rect dosage is extremely important for optimum
preservatives,
[Link]/
effectiveness and also to avoid undesirable side
Cytec Wetting and dispersing additives, effects. The dosage has to be determined in test
defoamers, surface additives, series.
antiskinning additives, catalysts,
driers, preservatives Many additives can be incorporated relatively
[Link]/ easily into the paint system during or after the
Degussa Wetting and dispersing additives, last phase of production (let down). In some
defoamers, surface additives,
rheology additives, adhesion cases, however (e.g., with many rheological ad-
promoters ditives), certain incorporation conditions have to
[Link]/ be observed. Wetting and dispersing additives,
[Link]/
Deuchem Wetting and dispersing additives,
for example, always have to be present in the
defoamers, surface additives, millbase to achieve the desired results.
adhesion promoters, catalysts Ideally, the effectiveness of an additive
[Link]/
Elementis Wetting and dispersing additives,
should be checked in the complete formulation
defoamers, waxes, rheology and under conditions as close as possible to those
additives, driers, corrosion prevailing in practice. Checking a defoamer just
inhibitors, UV stabilizers
[Link]/ in the binder system, for example, can only be
King Industries Wetting and dispersing additives, regarded as a preliminary test, because the be-
defoamers, rheology additives, havior in the complete formulation may differ
catalysts, corrosion inhibitors
substantially.
122 Paints and Coatings

Many defects that are to be eliminated by the The advantages of chemical paint removal
use of additives are also influenced by the sub- are that it can be used for almost all types of
strate to be coated and the application method. paints, geometries, and heat-sensitive items. In-
Differences between additives can be estab- vestment costs are low and waste air does not
lished in simple laboratory tests. However the cause serious environmental problems. The dis-
final composition of a specific formulation must advantages are the relatively long removal time
take into account as many application parame- and formation of a paint slurry which leads to
ters as possible (e.g., the state of substrate, ap- higher waste disposal costs.
plication method, and drying conditions).
In most cases additives influence not just one Hot Alkaline Paint Removal Baths. Paint
property of the coating. They may also have removal takes place in hot, aqueous, alkaline
undesirable or beneficial side effects. Additives baths (> pH 13) at 50–95 ◦ C. The alkalinity is
are not “magical” products but need to be used adjusted by adding large amounts of alkali-metal
rationally and carefully to provide the desired hydroxides or organic amine or hydroxy com-
satisfactory results. As detailed and complete a pounds. The chemical bonds in the paint binders
knowledge as possible of the mechanism of ac- are hydrolyzed by the high alkalinity. Penetra-
tion of the products, their possible effects and tion into the paint layer and migration under-
side effects, their limitations, and the underly- neath the film is promoted by adding surfactants.
ing causes of paint defects are certainly helpful, Hot paint removers may, for example, consist of:
but due to the complexity of paints and coatings
empirical knowledge is indispensible. 50–70 % alkali-metal hydroxides (KOH/NaOH)
0–20 % strongly basic organic hydroxy or amine compounds
(e.g., alkanolamines)
5–20 % high-boiling solvents (e.g., glycol ethers)
6. Paint Removal 5–20 % organic acids (e.g., gluconic acid) and their alkali-metal
salts
0–5 % surfactants
The nature, condition, and quality of the paint
and substrate are important in paint removal. Strongly hydrolyzing, aggressive alkali lyes
The paint binder plays a decisive role in paint can be used for removing paint from steel
dissolution; the substrate influences the choice whereas strong organic bases are used for light
of paint removal method. Various chemical and and nonferrous metals. The hot paint removal
physical methods exist for removing paint from bath is overlaid with a layer of an organic com-
different substrates (metals, wood, and mineral pound of low volatility (e.g., paraffin oil) to
substrates) [381, 382]. prevent evaporation of water and active con-
stituents. Alkaline hot paint removal agents are
extremely economical and can be used for most
6.1. Paint Removal from Metals paints.
6.1.1. Chemical Paint Removal
Neutral paint strippers include halogen-
Paint layers can be stripped (dissolved) or de- free organic solvents (e.g., glycols, glycol ethers,
graded with chemicals [383]. Paint dissolution is 1-methyl-2-pyrrolidinone) which are generally
performed with organic solvents, whose action is used at 20–40 ◦ C. In contrast to the alkaline
assisted by surfactants. Paint binders can be de- paint removers, neutral paint strippers result in
graded with strong alkali or acid. Depending on purely physical dissolution of the paint from the
their use, paint removers may also contain cosol- substrate. Their use is therefore restricted to re-
vents, activators (acid or alkali), wetting agents, moving physically drying paints.
emulsifiers, evaporation retarders, corrosion in-
hibitors, and thickening agents. The efficiency Acid Paint Removers. Like the alka-
of paint removers is improved by increasing the line products, the acid paint removal agents
temperature; the paint removal time can be sub- (pH < 1) based on mineral acids result in chem-
stantially shortened by raising the temperature ical degradation of the paint binders. They are
of the bath (2–6 h at 20–95 ◦ C). usually based on sulfuric acid and are covered
 Paints and Coatings 123

with a protective layer of paraffin wax. Alka- melt heated to 300–500 ◦ C. The short time re-
line agents have a pronounced swelling action, quired for paint removal (30–120 s) is the re-
whereas the acid agents result in disintegra- sult of the spontaneous heat transfer and high
tion of the binder. The acid products are used oxidation potential of the salt melt (e.g., alkali
only in special cases (e.g., to remove epoxy and nitrates).
polyamide powder coatings from heat-sensitive
substrates) because of their aggressive, corrosive
properties; bath temperature is 20–50 ◦ C. 6.1.3. Mechanical and Low-Temperature
Paint Removal
Cold Paint Removal. Up to a few years High-Pressure Removal with Water. Paint
ago, cold paint removal based on the use of di- can be removed from a metallic substrate (e.g.,
chloromethane [75-09-2] (methylene chloride) grids and skids) by the high kinetic energy of a
was the most widely used paint removal method. high-pressure (70–100 MPa) water jet.
Use of this method is declining in favor of chem-
ical or thermal methods due to concern about the Blasting. In analogy with sandblasting of
environmental and occupational safety of halo- metal surfaces, paint can be removed from vari-
genated hydrocarbons. ous substrates by blasting with air or water con-
taining abrasive blasting media (e.g., sand, plas-
tic granules, metal particles) and/or other addi-
6.1.2. Thermal Paint Removal tives (e.g., alkali salts). Paint is, for example,
removed from aircraft (aluminum) with a water
Thermal paint removal methods exploit the fact jet containing special additives.
that organic paint constituents can be readily py-
rolyzed or combusted, as well as the high heat Low-temperature paint removal exploits
capacity of the organic material. They can be the shrinkage and embrittlement of paint lay-
used to remove paint from steel and aluminum ers that occurs after cooling in liquid nitrogen
but not from heat-sensitive substrates (e.g., zinc (−196 ◦ C) for 1–3 min.
and zinc alloys). The short removal times and The mechanical methods and low-tempera-
small amount of waste ash formed are advan- ture paint removal are restricted to a few spe-
tages, although this is offset by the high capital cial areas of application. Chemical and thermal
investment resulting from stringent safety regu- methods have their specific advantages and dis-
lations and the need for equipment to combust advantages, not only as regards paint removal
the resultant pyrolysis gases. but also with respect to environmental pollution
by paint slurry, rinse water, effluent, and waste
Low-Temperature Carbonization air.
Method. Pyrolysis is performed for 3–9 h in
closed furnaces at 380–420 ◦ C in a controlled,
low-oxygen atmosphere. 6.2. Paint Removal from Wood and
Mineral Substrates [384]
Fluidized-Bed Method. The fluidized bed
consists of inert, finely granular, inorganic mate- Paint strippers used to remove coatings from
rial (usually alumina) that is fluidized by inject- wood and mineral substrates may be either al-
ing compressed air through a special fluidiza- kaline or based on organic solvents.
tion floor. Organic paint material is oxidatively Alkaline paint strippers (e.g., alkali-metal
degraded by the entrained atmospheric oxygen hydroxides, sodium carbonate, sodium metasili-
at 400–480 ◦ C in 20–60 min. This method is cate, trisodium phosphate) can be manufactured
not suitable for some geometries (e.g., hollow in liquid, paste, or powder form. They are only
items). suitable for removing hydrolyzable coating ma-
terials (e.g., alkyd resins and oil paints). Alkaline
Salt Bath Method. The object from which paint strippers may also be used to remove coat-
the paint is to be removed is immersed in a salt ings on facades. Tests should be carried out to
check that the coating is hydrolyzable.
124 Paints and Coatings

The solvent-containing paint strippers may This is because the quality and stability of the fi-
contain chlorinated hydrocarbons (dichloro- nal product is determined not only by the choice
methane) and cosolvents (e.g., alcohols and aro- and quantity of ingredients (pigments, film for-
matic hydrocarbons). Systems that do not con- mers, solvents, additives, etc.) but also by how
tain chlorinated hydrocarbons (CHC-free paint and in which order they are combined.
strippers) are, however, becoming increasingly
important because environmental considera- Source of Added Value. The main physi-
tions demand reduction in the use of chlorinated cal process involved in the production of coating
hydrocarbons. The dichloromethane-containing materials is the homogeneous, irreversible mix-
formulations evaporate relatively quickly and ing of the liquid components. In pigmented sys-
subsequently enter the atmosphere. The CHC- tems, complete wetting and a uniform, stabilized
free paint strippers are formulated with a com- distribution of pigment particles in the liquid
bination of various slowly evaporating but more medium (resin solution or dispersion) are also
effective solvents. Typical solvents are high- important. The main reason why these appar-
boiling glycol ethers, dicarboxylic acid esters, ently simple processes result in a relatively high
N-methylpyrrolidone, alcohols, and ketones in added value is the crucial but difficult to achieve
combination with auxiliary substances. CHC- requirement for microhomogeneity with a parti-
free paint strippers are suitable for removing fa- cle size of ≤ 1 µm. Homogeneity or dispersity
cade coatings whereby many paint layers can at this level is very important because of the in-
be removed simultaneously. Removal takes a teraction of the paints with the absorbed light
longer time than with CHC-containing paint with wavelengths in the visible region. High en-
strippers but this can be compensated for by ergy inputs are necessary to obtain microhomo-
using different application techniques. It is im- geneity (or dispersity) due to the interaction of
portant that the paint stripper wastes are readily strong adhesive forces in this region.
biodegradable.
Production Strategy. An all-embracing de-
scription of paint production processes cannot
7. Production Technology be given, mainly because paint manufacturers
range from very small operations producing
7.1. Principles only a few hundred tonnes of paint annually
up to large companies producing several hun-
A large number of paint formulations are pro- dred thousand tonnes annually. Large compa-
duced in a limited number of production steps. nies account for only about 20 % of the world-
The special know-how for paint production wide market (ca. 30×106 t). A further difficulty
therefore involves skilful adaptation of the pro- is the multiplicity of formulations: large paint
cessing steps to the relevant production plant factories must hold a range of up to 20 000 for-
(scale-up, quality planning). Until recently, paint mulations to be able to serve their markets. In
production was a traditional craft in which for- addition, national differences in environmental
mulations were adapted in a large number of pro- legislation make a uniform approach difficult.
duction stages. Quality testing was carried out at Since customer orders differ not only as re-
the end of the production process. Fluctuations gards paint formulation but also in the amount
in quality were rectified in time-consuming, and ordered, manufacturers must have a correspond-
thus expensive, correction steps. With the tran- ing “mix” of equipment (different sizes of mix-
sition to industrial production, quality planning ers, tanks, production equipment, filling and
and assurance systems were increasingly imple- packaging lines, etc.). Production according to
mented in conjunction with the scale-up of unit customer orders (including just-in-time deliv-
operations to achieve the necessary quality spec- ery) results in widely varying batch sizes, rang-
ifications without additional correction stages. ing from a few kilograms up to 20 or 50 t, but of
Many other factors besides the choice of suit- the same, constant quality. A large paint factory
able raw materials have to be taken into account therefore has a complex structure with regard
if a paint formulation is to serve as a basis for to material flow and the provision of materials,
commercial production of high-quality paints. equipment, and staff [394].
 Paints and Coatings 125

Figure 9. Material flow in paint production (for explanation of the numerals see text)

Table 22 shows the compositions of a filler binders, and is ready-for-use. Paste series dif-
and a one-pack topcoat (white and colored) for fer according to the nature of the film formers
application in automotive mass production. The used.
paint-making process can be subdivided into Smaller factories generally buy in their film-
four main stages: forming materials and if necessary convert them
into solutions. The major paint companies, on
1) Preparation of the millbase (premixing)
the other hand, produce considerable amounts
2) Continuous dispersion
of the film formers (resins) themselves and are
3) Completion of the formulation
therefore able to develop “tailor-made” film-
4) Correction and adjustment of the final prod-
forming agents that are optimized to the formu-
uct
lations, production conditions, application tech-
Two strategies are adopted for producing the nique, and intended use of the resulting coating
millbase: composition. Such companies can supply spe-
cial, high-quality products.
1) Ab initio production
2) Mixed production, using pastes
Material Flow. Figure 9 illustrates the ma-
Ab initio production generally starts from raw terial flow in paint and coating production, start-
materials, and pigment mixtures are dispersed ing with the reception and storage of the raw ma-
directly in the batch. Mixed production starts terials and finishing with the end product ready
from ready-prepared pigment pastes: only one for dispatch. The type of raw material, its consis-
kind of pigment is usually dispersed in the tency, the amount consumed, and the packaging
126 Paints and Coatings
Table 22. Examples of compositions of coating materials for automotive mass production (wt %)
Filler One-pack topcoat, white One-pack topcoat, colored
Component Ab initio Mixed Ab initio Mixed Ab initio
Dispenser formulation (comminuted
material)
Paste 1 99.5 60
Paste 2 0.5 30
Paste 3 7
Paste 4 2
Paste 5 1
Solvent 20 18 25
Film former (resin) (100 %) 15 20 23
Pigment 25 60 50
Extender 35
Additives (volatile) 5 2 2
Total liquid components 75 80 73
Pigment and extender 60 60 50
Film former (100 %) 15 20 23
Proportion of dispersed millbase in total 60 40 20
formulation

Total formulation
Solvent 31 40 45
Film former (100 %) 30 35 45
Pigment 15 24 10
Extender 21
Additives 4 1 1
Total liquid components 65 60 55
Liquid components, pigment and extender 35 25 10

in the as-supplied state are decisive for material The paint maker also produces semifinished
flow and metering. In large factories, large stor- products (e.g., pastes) for internal use. The
age tanks for resin solutions and solvents have to semifinished products from 12 are stored in 3.
be installed and equipped with the latest safety Packaging materials flow via 4 to the filling ar-
devices. The raw materials are usually delivered eas at the end of resin (9) and paint (10) produc-
in tank trains. These bulk raw materials can be tion. Many different packaging types, sizes, and
pumped and conveyed to the sites of use via designs are used. The end products may be dis-
pipes. A considerable number of other liquid, pensed into containers the size of a road tanker,
pasty, solid, or powder raw materials are sup- into drums and barrels, or into cans with a capac-
plied, palletized, and depalletized in containers, ity of as little as 50 mL. Finally, the ready-for-
barrels, drums, or sacks. Open-air storage facil- use material is sent to the storage area 13 before
ities and warehouses for free-standing stacking it is dispatched.
are provided for this purpose. The raw materials Production based on vertical material and
for 1, 2, 4, and in some cases 3, are delivered process flow is most commonly used and will
to the appropriate stores by road. The material now be considered in a conventional factory
flow then continues to the production facilities (Fig. 10). Smaller factories operate on a hori-
(9 and 10). zontal concept, but the principles are the same.
Four types of product are made (see Section The material and process flow proceeds
7.2): downward through four floors as follows:
Fourth Floor. The fourth floor is used for in-
1) Clear or colored varnishes (do not contain
termediate storage and metering of the raw mate-
pigment)
rials required to produce the millbase. Solid raw
2) Paints (contain pigment)
materials (e.g., pigments and fillers) are stored
3) Powder coatings
on pallets in sacks, drums, barrels, or cartons.
4) Special products (e.g., putties, fillers, plas-
Liquid or pasty raw materials are kept in drums
ters)
or cans. These materials are weighed (b) and
 Paints and Coatings 127

Figure 10. Process flow in conventional paint making

a) Disperser; b) Scales; c) Premixer, dissolver; d) Movable container; e) Pump; f) Agitator mill; g) Paste mixer; h) End product
mixer; i) Filter, sieve; j) Container; k) Packing machine
128 Paints and Coatings

charged into the premixers or dispersers (a, c). protection materials are, however, exceptions.
Solvents and solutions of film-forming materi- Paint factories producing these bulk products
als are fed from the storage tanks into premixers are highly automated but extremely inflexible
or dissolvers (c) via pipelines and filling stations as regards the use of different raw materials and
with oval disk meters. semifinished products and their proper schedul-
Third Floor. The mixture is dispersed using ing. Enterprises that manufacture “tailor-made”
agitator mills (f). With mixed production the dis- products must have a wide range of equipment,
persed millbase is then fed as a single-pigment and simple and flexible production methods.
paste to paste mixers (g) and then to the end
product mixers (h). In ab initio production the
multipigment paste is sent directly from the ag-
itator mills to the end product mixers (h).
Second Floor. A large number of end prod-
uct mixers (h) of different sizes are used. With
mixed production the mixed pastes are metered
from the paste mixers (g) into mobile contain-
ers and then added to the end product mixers
(h). In ab initio production the dispersed mate-
rial is pumped directly from the agitator mills
(f) into the end product mixers (h). Formulation
of the paste mixture or dispersion is completed
in the end product mixer by adding film-former
solutions, solvents (via oval disk meters), and
additives. The product is sampled, tested, and
adjusted (e.g., shade, viscosity, other technically
important properties).
First Floor. The end product is sieved, fil-
tered, and dispensed from the end product mix-
ers via filling lines into containers, drums, or Figure 11. Process flow in modern paint making
small packages. a) Premixer, dissolver; b) Pump; c) Agitator mill; d) End
The material flow system is complex because product mixer; e) Filter, sieve
the mixers and machines have to be changed in
accordance with the product type and batch size. Quality Assurance. Almost every aspect of
Equipment also has to be reserved for specific the paint-making process is subjected to qual-
product groups with special shades or chemi- ity assurance measures. Depending on the type
cal properties. Only in this way can the effec- of product, this involves a number of correc-
tive cleaning of equipment and pipelines during tion stages and delay periods, particularly in the
batch changes be guaranteed. end product mixers. In the most commonly em-
In large paint factories there is an increasing ployed correction strategy, the desired quality is
tendency to perform the precharging (i.e., the approached and achieved in small steps. Correc-
accurate weighing and preparation of the solid tion in this context does not mean the elimina-
paint constituents) centrally in the storage area tion of defects, but the addition of small amounts
(Fig. 11). This has economic and organizational of materials. Quality assurance corresponding
advantages; it also reduces the risk of contamina- to the ISO Standards 9000–9004 (e.g., failure
tion. Filling is also centralized for the same rea- mode-and-effect analysis (FMEA) and statisti-
sons. Materials are conveyed in mobile contain- cal process control (SPC) [395]) has been intro-
ers or via pipelines. Cleaning inside pipelines duced in modern paint factories.
can be optimized by using scraper (go-devil)
techniques. Environmental Protection. The paint in-
Very few product lines in the paint indus- dustry has adopted a two-pronged strategy to
try are mass-produced; white emulsion paints, ensure environmental protection:
plasters, rust protection paints, and underbody
 Paints and Coatings 129

1) Apparatus and processes are enclosed as far 7.2.1. Varnishes

as possible to minimize emissions
2) If enclosure is not possible, the sources of Varnishes are usually colorless but may be
emission are selectively aspirated. Gaseous slightly colored due to the intrinsic color of
pollutants and vapors are collected and the binders, driers, or other additives. Colored
passed to central or decentralized disposal transparent varnishes contain soluble dyes or a
equipment [e.g., combustion plants (thermal small amount of finely dispersed pigments. Matt
or catalytic) or adsorption units], particulate varnishes may be opaque (milky), colorless, or
impurities being retained in filters. transparent; after drying they have a matt to
semigloss surface due to the presence of dulling
(mainly inorganic) additives.
7.2. Paint-Making Processes Liquid raw materials are mixed in a specific
sequence in slow- to high-speed stirrers or mix-
The wide variety of paint formulations are re- ers to give a homogeneous, streak-free mixture
flected in the variety of paint-making processes. (see Section 7.3.3). In larger mixers and tanks
Figure 12 summarizes the essential features of (up to 50 000 L capacity) the mixing device is
these processes. Only a few special products permanently installed in the vessels. Preconden-
(e.g., putties, plasters, or underbody protection sates and wax solutions are prepared in heatable
materials) are not covered by this scheme; they and coolable vessels equipped with stirrers.
are produced by special proprietary procedures Solids are usually dissolved in liquids using
(generally of the one-pot type). high-speed stirring equipment. If the formula-
tion contains dissolving and nondissolving sol-
vents (diluents), then the nondissolving solvents
are often added first, followed by the solid raw
materials (e.g., powders, granules, fibers), and
then finally the “true” solvent. With this order
of addition the surfaces of the solid particles
are wetted more effectively, resulting in uniform
penetration of the “dissolvers” into the solids.
Agglomeration is thereby avoided and dissolu-
tion is speeded up. In Figure 12 the sequence of
operations is 1, 2, 3, or 4, 7, 8, 9.

7.2.2. Paints

Dispersion. The liquid semifinished prod-

ucts (intermediates) used in paint making are
prepared in a similar manner to varnishes (see
Section 7.2.1). The most important stage in the
production of pigment-containing paints is com-
plete wetting and uniform distribution (i.e., dis-
persion) of the solid pigment particles in the
liquid, film-forming material. To obtain opti-
mal paint properties the pigment must be opti-
mally dispersed in the liquid. Many pigments are
surface-finished. An extremely fine grain size in
the finished paint results in undesirable effects
Figure 12. General flow diagram of the paint-making (e.g., gloss streaks).
process
Historically, to obtain homogeneous pigment
wetting and dispersion, kneaders, rotor and sta-
tor mills, and roller mills came first. These were
130 Paints and Coatings

Figure 13. Powder coating production

a) Premixer; b) Extruder; c) Cooling belt; d) Roll crusher; e) Tipping device; f) Ventilator; g) Bag filter; h) Explosion valve;
i) Hopper; j) Cellular wheel sluice; k) Air separation mill; l) Cellular wheel sluice; m) Screening device; n) Packaging

followed by ball mills, tank mills, attritors, and formulation vessels equipped with appropriate
(open) sand (bead) mills. Enclosed ball mills are stirrers. This stage can present serious problems
now widely used to comply with increasingly because the widely differing solvent concentra-
stringent quality and environmental protection tions of the two substance streams may cause
requirements. Fitted with an enclosure, a roller irreversible diffusion.
mill is still acceptable for some product lines Since the solvent molecules are more mo-
(e.g., pasty printing inks). Paint production pro- bile than the film-former molecules, they mi-
ceeds according to steps 1, 2, 4, 5, 6, 7, 8, and 9 grate down their concentration gradient from
in Figure 12. the millbase into the paint solution, resulting in
Commercial coating materials seldom have a decrease in volume of the pigmented phase.
the same composition as the ready-dispersed The distance between the pigment particles is
millbase. The proportion of film former in the reduced to such an extent that, even in stabi-
final product is generally higher. Highly concen- lized pigment dispersions, repulsive forces bet-
trated (high-solids) paint resins must be added ween individual pigment particles are overcome
to increase the proportion of film former to the and flocculation occurs. This process (pigment
required value. This is generally performed in shock) can be avoided by modifying the com-
 Paints and Coatings 131

positions of the millbase and the final formu- an extruder (b) where it is melted and homoge-
lation, or by suitable process technology (e.g., nized at temperatures above the softening point
rapid homogenization during final formulation). of the binder and below the activation tempera-
Flocculation may also occur when solvents are ture of the catalyst. The extruded paste is rolled
added because they remove the stabilizing film- out to a thickness of 2–3 mm and transported on
forming layers from the pigment surface. a cooling belt (c) or drum to a roll crusher (d)
which comminutes the cold mass into chips. The
Flushing was developed industrially in chips are finely ground in an impact pulverizer
the early 1930s. Aqueous pigment press cakes or air separation mill (k). The powder is then
or doughs are kneaded with binders, wetting screened (m) and classified to the desired parti-
agents, and additives until phase inversion oc- cle size fineness. Oversize particles are reground
curs, i.e., until the binder has displaced the wa- [396–398]. In addition to the vertical plant de-
ter from the pigment surface and the hydrophilic sign illustrated in Figure 13 production may also
pigment–water mixture has been converted into be performed horizontally.
a hydrophobic pigment–binder system. The bulk
of the water is decanted, any residual water be-
ing removed by applying a vacuum or in heated 7.3. Apparatus
roller mills.
Flushing has the advantage that the original 7.3.1. Mixers
primary form of the finely divided pigment par-
ticles found in the aqueous dough is retained. Ef- See also → Stirring; → Mixing of Highly Vis-
ficiently flushed pigments exhibit a purer shade, cous Media.
better transparency, and possibly higher yield in A wide variety of containers and tanks are
paints. used as mixers in the paint industry. Their mate-
rials of construction must be appropriate to the
contents being mixed. Paints containing organic
solvents are produced in steel or aluminum ves-
sels. Waterborne paints generally require stain-
less steel because of their high corrosion poten-
tial. The tanks may also be lined with enamel or
plastics.
The stirrers are mainly of the flat-blade, disk,
propeller, or turbine type [399–402]. Rotor–
stator systems are also used as continuous mix-
ers (Fig. 14). These machines are employed
particularly if an emulsion or an emulsion-like
product has to be produced (e.g., waterborne
paints) [403–405].

Figure 14. Continuous mixer for paint making (rotor–stator

system) 7.3.2. Dissolvers
a) Rotor; b) Stator; c) Housing
Dissolvers are specially modified mixers
(Fig. 15), and are mainly used in paint mak-
7.2.3. Powder Coatings
ing for mixing solids (pigments) and resin so-
lutions [406]. They have a good mixing effect
In order to produce powder coatings (see Section
and are even capable of breaking down coarse
3.4) solid binders (e.g., epoxy, polyurethane,
pigment agglomerates. The high shear forces re-
acrylic–polyester resins) are comminuted and
quired are produced by appropriate design and
thoroughly mixed with pigments, catalysts,
high speeds (up to 30 m/s at the stirrer tip).
hardeners, and additives (Fig. 13, a). The mix-
Power consumption may reach 50 kW/m3 . Dis-
ture then passes through a metering device into
solvers exist in single-shaft and multishaft ver-
132 Paints and Coatings

Figure 15. Types of dissolvers and dissolver disks

A) Simple dissolver; B) Dissolver with stator system; C) Double-shaft dissolver with three disks; D) Dissolver with disk for
pumping and shearing; E) Dissolver with two drives for separate functions

sions. Vacuum dissolvers are used for product 7.3.3. Kneaders and Kneader Mixers
degassing.
Various kneader designs (e.g., ram, internal,
screw, paddle, Z-, arm, and planetary knead-
ers, Fig. 16) are used to produce highly
viscous (pasty) paint concentrates (master
batches), uncured rubber compositions, and put-
ties (→ Mixing of Highly Viscous Media).
Kneaders have a high energy consumption be-
cause they are generally used to produce systems
that have a low binder content or are difficult to
wet [406].
Heatable and coolable kneaders are available
and both types can be fitted with a vacuum de-
vice. They may operate batchwise or continu-
ously and are equipped with screw conveyors.

7.3.4. Media Mills

See also → Size Reduction.

On account of the widely varying produc-
tion requirements (see Section 7.1), a wide
range of mills are used for dispersion. Ball
mills, rotating vessels filled with balls (diam-
eter > 10 mm), were developed first (→ Size
Reduction, Chap. 3.2). Ball mills are inefficient
compared with modern units because they oper-
ate batchwise and large batches cannot be pro-
Figure 16. Planetary (A) and vat (B) kneaders duced. In addition to safety problems, their high
a) Drive; b) Vat; c) Kneader hock
noise level is a disadvantage.
 Paints and Coatings 133

Figure 17. Closed agitator mills [387]

a) Grinding media; b) Rotor; c) Grinding chamber; d) Sealing system; e) Separator; f) Pump

To overcome the safety problems associated is installed to improve separation. The name of
with rotating ball mills, tank mills were de- the mill is derived from the fact that Ottawa sand
veloped which consist of a stationary vessel (particle size ca. 0.5–3 mm) is usually used as
equipped with a slowly rotating stirrer. Use of the grinding medium. The development of sand
grinding media less than 10 mm in size in- mills increased both product quality and produc-
creased product quality, grinding efficiency, and tivity. Throughput was, however, restricted by
thus output. the force of gravity. The viscosity of the paint
Increasing the stirring power, optimizing the pastes therefore had to be relatively low, which
geometry, and introducing an external forced cir- did not promote optimum dispersion. Another
culation led to further advantages and the devel- disadvantage is the open construction, which led
opment of the attritor (attrition mill). to additional emission problems.
The transition from batch production to con- A further advance was the development of
tinuous production required the development of enclosed agitator mills. The horizontal design
sand mills. Sand mills can be regarded as slender was intended to eliminate the influence of
attritors with a forced product circulation. They gravitational forces. Numerous design features
are charged with product vertically from the bot- have been optimized [401, 402, 405–415]. The
tom upward, gravity being mainly responsible most important developments are illustrated in
for the separation of the grinding media. A sieve Fig. 17.
134 Paints and Coatings

Figure 18. Centrifugal vortex mill

a) Grinding media; b) Rotor; c) Grinding chamber; d) Sealing system; e) Separator; f) Pump

Disadvantages associated with these mills are

the high wear of the stirrer elements, the expen-
sive axial face seals, and the limited throughput
due to the often extremely narrow devices used
to separate the grinding media (friction gaps,
sieve). Since the free cross-sectional area of the
separation devices can only be decreased within
certain limits, small grinding media (< 1 mm)
cannot be used to increase product quality [416].
The breakthrough in wet mill technology
came with the development of the centrifugal
vortex mill (Fig. 18) [416, 417]. The major in-
novation in this mill is the separation of the ac-
tive grinding zone from the passive separation
and sealing zone. This results in two advantages:
(1) very low wear in the passive separation and
sealing zone, and (2) the incorporation of large
surface areas for separation (sieves). The sec-
ond advantage is essential for any substantial
increase in output: the large sieve areas allow
throughput performance to be considerably in-
creased (by a factor of 10–20). The dwell time
is considerably shortened by a recirculation or Figure 19. Dispersion methods
multipass system. A fine, narrow particle size A) Passage; B) Cascade; C) Swing-batch, circulation
distribution can then be obtained more quickly. a) Mixer; b) Pump; c) Conventional mill; d) Let-down tank;
e) Centrifugal vortex mill
A device that combines the advantages of a large
product throughput and the use of small grinding
media, is the double cylinder bead mill. This mill A cascade of agitator mills (Fig. 19 B) pro-
has an internal grinding medium circulation to duces a considerably narrower particle size dis-
avoid compression of the grinding media [418]. tribution. Control is, however, more complex
than with the single-pass procedure.
Dispersion Methods. The dispersion meth- The swing-batch and circulation procedures
ods most commonly used in the paint indus- (Fig. 19 C) are suitable for machines with high
try are illustrated in Figure 19. The single-pass product throughputs (e.g., the centrifugal vortex
batch procedure (Fig. 19 A) is the most common mill and double cylinder bead mill). Control is
method. Its disadvantage is the broad dwell time simple.
distribution and the resulting wide particle size The swing-batch procedure involves two
distribution. It is also extremely difficult to con- vessels whose contents are alternately passed
trol, i.e., productivity falls sharply if the batch
has to be treated again to improve its quality.
 Paints and Coatings 135

through the agitator mill. The circulation proce- ten used, the rolls being arranged in various ways
dure is even simpler to control because the prod- (e.g., horizontal, inclined, or chair arrangement).
uct can be recirculated until the desired quality In modern high-speed systems the axis of the
and properties have been obtained. Only one ves- third roll is generally fixed in position, while the
sel is required per machine, which is an advan- first two rolls are hydraulically actuated. The
tage with frequent changes of product. A dis- rotational velocities are 40–100 min−1 for the
advantage is the backmixing which occurs in front roll, 140–200 min−1 for the middle roll,
the vessel, making the dwell time distribution and 300–600 min−1 for the third roll. Shear en-
less favorable than in the pendulum procedure. ergy for dispersion depends on rotational speed
Above about 20 cycles or passes the difference differences, and the roll nip clearance (con-
is negligible and the particle size distributions in trolled by the compression force). In order to
the two procedures are similar. compensate for viscosity fluctuations the roller
mills are generally designed so that they can be
heated or cooled.
7.3.5. Roller Mills
Like agitator mills, roller mills are also used 7.3.6. Auxiliary Equipment
to disperse and homogenize highly viscous pig-
ment pastes (Fig. 20). Roller mills are often also Sieves. Paints containing undesirably coarse
used for finishing (postdispersion or fine disper- particles must be screened. The simplest method
sion). The fact that dirt and coarse particles float is to sieve them through metal (steel) or plastic
to the top in the feed nip is a beneficial side ef- fabrics of specific mesh size. Polyamide screen
fect: the roller mill acts as a filter. bags are employed to facilitate handling. Metal
fabric is fastened or soldered onto cylindrical
metal frames.
Vibrating screens are used for products (e.g.,
metallic effect paints) that are difficult to screen
with fabrics. These screens have a driven cam
which causes the oscillating frame to roll.
The material is vibrated horizontally and flows
rapidly through the sieve.

Filters. In the production of intermediates,

varnishes, and synthetic resin solutions, turbid-
ity sometimes occurs which has to be eliminated
by filtration. The simplest method is filtration
through bag filters made of needled nonwovens.
The bag filters can be installed in metal filter
housings with closable, sealable covers. A per-
forated sheet-metal basket protects the filter bag
against overloading.
If impurities cannot be removed with bag fil-
ters, filter cartridges or candles are used. The
filter cartridges are inserted in individual hous-
ings or, in large-scale equipment, up to 24 car-
tridges are inserted side by side or one above the
other and held in place with quick-release mech-
Figure 20. Roller mills (one- and three-roller) anisms. Resin-bonded, needled nonwovens or,
a) Filling; b) Compression bar; c) Scraper in special cases, sintered metals are used as fil-
ter material. The fineness of the filter fabric (5–
Roller mills may have one to five smooth 100 µm) determines the filtration effect. Water is
rollers (rolls). Triple-roll systems are most of- first pumped through the filtration equipment to
136 Paints and Coatings

remove loose fabric constituents, lint, etc. from 8.2. Pretreatment of Substrate Surfaces
the filter. If serious problems arise (gel particles
or turbidity), layered filters such as plate and disk The surface of workpieces may be covered or
filters with or without a diatomaceous earth bed contaminated with coherent or discontinuous
are used. layers of the following materials:
An extremely time-consuming and expensive
method of removing unwanted coarse material Lubricants mineral oil products
(“oversize”) from paints and paint pastes, is cen- metallic soaps
graphite
trifugation. This technique should only be used molybdenum disulfide
if filters and screens prove unsuccessful because Corrosion-inhibiting oils petroleum sulfonates
it is often accompanied by a high product loss. inhibitors
With the increasing intensification of qual- mineral oil products
Fluxes inorganic salts
ity assurance measures before (incoming inspec- Polishing pastes mineral oils
tion, FMEA) and during manufacture (cleanli- waxes
ness tests, on-line particle size measurement) Scale, corrosion products metal oxides
metal salts
the use of auxiliary equipment is declining or Finely divided, foreign dust
limited to a protective function (“policing filtra- substances ash
tion”). slag
(from welding work)
Miscellaneous dermal deposition from
fingers/hands
8. Paint Application absorbed gas films
old coatings
adhering moisture
8.1. Types of Substrate [419]
These foreign materials all have adverse ef-
All solid substrates can be coated, including met- fects on the wetting behavior, adhesion, and cor-
als, plastics, wood, minerals, paper, and leather. rosion resistance of coating materials. The pur-
The surface structure of metals, their melt- pose of treatment prior to coating is therefore to
ing point, and susceptibility to the effects of remove foreign material from the workpiece sur-
weathering and chemicals (corrosion) can sub- face. Another important function is to create a
stantially influence the coating process and qual- reproducible surface state that ensures long-term
ity. protection against corrosion subsurface migra-
The coatability of plastics depends to a large tion and paint flaking at weak points or locally
extent on the material, design of the article, damaged areas of the paint film.
forming process, and the processing agents used
for this purpose.
The coating of wood is strongly influenced by 8.2.1. Pretreatment of Metallic Substrates
its structure and properties (elasticity, hardness,
strength, shrinking tendency). Some wood con- Many processes and techniques are used for pre-
stituents (e.g., pigments, resins, or tanning acids) treating metallic substrates (Table 23), [419–
can interfere with the coating process. See also 422].
→ Wood, Surface Treatment.
Coatings are used for different purposes:
1) Protection of an object against its environ- [Link]. Cleaning
ment (e.g., corrosion protection)
2) Improvement of appearance Mechanical cleaning is mainly used to re-
3) Surface modification to meet special physi- move scale, rolling skin, rust, burr, and paint
cal and functional requirements residues. Hammering, brushing, and lapping
The choice of coating technology and the jelly are used in smaller workshops and on
quality of the coat applied to a given article pri- building and construction sites. Grinding is also
marily depends on the substrate, its geometry,
design, and surface state.
 Paints and Coatings 137
Table 23. Summary of pretreatment methods
Method Material Impurities Temporary Improved
corrosion corrosion
Fe Al Zn Lubricants, Scale, Dirt, Drawing Corrosion Old protection protection
corrosion rolling shavings agents products paint after with
protection skin layers treatment coatings
oils
Mechanical methods
Steam and high-pressure water + + + + − + − − −
blasting ◦ *
Jet blasting (e.g., wet jets) + + + − ++ + ++ + −− −
◦
Manual abrasive methods (e.g.,
brushing,
grinding) + + + − + + + + −− −
◦
Wet chemical methods
Solvent degreasing
Steam + + + + − − − − −
◦ ◦
Dipping + + + + − − − − − −
◦
Ultrasonic dipping + + + + − + − − − −
◦
Alkaline degreasing
Spraying + + + + − + − − − − −
Dipping + + + + − − − − − −
◦
Pickling
Phosphoric acid + + + + − + −
* * ◦ *
Sulfuric acid + −− + + + −− −
* ◦ ◦
Hydrochloric acid + −− + + + −− −
* ◦ ◦
Caustic soda −+ − + + − −
* * * *
Phosphating
Alkali phosphate + + + − − − − + +
* *
Zinc phosphate + + + − − − − − − + ++
Chromating −+ + − − − − − − + ++
Adhesion promoters (wash + + + − − − − − − ++ ++
primer)
The symbols have the following meanings: ++ Extremely satisfactory. + Satisfactory. ◦ Moderately satisfactory. − Unsatisfactory.
−− Particularly critical.* Satisfactory only with special methods.

widely employed for finishing weld seams and include pickling, which can be used to remove
soldering points, smoothing and leveling file or scale and metal oxides. Sulfuric acid and hy-
tool marks, as well as for roughening mate- drochloric acid are usually used to treat steel and
rial surfaces to improve paint adhesion. Blasting zinc, while nitric acid, nitric acid–hydrofluoric
methods (sandblasting, compressed air, or water acid, or sulfuric acid–hydrofluoric acid are used
jet) remove impurities as a result of the kinetic for aluminum. Although pickling in phosphoric
energy of small hard particles. Abrasives may be acid is somewhat slower, it has the advantage
metallic (e.g., spherical cast iron shot) or non- that a thin conversion layer of the substrate
metallic products (e.g., corundum). Blasted and phosphates is produced, which provides tempo-
abraded surfaces are extremely dusty and have rary corrosion protection and is a good base for
to be cleaned by blowing, wiping, or washing. the subsequent coating. Previously, sulfuric acid
was preferred for pickling because of its low
Chemical Methods. See also → Metals, vapor pressure; acid losses are therefore slight
Surface Treatment, Chap. 2. Chemical methods and environmental pollution is low. Nowadays
138 Paints and Coatings

the tendency is to use hydrochloric acid because 0.15–0.25 MPa) and 50 g/L (dipping methods).
it allows better cleaning of the metal surface Both stationary and flow-through baths are used.
(even slightly alloyed steels). Evaporation of hy-
drochloric acid from the pickling baths is limited
by using self-contained or completely enclosed [Link]. Formation of Conversion Layers
units. Organic inhibitors are generally added to [419–423]
pickling acids to limit the pickling action to the
oxidic impurities and to minimize the dissolu- Conversion layers generally consist of inorganic
tion of the base material. Addition of surfactants compounds formed on the metal surface. They
has a limited degreasing effect. are used to increase the corrosion resistance and
Pickling in aqueous caustic soda solution is to improve the paint adhesion of the metal sur-
widely used for cleaning aluminum workpieces face.
on account of their amphoteric behavior. How- Industrially, phosphate layers are the most
ever, after alkaline pickling the article generally important and phosphating is used to treat steel,
has to be treated with acid to remove loosely ad- aluminum, and zinc. Chromating produces lay-
hering layers of pickling sludge and to brighten ers containing trivalent or hexavalent chromium
the surface. compounds and is mainly used with aluminum
and zinc. Special oxide layers and inorganic–
organic coatings are used for special purposes
[Link]. Degreasing in strip treatment.
The surface weight of conversion layers is
Processes using aqueous solutions or organic 0.05–5 g/m2 . With higher surface weights the
solvents have become extremely important for flexibility of the layers decreases, which has an
removing organic impurities. In special cases, adverse effect on the flexural adhesion of the or-
salt melts and treatments at elevated tempera- ganic coating.
ture in the gas phase are also employed. See also
→ Metals, Surface Treatment, Chap. 2. Phosphating Processes. See also
→ Metals, Surface Treatment, Chap. 3. The
Organic Solvents. Chlorinated hydrocar- most important phosphating processes are al-
bons are widely used. They remove oils and kali, zinc, and zinc–calcium phosphating. In al-
greases extremely effectively (generally in the kali phosphating the layer-forming cation orig-
vapor phase). Cleaning in immersion baths can inates from the substrate, in zinc phosphating
be significantly improved by using ultrasound. processes it originates from the phosphating
Increasingly stringent environmental protection solution.
legislation will, however, greatly restrict the fu- Alkali phosphating (iron phosphating) is
ture use of chlorohydrocarbon solvents. mainly used when corrosion protection does not
have to satisfy stringent requirements. The solu-
Aqueous Media. Degreasing may be per- tions (pH 4–6) consist of acid alkali phosphates,
formed with alkaline, neutral, or acidic aque- free phosphoric acid, and small amounts of ad-
ous media. Approximately neutral (mild alka- ditives; oxidizing agents (e.g., chlorates, chro-
line) degreasing agents with fairly high concen- mates, or nitrites), condensed phosphates (e.g.,
trations of wetting agents and surfactants are pyrophosphate or tripolyphosphate), and special
mainly used. An advantage of these agents over activators (e.g., fluorides or molybdates). The
alkaline or acidic media is a simpler and more first reaction is the pickling reaction which pro-
economical effluent treatment. The degreasing duces Fe2+ ions from the substrate (steel). These
agents hydrolyze animal and plant oils and ions react with phosphate ions from the solution
grease. Non-hydrolyzable components (mineral to form sparingly soluble iron phosphate that
oils and grease) are dissolved and dispersed by precipitates and adheres strongly to the metal
adding colloidal emulsifiers and wetting agents. surface. Zinc phosphate layers are formed in an
These baths are operated at 60–80 ◦ C and a pH analogous reaction sequence on zinc surfaces.
of 8–9. The concentration of cleansing agents Aluminum is usually treated with fluoride-con-
is between 1 g/L (spraying methods, pressure taining solutions; thin, complex coatings are
 Paints and Coatings 139

formed that contain aluminum, phosphate, and Chromating. See also → Electrochemical
fluoride. The baths are adjusted to a concentra- and Chemical Deposition, Chap. 11 In chromat-
tion of 2–15 g/L. Contact with the surface may ing, metal surfaces (mainly aluminum and mag-
take place via spraying, flooding, or dipping. The nesium) are brought into contact with aqueous
bath temperature is normally 40–70 ◦ C, but can acid solutions of chromium(VI) compounds and
be lowered to 25–35 ◦ C with special bath com- additives that activate and accelerate pickling.
positions. Treatment times are 5–10 s (spray- The pickling reaction converts acidic Cr(VI)
ing of strip material) and 1–3 min (spraying into basic Cr(III); cations of the treated metal
or dipping of individual parts). Iron phosphat- simultaneously accumulate in the liquid film
ing includes both thin-coating (0.2–0.4 g/m2 ) on the metal surface leading to precipitation
and thick-coating methods (0.6–1.0 g/m2 ). The of a gel-like layer containing chromium (III),
color of the layers is blue-green, and in some chromium(VI), cations of the treated metal, and
cases also reddish iridescent. The surfaces be- other components. The final conversion layer is
come matter and grayer with increasing coating formed after aging and drying. Treatment can be
weight. carried out by spraying or dipping (6–120 s) at
Zinc phosphating is primarily used for the 25–60 ◦ C. Effluent waste must be treated to re-
surface treatment of steel and zinc as well move Cr(VI); the most common method being
as composites of these metals with aluminum. reduction with sulfite to form Cr(III) followed by
Aqueous phosphoric acid solutions (pH 2.0– precipitation of chromium (III) hydroxide with
3.6) containing dissolved acidic zinc phosphate, milk of lime.
Zn(H2 PO4 )2 , are used. For further details, see For the yellow chromating of aluminum, so-
→ Metals, Surface Treatment, Chap. 3.1. lutions containing chromium(VI) compounds as
The phosphate layers are gray in color well as simple or complex fluorides and acti-
(weight 1.2–6.0 g/m2 ) and consist of Zn3 (PO4 )2 vators are used to accelerate layer formation.
·4 H2 O (hopeite), Zn2 Fe(PO4 )2 ·4 H2 O The pH value is 1.5–2.5 at total bath concentra-
(phosphophyllite), and Zn2 Ca(PO4 )2 ·4 H2 O tions of 5–20 g/L. The conversion layers con-
(scholzite). Layer formation is complete when sist of oxides or hydrated oxides of trivalent and
the metal is completely covered with a phos- hexavalent chromium and aluminum. The color
phate layer, and the pickling action initiating of the layer may range from colorless through
layer formation has stopped. The treatment baths yellowish iridescent to yellowish brown, corre-
contain 0.4–5 g/L of zinc and 6–25 g/L of phos- sponding to an increase in the surface weight
phate, calculated as P2 O5 . from 0.1 to 3 g/m2 .
The phosphating baths are usually used in The essential constituents of the aqueous so-
automatic or semiautomatic dipping, spraying, lutions for green chromating are chromic acid,
or flooding plants at 45–70 ◦ C; low-tempera- fluorides, and phosphates. The pH value of the
ture processes operating at 25–35 ◦ C also ex- baths is slightly less than in the case of yellow
ist. Treatment times are 60–120 s (spraying pro- chromating, and the bath concentration is nor-
cess) and 3–5 min (dipping process). The iron mally 20–60 g/L. The conversion layers con-
phosphate sludge must be removed periodically sist largely of chromium(III) phosphate and
or continuously from the bath. aluminum(III) phosphate, with small amounts
Low-zinc processes were developed with the of fluorides and hydrated oxides. The surface
introduction of cathodic electrodeposition coat- weight is 0.1–4.5 g/m2 , and the color ranges
ing. In the normal zinc processes flat, sheetlike from iridescent green to deep green.
crystallites (mainly hopeite) are formed which Aqueous, chromium-free acidic solutions
may project from the surface. In the low-zinc have also been developed for aluminum mate-
process the layers mainly consist of phospho- rials that may contain complex fluorides of tita-
phyllite. They have a parallel orientation rela- nium and zirconium, phosphate, and special or-
tive to the metal substrate and are more finely ganic compounds. These solutions are applied
crystalline and compact than the hopeite layers. by spraying or dipping (up to 60 ◦ C) and pro-
Very thin layers with a higher iron content are duce thin, almost colorless conversion layers
produced with nitrite-free low-zinc processes. with a surface weight < 0.1 g/m2 .
140 Paints and Coatings
Table 24. Pretreatment methods for plastics

Aqueous chromic acid solutions containing 8.2.2. Pretreatment of Plastics [419–421,

chlorides, simple and complex fluorides, sul- 424–426]
fates and formates as activators, are used for
chromating zinc. The total bath concentration is Pretreatment of plastic surfaces is necessary for
5–30 g/L, the pH value 1.2–3.0. The bath tem- the following reasons:
perature is in the range 25–50 ◦ C, the process
1) To increase adhesion strength
times are 5–120 s, the achievable surface weight
2) To reduce the concentration of interfering
is 0.1 –3 g/m2 . The layer color changes with in-
constituents and mold release agents
creasing surface weight from iridescent through
3) To eliminate surface defects (e.g., bubbles)
yellow to brown or olive green.
4) To remove interfering foreign substances
Rinsing. A passivating rinse is necessary 5) To increase electrical conductivity
to exploit the quality-improving properties of Many pretreatment techniques are used in
conversion layers. The most important rinsing practice (Table 24). The normal physical method
agents are dilute aqueous solutions of chromic used to improve the adhesive strength of the
acid, optionally with additional amounts of chro- coating to the substrate is to slightly roughen the
mium(III). Equally good or only slightly worse surface by solvent treatment, abrasion, or blast-
results can be obtained with solutions free from ing. Some plastics (e.g., polyolefins) require spe-
chromic acid and containing polyvalent metal cial pretreatment methods; processes that mod-
cations (e.g., chromium(III) or also organic com- ify the surface molecular layers of the plastic
ponents). The concentration of active substances to increase their polarity have proved suitable
in the rinsing baths is 100–250 mg/L. Rinsing is (e.g., flaming, immersion in an oxidizing acid,
performed at 20–50 ◦ C, treatment time ranges immersion in a benzophenone solution with UV
from a few seconds to about a minute. The sur- irradiation, corona treatment, plasma treatment).
faces should be sprayed with demineralized wa-
ter as a last rinse to prevent crystallization of
water-soluble salt residues.
 Paints and Coatings 141

Corona discharge is performed in a high- 3) Rectification (filling, patching) of processing

frequency alternating field (14–40 kHz) at 10– and growth defects in the wood
20 kV between two electrodes. The plastic sur- 4) Structuring by brushing, burning, sandblast-
face is oxidized in a very short period (millisec- ing, embossing, or leaching
onds). Plasma treatment is carried out under a 5) Staining with dyes dissolved in water or sol-
moderate vacuum down to ca. 10 Pa. The ad- vents, or with pigment dispersions
vantage of this technique is the better penetra-
tion depth and the fact that it is also possible to
treat shaped parts more easily. The plasma can 8.3. Application Methods
also burn in gases (e.g., argon), whereby spe-
cial effects (e.g., plasma polymerization) can be Many techniques have been developed for the in-
achieved. dustrial application of coatings. The individual
Adhering processing additives (lubricants, industrial coating methods can, however, only be
release agents) can be removed by cleaning with employed in limited areas if design and produc-
solvents or aqueous surfactants. The solvent sta- tion sequence are not matched to the require-
bility and solvent and water absorption of the ments of the coating technique. Adoption of
plastic material should be taken into account. In more environmentally friendly coating methods
order to reduce migration of constituents (shap- is therefore often less a problem of investment,
ing agents, plasticizers, dyes, organic pigments, than a problem of the application limits of the
stabilizers) during and after coating, preliminary relevant processes. Analysis of the criteria for
tempering is often recommended (at the same choosing a coating method is a complex task.
time surface defects can also be detected). Of particular importance are the workpiece (de-
Surface defects resulting from production sign, material), the coating material, the number
(e.g., pores, bubbles, flow seams and project- of workpieces and batch sizes, range of work-
ing fibers) are rectified by surface appearance pieces, requirements demanded of the coating
enhancement. Deeper-lying defects are filled in (e.g., decorative appearance, corrosion protec-
and smoothed with putties. tion), economic factors, legal provisions, and
Elimination of foreign substances (e.g., dirt available facilities, premises, and equipment.
particles and fibers) is very difficult due to the Economic factors generally have top priority for
electrostatic charge of the plastics material. Al- choosing an application method on a commer-
ternative methods are wiping with a lint-free cial basis. Coating systems and processes are
cloth wetted with water or a water–alcohol mix- usually preferred that best satisfy the demands
ture or blowing with ionized compressed air. and requirements for thin coatings, high degree
Plastics can also be made permanently antistatic of material utilization, low energy costs, and
by applying a dielectric coating. good automation. Modern coating methods that
best comply with these requirements are elec-
trodeposition coating, electrostatic atomization,
8.2.3. Pretreatment of Wood [419, 420] and electrostatic powder spraying.

Properly graded sanding with appropriate sand-

papers is a prerequisite for a satisfactory wood 8.3.1. Spraying (Atomization) [419–421,
surface. Industrially, sanding is performed on 427]
cylindrical abrasive-belt machines or automatic
grinders, followed by brushing and suction to In conventional spraying, atomization is the re-
remove abrasive dust. sult of external mechanical forces, i.e., the ex-
Surface pretreatment includes the following change of momentum between two free jets (air
steps: and paint). See also → Spraying and Atomiz-
ing of Liquids. Atomization may be classified as
1) Removal of resins, e.g., by hydrolysis (wood compressed air atomization (air 0.02–0.7 MPa,
soaps or soda solution) or dissolution (e.g., paint 0.02–0.3 MPa), airless atomization (paint
alcohol, acetone) 8–40 MPa), and air-assisted airless atomization,
2) Removal of adhesive residues also termed airmix process (air 0.02–0.25 MPa,
142 Paints and Coatings
Table 25. Nonelectrostatic atomization methods

paint 2–8 MPa), and special technologies (Table late the jet shape and assist atomization. The ex-
25). panding compressed air leaves the paint nozzle
In compressed air (pneumatic) atomization, at high velocity. A low-pressure area is formed in
compressed air flows through an annular gap in the nozzle aperture which exerts a suction effect
the head of the spray gun that is formed between and assists outflow of the paint. The difference
a bore in the air cap and the concentric paint between the velocities of the compressed air and
nozzle. Further air jets from air-cap bores regu- the exiting paint atomizes the paint into particles
 Paints and Coatings 143
Table 26. Electrostatic atomization methods

that are conveyed as spherical droplets in the free compressed air atomization, a low-mist coating
jet. In the high-pressure process (0.2–0.7 MPa) is possible.
the exiting air jets can atomize the paint material Hot spraying can be combined with all of
extremely finely. The size of the liquid droplets the spraying methods described above and is
varies from ca. 10 µm to 100 µm (depends on used for large film thicknesses or highly viscous,
the liquid viscosity, amount of delivered paint, high-solids paints (lower solvent consumption).
and air pressure). In the low-pressure process The paint is heated to 50–80 ◦ C in a heat ex-
(0.02–0.2 MPa) atomization is correspondingly changer. Immediately after atomization the heat
coarser (20–300 µm). Depending on the viscos- content of paint droplets is transferred to the air
ity and throughput, the paint can be fed to the and the workpiece. The droplets therefore cool
nozzle via a suction cup, a pressure cup, a flow and their viscosity rapidly increases; the risk of
cup, or pressure tank. sagging at larger layer thicknesses is thus re-
In airless (hydraulic) atomization the paint duced.
is forced through a slit nozzle of hard metal un- In two-pack paints both the binder and the
der high pressure (8–40 MPa). On account of the hardener have to be mixed before application.
high degree of turbulence, the paint stream disin- In paints with a short pot life the paint must be
tegrates immediately after leaving the fluid tip. metered and mixed in the atomization equipment
A similar atomization process occurs in spray immediately prior to use. The two reactive com-
cans where the paint pressure is produced by the ponents are normally mixed in static mixers after
propellant gas. metering.
The combined airmix process operates at
a lower paint pressure (2–8 MPa). Additional
low-pressure air jets (0.02–0.25 MPa) from the 8.3.2. Electrostatic Atomization [419–421,
air-cap bores impinge on the spray jet to mix and 427]
homogenize it. In addition to the atomizer and
a compressed air generator (airless pump), the In purely electrostatic spraying, the paint is at-
airmix unit therefore also requires compressed omized solely by electrostatic forces. In electro-
air for postatomization. Advantages over the air- statically assisted spraying, atomization takes
less method are the less sharply defined spray place by the methods described in Section
jet and the smaller droplet size. Compared with 8.3.1, with simultaneous or subsequent electri-
cal charging.
144 Paints and Coatings
Table 27. Dipping methods

In all electrostatic coating methods an electric cial cases on account of their limitations (work-
field is applied between the atomization equip- piece geometries, type and throughput of the
ment and the workpiece. The advantages and paint).
disadvantages of this technology are listed in Electrostatically assisted atomization methods
Table 26. The paint is electrically charged by a are more versatile than purely electrostatic meth-
concentrated electric field at a high-voltage elec- ods because atomization takes place mechani-
trode. In “lead charging” the nonatomized paint cally. The electric field serves only to charge
is charged by direct contact with the electrode. the paint material and to transport the charged
In “ionization charging” mechanically produced droplets to the workpiece. The following sys-
paint droplets are charged by attachment of ions tems are used:
from the air; the electrode serves as a corona tip 1) Electrostatic high-speed turbo bells (diam-
that generates these ions. eter 30–80 mm, rotational speed 15 000–
In purely electrostatic spraying the paint is at- 40 000 min−1 , voltage 70–120 kV)
omized solely by electric field forces. The paint 2) Electrostatic high-speed disks (diame-
flows as a thin film over a high-voltage sharp ter 150–250 mm, rotational speed up to
edge, where it is subjected to high field forces. 20 000 min−1 , voltage 70–120 kV)
The paint film breaks up into threads and then 3) Electrostatically assisted atomization guns
into charged droplets that follow the electric (charging by means of needle-shaped elec-
force lines to the workpiece. Only paints with a trodes arranged directly in or on the paint
moderate viscosity and an electrical conductiv- nozzle, voltage 50–100 kV).
ity in the range 5×10−6 to 5×10−9 S/cm can be
applied in this way. The best known designs are The extremely high electrical conductivity
the electrostatic spray gap (AEG method), the and high dielectric constant of waterborne paints
electrostatic spray cone (diameter 70–250 mm, should be taken into account. The paint supply
max. rotational speed 1500 min−1 ), and the system must be electrically insulated to prevent
electrostatic spray disk (diameter 400–700 mm, short circuiting. Ionization charging or, in the
max. rotational speed 3000 min−1 ). Purely elec- case of automatic equipment, the installation of
trostatic spraying methods are only used in spe- an insulated paint supply system have proved of
value.
 Paints and Coatings 145

8.3.3. Dipping [419][420][421, 428] the lower paint price and lower expenditure on
plant technology.
Dip coating is one of the simplest and old- In cathodic electrodeposition the workpiece
est coating methods. In addition to dipping in acts as the cathode; this method is more
solvent- or waterborne paints, electrodeposition important than anodic electrodeposition. The
has become important for large-scale series pro- binders consist largely of non-water-soluble
duction (Table 27). epoxy resins, and to a lesser extent of acrylic
resins (one-layer coatings). These resins are con-
Conventional Dipping. In conventional verted into a water-soluble (i.e., ionized) state
dipping the workpieces are immersed in the by neutralization with organic acids (e.g., acetic
paint and then removed (Fig. 21). The liquid acid):
paint adheres to the surface and is then dried or
stoved. Care should be taken to ensure that the
workpieces do not float during dipping and that
air bubbles do not become trapped. The speed at
which the workpiece is removed from the bath
must be selected so that excess paint adhering to Water is decomposed by electrolysis at the
the surface can run off. The draining and evap- electrodes
oration time must be sufficiently long to ensure
satisfactory evaporation of the solvents (if nec- 2 H2 O→O2 +4H+ +4 e−
essary a hot air zone should be included for wa- and at the workpiece
terborne paints).
2 H2 O+2e− →H2 +2 OH−

Iron from the high-grade steel anodes is also ox-

idized at the anode and passes into solution. Hy-
droxyl ions are formed at the cathode and react
with the solubilized resin causing reversal of the
neutralization:

Figure 21. A conventional dipping unit

a) Edge suction; b) Overflow; c) Circulation system The binder then coagulates and is deposited
with pump, filter, piping, and nozzles; d) Dipping tank; as an irregular, porous layer on the workpiece.
e) Heating and cooling device; f) Cover (in the form It is converted into a uniform, sealed paint film
of roller-type covers); g) Raising and lowering system;
h) Workpiece by stoving.
Electrodeposition equipment and technology
is expensive and is therefore practicable only for
Electrodeposition. Electrodeposition large-scale series coating (Fig. 22). In addition
paints are suspensions of binders and pigments to the dipping tank and a storage tank, circu-
in fully demineralized water with low concentra- lation systems for the paint and auxiliary ma-
tions (ca. 3 %) of organic solvents (see Section terials, rinsing systems (ultrafiltrate, fully dem-
3.8). Electrodeposition coating may be either ineralized water), a regulated d.c. supply (200–
anodic or cathodic. 400 V), and the workpiece transporting sys-
In anodic electrodeposition the workpiece tem (curent supply) also have to be installed.
acts as the anode. This method is only used to a Since electrodeposition systems require tem-
small extent. Disadvantages compared with ca- perature control, production tanks are equipped
thodic electrodeposition are its poorer handling with heaters and chillers.
and corrosion protection. Advantages include
146 Paints and Coatings
Table 28. Miscellaneous wet coating methods

8.3.4. Miscellaneous Wet Paint Coating portant because they are easily automated, have
Methods [419–421, 428] a high material yield, and are environmentally
friendly. With roller coating the paint material
Other wet paint coating methods are summa- is transferred from rotating rubber rollers to one
rized in Table 28. Application with a brush or or both surfaces of the workpiece (Fig. 23). In
roller is now only used to a great extent in the forward roller coating (layer thickness ≤ ca.
handicrafts sector, do-it-yourself sector, or on 12 µm) the workpiece and paint application
building sites. roller run in the same direction. With reverse
Flat workpieces (e.g., paper sheets, films, roller coating (layer thickness 3–100 µm) they
wooden boards, and panels) can be coated eco- run in opposite directions.
nomically and quickly by rolling, pouring, or The pouring method is commonly used in the
knife coating. These methods have become im- wood and timber trade. Here the paint is pumped
 Paints and Coatings 147

Figure 22. Cathodic electrodeposition coating unit

a) Dipping tank with overflow; b) Recycle circulation; c) Paint filter circulation; d) Paint cooling circulation; e) Ultrafiltration;
f) Anolyte circulation; g) Anodes; h) Metering of paint; i) Rinsing system; j) Ultrafiltration rinsing; k) Recirculated material
rinsing; l) Water rinsing; m) Power supply; n) Transportation system; o) Storage tank

into a pouring head that has a paint outflow slit Highly pigmented, pasty coatings and vis-
with adjustable lips (Fig. 24). Paint that does cous putties and fillers are applied by troweling.
not come into contact with the workpiece is re- The materials are applied with a pair of coun-
turned to the tank via a collecting channel. Since terrotating rollers. Excess material is smoothed
the paint is constantly circulated and is heated and “pressed” into the workpiece surface. This
by the circulation pump, it must be cooled and method can only be used for flat, striplike, or
must contain high-boiling solvents. panel-shaped workpieces (e.g., wooden panels).

Figure 23. Roller coating

A) Reverse roller coating; B) Forward roller coating
a) Metering roller; b) Coating material; c) Paint roller;
d) Workpiece

Knife coating is used in the paper and tex-

tile industry for coating continuous material.
Figure 24. Pouring method
Knife coating can also be used to print and coat a) Paint tank; b) Drip pan; c) Transporting belt; d) Article
flat, two-dimensional workpieces. The coating being coated; e) Aperture regulation; f) Pouring head;
is applied to the substrate which then passes g) Paint film; h) Pressure release value; i) Paint filter;
under a doctor knife. The coating material is j) Paint line; k) Valve for quantitative adjustment; l) Pump
pressed onto the workpiece with the doctor knife
(Fig. 25). The knife also removes excess coating With flow coating gentle streams of paint are
material and smooths the surface. pumped over the workpieces via nozzles. Excess
148 Paints and Coatings

Figure 25. Knife coating

A) Coating of unit items (panels, plates, disks, etc.); B) Coating of semifinished articles (strips, sheets)
a) Coating material; b) Doctor knife; c) Substrate

paint flows into a collecting trough and can be

recirculated (Fig. 26).
Small items (e.g., hooks, eyelets, clasps, and
buckles) can be coated by centrifugation or drum
coating. The workpieces must not adhere to one
another, nor must they become entangled. In
centrifugation the workpieces are placed in a
wire basket, and then immersed in a paint bath
and centrifuged at a rotational speed of about
500 min−1 . With drum coating paint is fed into
a rotating drum containing the workpieces. The
paint feed can be achieved by adding special,
low-viscosity paint or by spraying with spray
guns.
Coil coating denotes the continuous coating
of cold-rolled steel strip (including galvanized
strip) or aluminum with organic polymers. In au-
tomated plants the metal strip is first cleaned and
chemically pretreated. The strip is then roller-
coated on one or both sides, with one or more
coats of liquid, thermosetting or thermoplastic
coating materials. The paint coat is dried in an
oven after each application. Throughput rates
are of the order of 1–3 m/s. Constant production
conditions using appropriate control devices en- Figure 26. Flow-coating method
sure high quality. a) Paint nozzle; b) Drip pan; c) Filter; d) Paint adjustment
valve; e) Pump; f) Paint tank
 Paints and Coatings 149

8.3.5. Powder Coating [420, 421] ject. Increasing the number of guns or reducing
the gun output often improves coating applica-
In powder coating the coating material is applied tion. Parts with complicated shapes, particularly
to the workpiece in the form of dry (i.e., solvent- those with Faraday cages, are extremely difficult
free) thermoplastic or thermosetting powder. to coat, at least with a constant layer thickness.
The powder particles are heated and melt to form Good grounding (earthing) is necessary for
a sealed film. The thermoplastic powders melt satisfactory results. For safety reasons, earth
and fuse on heating whereas the thermosetting leakage resistances of less than 1 MΩ (at 5 kV)
powders also become chemically cross-linked. are required. Good grounding can also be ob-
Two main application processes are used: elec- tained via contactless, electrostatic processes.
trostatic spraying and fluidized-bed coating. A large proportion of coating powder plants
operate partly or fully automatically. Many types
Electrostatic Spraying. The principle of of equipment are commercially available [429,
electrostatic spraying is simple. A coating pow- 430]. The most important cabin type is the com-
der is a dust with a particle size in the range pact unit with replaceable filters in which the
10–80 µm. When dispersed (fluidized) in air the air that entrains and removes nonadherent pow-
powder flows in the same way as a liquid and is der is fed to a filter housing, flange-mounted on
applied in spray cabins using special spray guns the rear wall. In the filter the powder is sepa-
onto the cold or hot workpiece. The coating pow- rated from the air and concentrated. The air is
der adheres to cold workpieces electrostatically, then vented into the atmosphere or directly re-
whereas on hot workpieces it adheres by fusion. cycled to the working area. If the color has to
The workpiece generally passes through a dryer. be changed the cabin is cleaned and a new filter
The coating powder overspray is suctioned off, housing is mounted. If the unit operates with one
separated from the air, screened, and reused. filter housing only, the filter housing is cleaned.
Care should be taken to minimize the length Criteria for spray cabins, powder recovery
of pipes for powder transport and to maximize systems, and powder preparation systems are
the deposition efficiency in order to avoid prob- mainly determined by the time required to
lems caused by a shift in the particle size dis- change colors. A compact unit with one replace-
tribution. A sufficiently large number of guns, able filter is used for one or a few colors. A com-
a coating powder cloud size matching the size pact unit with one or more replaceable filters or
of the workpiece, adjustment of the oscillating a filter carpet unit is used for several colors. For
movement of the gun supports, gun triggering, many colors a unit equipped with cyclones (or a
and a continuous powder metering system with filter carpet unit) or a compact unit with several
maximum accuracy are advantageous. Minimiz- replaceable filters should be used. If necessary,
ing the powder content of a plant facilitates secondary colors can be applied without recov-
cleaning. ery or with liquid paints.
Coating powders are mainly sprayed with After the coating powder has been applied the
guns with negative corona charging. Guns with workpiece can be passed directly to the dryer.
friction charging (positive charging by charge An evaporation zone is not required as is the
separation on polytetrafluoroethylene), in some case for solvent-based paints. Since only the
cases with additional corona charging are, how- carrier medium air, and not a solvent, has to
ever, also used. A new generation of corona- escape from the film, the coating powder can
charged guns with ventilated deflector plates or be heated much more quickly at the oven inlet
without deflectors need to be cleaned far less than is the case with conventional solvent-based
frequently. paints. Heating can be performed with IR zones
Further developments include systems with or, after the coating powder has fused, with spe-
more uniform metering, low-voltage guns pro- cial blowing zones. Rapid heating results in short
ducing fewer free ions and therefore better pene- oven lengths and usually improves leveling and
tration into corners and cavities (Faraday cages), wetting. Since the stoving loss of coating pow-
and higher deposition efficiencies obtained by ders is very low the ovens can be operated in a
using slit-shaped nozzles and a triggered powder highly energy-efficient manner with a relatively
output that may be related to the shape of the ob- low rate of exhaust air.
150 Paints and Coatings

Fluidized-bed coating leads to substantially thermally cross-linking paint can only be guar-
thicker layers than electrostatic spraying. The anteed if curing is adequate. In undercured paint
workpieces are preheated to 200–400 ◦ C in an systems, adhesion to a subsequent layer may be
oven, dipped briefly (1–10 s) in vessels con- adversely affected. If, however, the maximum
taining fluidized coating powder (particle size curing temperature is exceeded the paint layer
40 –200 µm). The excess powder is removed may become brittle or yellow. The curing time
by vibration, shaking, or blowing and the work- is also important.
piece is optionally postheated and then cooled Curing and hardening may be either physi-
with air or water. The capacity of the fluidiza- cal or chemical. With a suitable combination of
tion basins ranges from a few grams to several binders, both types of curing methods may pro-
tonnes. ceed in parallel or overlap.
The layer thickness is determined by the
preheating temperature, the heat content of the Physical Curing [419]. Physical curing oc-
parts, the dipping time, and the coating powder. curs when polymers dissolved in organic sol-
Parts with complicated shapes or with different vents gradually cohere to form a solid film and
substrate thicknesses are difficult to coat. The then a network. Cohesion occurs solely as a
layer thicknesses obtained by the various appli- result of solvent evaporation without chemical
cation methods and the resultant use profiles are cross-linking. Such polymer films are generally
summarized in Table 29. reversible, i.e., they dissolve in the original sol-
vent. Physically drying binders (e.g., nitrocel-
lulose and its esters, vinyl resins, polystyrene,
8.3.6. Coating of Plastics and Wood [420] acrylate esters, chlorinated rubber, bitumen) are
mostly chainlike or threadlike molecules with
Most coating methods described in Sections short side chains.
8.3.1, 8.3.2, 8.3.3, 8.3.4, and 8.3.5 are also suit-
able for plastics and wood. The resistance to sol- Chemical Curing [419]. During chemical
vents and heat as well as the electrical conduc- curing film formation occurs as a result of for-
tivity of the plastics or wood must, however, be mation of chemical bonds between the binder
borne in mind. molecules. The binders become increasingly in-
Inmold coating (IMC) is an application tech- soluble as cross-linking proceeds, and ultimately
nique used for plastics in which the coating ma- form irreversible (i.e., insoluble) thermosetting
terial is applied during production of the plastics. films. In solvent-containing systems physical
The coating material is first injected (generally curing also occurs simultaneously.
electrostatically) into the mold that is previously
coated with a release agent. After the mold has Curing methods may be divided into three
been closed the plastic is then injected, foamed, groups:
and hardened. This method can be used for
glass-fiber-reinforced plastics and polyurethane 1) Curing with a heat carrier (air)
foams. A similar method is used with sheet 2) Curing with radiation (IR, UV, electron
molding compounds (SMC resin mats). After beams, laser beams, plasma arc)
the resin mat has been inserted in the mold, the 3) Curing by means of electrical processes (in-
SMC is compressed and hardened. The mold ductive curing, resistance, high-frequency
tool is then opened and coating material is in- and microwave curing)
jected through the slit opening, compressed, and
hardened. Curing with Heat Carriers. Curing with
a circulating hot air stream is the most impor-
tant curing method. The heat causes the solvent
8.4. Paint Curing Methods [419–426] vapors to evaporate from the coating film and
they are removed by the air current. Heat trans-
The performance of a coating depends on the fer and thus film formation occur from the exte-
chosen curing conditions. For example, mechan- rior to the interior. Paint curing is also possible
ical and other properties associated with a given with parts having a complicated shape. Since
 Paints and Coatings 151
Table 29. Layer thicknesses and typical uses in powder coating
Application method Temperature of workpiece Typical layer thickness, µm Uses
Electrostatic cold 25–100 interior: decoration, corrosion protection
Electrostatic cold 50–120 exterior: weather resistance, decoration, corrosion
protection
Electrostatic cold 50–250 resistance to chemicals, electrical insulation, corrosion
protection
Electrostatic hot 150–600
Fluidized bed, flocking hot 200–>1000

the whole workpiece has to be heated, long cur- may be up to 100 kW/m2 if appropriate regulat-
ing times and thus also large ovens are required. ing equipment is used.
Heat consumption is relatively high because the UV radiation with a wavelength range of
workpiece, paint film, transporting device, parts 0.32–0.4 µm is used for curing paints. The
of the conveying system, as well as the fresh air UV radiation initiates photochemical reactions
(maximum permissible concentration of com- which lead to cross-linking. An added photoini-
bustible solvents in the oven is 0.8 vol %) all tiator (sensitizer) decomposes in the paint into
have to be heated. free radicals that initiate polymerization of the
binder. Curing with UV radiation is of practi-
Curing with Radiation. See also Section cal importance for hardening colorless polyester
3.7. Radiation curing methods have become in- putties or primers, and offset and printing inks.
creasingly important in the last few years. Paint The hardening times are of the order of a few
curing proceeds more rapidly than in circulating seconds.
air curing since the whole workpiece does not In pulsed radiation curing (PRC) exothermi-
have to be heated. However, only large flat parts cally reacting paints and printing inks are cured
can be satisfactorily treated. by UV pulses at a wavelength of ca. 197 nm.
Microwaves (frequencies 3–600 GHz, wave- The pulses break the carbon double bonds of
length 0.5 mm–10 cm) are generated in mag- the binder because this wavelength range cor-
netrons and transmitted in hollow conductors. responds to their resonance frequency. A chain
They exhibit wave effects such as interference reaction starts throughout the whole layer, and
which lead to localized concentrations of energy curing takes place within a few seconds.
(wave peaks). Interaction between the polar ma- Electron beams are generated by applying an
terial in the paint film and the electromagnetic al- accelerating voltage (150 kV) to a thermionic
ternating field is manifested macroscopically as cathode. An electron beam (ca. 6 mm diameter)
a heating effect. Since microwaves are reflected is spread out into a curtain beam by a beam split-
by electrically conducting surfaces, this method ter. The electrons leave the beam distribution
can be used only for nonconducting substrates housing through a very thin metal sheet. When
(plastics, wood, or paper). these electron beams strike binder monomers,
Infrared (IR) radiation (wavelength they initiate polymerization in the paint film. Po-
0.76 µm–1 mm) is absorbed, reflected, or trans- lymerization occurs in a fraction of a second and
mitted by an object. In the paint film absorbed must be performed in a vacuum or in an inert gas
radiation is converted into heat. The paint film atmosphere. The equipment must be screened to
cures from underneath and the paint surface protect the operators.
does not harden initially (solvents can, however, Sharply localized curing can be achieved with
still escape without any problem). The wave- laser beams. The carbon dioxide laser, which has
length and intensity of the IR radiation must be a total beam output of 100 W/cm2 at a wave-
matched to the paint being hardened. Absorption length of 10.6 µm, can be used for this purpose.
behavior is determined by the pigment, pigment A plasma arc may also initiate cross-linking
volume concentration, and binder. Longwave in a paint film. The high temperatures produced
IR radiation (4.0 µm–1 mm) is absorbed by in the interior of the plasma arc are transmitted
the pigments at the surface, while shortwave only to a small extent to the paint film.
radiation (0.76–2 µm) can penetrate the paint.
Normal thermal outputs are 5–25 kW/m2 , and
152 Paints and Coatings

Drying by Electrical Methods. In electri- fore starting the tests are described in ISO 1513.
cal methods electric current is directly converted Only those tests that are important for paint
into heat (resistance drying) in the workpiece or storage, transportation, and application are de-
in the paint film. scribed here.
In inductive curing an induction coil is lo-
cated close to a metallic workpiece and gener- Viscosity. Although paint viscosity can
ates eddy currents in the latter. The workpiece be accurately measured with viscometers, paint
therefore becomes hot and the paint is heated consistency is normally assessed with flow cups.
from beneath the film; solvent loss or curing oc- The time in seconds required for a known vol-
curs. ume of paint to flow out of the cup through a jet
In high-frequency curing the workpieces are is measured. Paints of higher or lower viscosity
arranged between two capacitor plates in a can be matched by using cups with different jet
radiofrequency field (108 –109 Hz). Molecules diameters.
(dipoles) align themselves and are polarized in Measurement of the run-out time from flow
the alternating electric field. They therefore os- cups has been adopted worldwide since this test
cillate about their equilibrium position, resulting can be performed anywhere (e.g., in the labora-
in heating. tory, during production, or on a building site).
Nationally standardized sets of flow cups are
normally used in major industrial countries and
9. Properties and Testing give similar but not identical results. An inter-
nationally standardized system of flow cups has
Anyone wishing to test the quality of a paint or been introduced (ISO 2431) to overcome this
coating quickly realizes that only a few prop- problem. Since temperature fluctuations greatly
erties can be accurately scientifically defined. affect the viscosity measurement, the flow cups
In many cases there is a good correlation bet- should only be used in conjunction with ther-
ween defined physical properties and the behav- mostated jackets.
ior of interest to the scientist or practitioner. In Measurements should be made at
some cases, however, it is impossible to obtain 23 ± 0.5 ◦ C. According to ISO 2431 flow cups
such a correlation. A large number of laboratory should only be used for substances exhibiting
testing methods have therefore been developed Newtonian flow. However, they are also often
for paints and coatings that are intended to sim- employed for near-Newtonian paints where the
ulate in-use conditions. These testing methods flow behavior at the desired viscosity deviates
are often similar but their results are not fully only slightly from Newtonian behavior (e.g.,
comparable. Standard manuals provide a good when adjusting the application consistency by
overview of available test methods [431–435]. dilution).
In this chapter attention is focused on methods Viscometers are being increasingly used for
that are widely known and internationally stan- accurate measurements on modern industrial
dardized, or whose international standardization paints, especially waterborne paints. Rotating
is in progress. viscometers with a concentric cylindrical geom-
etry (Searle system, Fig. 27) are advantageous
for paints. Precise thermostatic control is easily
9.1. Properties of Coating Materials achieved because the outer cylinder does not ro-
tate. The drive and torque sensor are combined
Many properties of liquid paints can be mea- to form a single unit with the rotating inner cylin-
sured with considerable accuracy. Samples must der.
be homogeneous. They must also be sufficiently The Couette system (Fig. 28) is another con-
large to be representative for a given batch. Im- centric cylinder system with the advantage that
purities and permanent material defects (e.g., the drive and sensor are separate. The motor
skin formation, a hard sediment, or gelling of drives the outer cylinder; the inner, stationary
the paint) can be detected. The most common cylinder is connected to the sensor.
investigations to which a sample is subjected be-
 Paints and Coatings 153

Falling ball viscometers and capillary vis-

cometers are not generally used for testing
paints. Flow cups are, however, special capil-
lary viscometers with a short capillary in which
the force of gravity acts on the paint.

Other Rheological Properties. Paint

brushability, sagging, and leveling are highly
dependent on viscosity and are usually evalu-
ated subjectively in an application test.
Brushability (the ease with which a paint can
be brushed) is evaluated by actual brushout of the
paint by a painter. To evaluate the force required
for brushing, the viscosity should be measured
at a high shear rate of about 10 000 s−1 .
Sagging is the downward movement of a
paint film that occurs between the time of ap-
Figure 27. Rotating viscometer: Searle system plication and setting. The viscosity has to be
considered at a shear rate of at most 1 s−1 (low-
shear viscometers) in order to assess sagging on
vertical walls. The run-out rate depends on the
square of the layer thickness. Irregularities in
the layer thickness can cause undesirable sag-
ging (curtaining or crawling).
Leveling is the measure of the ability of a
paint to flow out after application (e.g., to oblit-
erate brush marks). It is measured by comb
tests. Theoretical correlations have been es-
tablished between viscosity measurements and
practical results. Surface irregularities can be
sensed mechanically and visualized with mod-
ern methods of image analysis [438].

Pot Life. The pot life is the length of time

that a paint can be used after necessary prepa-
rations for application have been made. Twice
the flow time measured with a flow cup is often
used to assess the pot-life time.
Figure 28. Rotating viscometer: Couette system
Flash Point. The flash point of a liquid is
a measure of the flammability of its vapors on
Viscometers with cylinder and cone/plate ge-
application of an external flame. It is used to as-
ometries can also be employed. The cylinder vis-
sess fire hazards. The flash point of paints may
cometers are easier to use and provide more re-
have to be measured to comply with legal re-
producible results. Cone and plate systems can
quirements relating to the storage, transporta-
be used to investigate the hardening behavior of
tion, and use of flammable products. Accord-
paints. The system can easily be cleaned and
ing to ISO 1523, the flash point (closed cup) is
only a small amount of sample is required. High
the minimum temperature to which a product,
velocity gradients can be achieved with small
confined in a closed cup, must be heated for the
cone angles. The potential uses of cone and plate
vapors emitted to ignite momentarily in the pres-
systems are limited for several reasons and they
ence of a flame, when operated under standard
cannot be used with dispersions [436, 437].
conditions.
154 Paints and Coatings

– ISO 1523 states that the Abel, Abel–Pensky, in a given tube volume and thus on the density of
and Pensky–Martens cups satisfy the neces- the paint. The tube is calibrated with two media
sary requirements. of known density and the density of the sample
– ISO 3679 specifies another apparatus that is then calculated from the resonance frequency.
provides similar results using a more rapid This method is used for liquid and pasty coating
procedure and with a smaller test portion materials [439].
(2 mL).
– ISO 9038 aims to test the combustibility of Fineness of Grind (ISO 1524). The fine-
paints, and involves the use of a Cleveland ness of grind of paints is determined with a gauge
cup (ISO 2592) or a similar device. graduated in micrometers. The reading obtained
on the standard gauge under specific test condi-
Content of Nonvolatile Matter. Non- tions, indicates the depth of the groove of the
volatile matter is defined in ISO 3251 as the gauge at which discrete solid particles in the
residue left when the product is heated at an paint are readily discernible.
elevated temperature for a definite period un-
der prescribed test conditions. A 1 g sample is
evenly distributed in a flat-bottomed metal or 9.2. Properties of Coatings
glass dish (diameter 75 mm) and weighed be-
fore and after heating. Six different heating con- 9.2.1. Films for Testing
ditions are recommended in ISO 3251. The non-
volatile content of a paint is not an absolute quan- Preparation of Test Samples. Almost all
tity, but depends upon the temperature and pe- properties of coatings depend on the layer thick-
riod of heating used for the test as well as upon ness of the film. To obtain reproducible compa-
the test portion. If the test method specified by rable test results, measurements must be made
ISO 3251 is used, only relative values are ob- on carefully prepared films with a defined layer
tained due to solvent retention, thermal decom- thickness. Films may be either free or applied to
position, and evaporation of low molecular mass a substrate. In some cases film properties are also
constituents. The method is therefore primarily measured on films with different thicknesses.
intended for testing subsequent deliveries of a Many properties of coatings also depend on
given product. the substrate and the method of application. The
substrate and method of application must there-
Density. Paint density is usually expressed fore be described in detail when citing results.
in grams per milliliter at a reference temperature Paint-making conditions should be repro-
of 20 ◦ C. duced in the laboratory when necessary. Often it
Pyknometer Method (ISO 2811). A py- is also useful to take into account the production
knometer is filled with paint of known mass. boundary conditions (e.g., maximum and mini-
The density is calculated from the mass of the mum temperature during stoving). If particularly
paint and the volume of the pyknometer. Cylin- good correlation of test results between a paint
drical metal pyknometers and glass Gay–Lussac manufacturer and paint user is necessary, iden-
or Hubbard pyknometers are suitable. The Hub- tical equipment (panels, spray units, etc.) must
bard pyknometer is especially useful for highly be used for sample preparation.
viscous paints. The use of standard panels according to
Immersed Body Method (DIN 53 217 ISO 1514 also has advantages. Standard panels
T 3). The density is calculated from the buoy- are marketed by several companies. It is advan-
ancy of spherical bodies immersed in the paint. tageous to use flat, inert substrates for optical
This method is used for low- and medium- and some mechanical tests if the reproduction
viscosity paints and is particularly suitable for of identical substrate surfaces presents serious
production control. difficulties (e.g., surfaces of wood or mineral
Vibration Method (DIN 53 217 T 5). A U- substrates). For example, glass plates are used
shaped tube is clamped at both ends and filled to test gloss and color; polished steel sheets are
with paint. When the tube is subjected to vibra- used to test flexibility.
tion its resonance frequency depends on the mass
 Paints and Coatings 155

either the film applicator or the test panel is uni-

formly moved by a motor-driven unit.
Combination of the drawdown technique
with standard panels is quicker, universally ap-
plicable, and cheaper than simulating large-scale
industrial application conditions, and is satisfac-
tory for many tests. Drawdowns give more re-
producible results than spray application.

Sample Conditioning. The physical and

mechanical properties of paints and coatings
generally depend on the environmental condi-
tions used during testing; the most important
variables are temperature and humidity. The de-
gree to which each of these variables need to be
controlled is determined by the effect the vari-
able has on the property being measured. Thus
for the measurement of viscosity and density the
temperature must be held constant within limits
of ± 0.5 ◦ C. Standard conditions recommended
in ISO 3270 are 23 ± 2 ◦ C and 50 ± 5 % rela-
tive humidity. Paints that dry at ambient temper-
ature should be dried under these standard condi-
tions for the specified period of time. Paints that
are dried at high temperature should be stored
for two days under these conditions before be-
ing tested. Samples subjected to such conditions
have the properties of a new coating. A coating
that has been in use for a year exhibits different
properties. Surprisingly, however, the properties
of coatings are rarely tested after artificial aging.

Measurement of Film Thickness. An ac-

curate definition of film thickness can only be
given if the coating has even upper and lower
surfaces and a defined density. In practice, nei-
ther the surface of the coating nor that of the
Figure 29. Devices for producing films on test panels (Cour- substrate is even. Surface irregularities and den-
tesy of Erichsen GmbH+Co KG, Hemer, FRG) sity variations influence the results of each test
A) Film applicator with adjustable blade; B) Film applicator
with four fixed blades of different clearance; C) Grooved- method in a specific way. Results of different
rod film applicator tests performed on the same sample may there-
fore differ substantially. Results of film thick-
In the laboratory, large-scale industrial plants ness measurements therefore always have to be
for paint application are often simulated with quoted together with details of the measurement
simple coating equipment. The most commonly method and instrument used [440, 441]. A sur-
used devices for producing films on test panels vey of methods used to measure paint thickness
are the film applicator, film caster, film spreader, is given in ISO 2808.
and drawdown bar (Fig. 29). When operated at a Two instruments are generally used for de-
constant rate these devices produce a uniform termining the wet film thickness: the Interchem-
layer thickness on the test panels. Small ma- ical Wet Film Thickness Gauge (ASTM D 1212,
chines are often used to coat test panels, in which Wheel Gauge) and the Comb Gauge. With the
wheel gauge (Fig. 30) contact of the wet film
156 Paints and Coatings

and eccentric rim of the wheel is influenced by methods include the wedge-cut method and the
the surface tension of the paint. It is therefore profile-measuring microscope method.
necessary to observe the first and last contacts Magnetic instruments based on the magnetic
and calculate the mean value. The influence of induction principle or on the permanent mag-
surface tension is excluded if the comb gauge net pull-off principle are often used on magnetic
(Fig. 31) is used. metallic substrates (ISO 2178, ASTM D 1186).
Instruments that operate on the eddy current
principle are used for nonmagnetic metallic sub-
strates (ISO 2360, ASTM E 376).
Two contact-free methods employ instru-
ments based on the back scattering of β-particles
(ISO 3543) or X-ray fluorescence (ISO 3497).
The uncertainty of film thickness measure-
ment is usually 10 % of the thickness or ca.
1.5 µm, whichever is the greater. The measure-
ment uncertainty of reference methods is nor-
mally < 10 % of the film thickness; microscopy
methods have a minimum error of 0.8 µm.

Determination of Hiding Power. The hid-

ing power is the ability of a paint to hide a sur-
Figure 30. Wheel gauge
face over which it has been uniformly applied.
The hiding power of light-colored paints can be
determined to an accuracy of ca. ± 10 % by a
simple method. Films are applied in different
thicknesses to charts that are printed and var-
nished so as to produce an array of adjacent black
and white areas. After drying, the surface is illu-
minated (1000–4000 lx) and visually examined.
The layer thickness (in micrometers) at which
contrast between the black and white areas is no
longer visible is determined and is taken as a
measure of the hiding power.
ISO 6504/1 describes a modification of this
method in which the hiding power (V in m2 /L)
Figure 31. Comb gauge
is measured with a reflectometer; reproducibil-
ity is 2 %.
The contrast ratio (opacity, hiding power) for
Many methods are used for measuring the a defined area covered by a given volume of
dry film thickness. Thickness can be determined paint is determined according to ISO 3905 us-
by mechanical contact instruments such as hand- ing black and white charts, and according to
held or stationary micrometers (ASTM D 1005). ISO 3906 using a polyester film substrate. The
The apparatus comprises a dial comparator, dial contrast ratios of paints of the same type and
gauge, or suitable indicator for linear measure- color can be compared according to ISO 2814
ment, equipped with a mechanical contact foot [442].
and a mechanical, optical, or electronic indica-
tor. Drying Time. Evaluation of the drying time
Two reference methods are recommended for is simple in the case of stoving materials, but is a
painted surfaces: A method in which the sur- major problem with all paints and varnishes that
face profile is measured (ISO 4518) and a mi- dry physically or chemically at ambient temper-
croscopy method (ASTM D 2691) for coatings ature.
on wood and other substrates. Other optical
 Paints and Coatings 157

Many expressions are used in connection Specular gloss denotes the degree of mirror
with drying (e.g., dust-free, tack-free, surface- reflection and is the primary visual gloss impres-
dry, dry-to-touch, dry-to-handle, dry-through, sion. Flat coated panels can be visually classified
dry-to-recoat) but these terms do not have ac- according to their specular gloss. The ISO 4628
curate definitions. However, equipment is avail- system classifies specular gloss as high gloss,
able for measuring drying times in the laboratory gloss, semigloss, semimatt, matt, and dull matt.
under defined temperature and humidity condi- Arbitrary gloss scales were used initially. Lit-
tions (Fig. 32). Internationally standardized test tle effort was made to establish perceptual gloss
methods also exist: scales. “Psychromatic scaling of gloss” has been
proposed and describes a method devised for the
multidimensional assessment of gloss [444].
Although specimen panels can be classi-
fied according to the specular gloss criterion,
the human eye recognizes additional gloss phe-
nomena. These phenomena are generally de-
scribed according to R. S. Hunter who, in
1939, proposed six types of gloss: specu-
lar gloss, sheen, contrast gloss/luster, absence
of bloom/reflection haze, distinctness of im-
age/image clarity, and directional/surface uni-
formity.
Specular gloss and the distinctness of image
Figure 32. Electromotive drying equipment (Courtesy of
Erichsen GmbH+Co KG, Hemer, FRG)
are of practical importance. In many paint uses
maximum gloss is required. Humans experience
gloss as particularly brilliant if images are re-
Ballotini Method (ISO 1517). Small glass flected with clear definition from a plane sur-
beads are poured onto a horizontal film surface. face. Various forms of black–white contrasts are
After 10 s the panel is inclined and brushed formed on the paint surface for the visual eval-
lightly. The coating is “surface-dry” if all the uation of the distinctness of image (DOI).
spheres can be brushed away. Specular gloss and distinctness are also most
Print-Free Test (ISO 3678). A square of accessible to objective measurement. In 1939
polyamide gauze is pressed onto the surface. The Hunter and Judd found that specular gloss mea-
surface is “print-free” if no imprint can be seen. sured at 60◦ in a reflectometer with specified
Pressure Test for Stackability (ISO 4622). light source and receptor apertures provided a
Two panels are coated and dried; one panel is useful classification of paint finishes according
placed on top of the other and set under pres- to glossy appearance [445]. The instrument was
sure. No damage to the coating must occur. standardized as ASTM D 523, improved, and
subsequently standardized as ISO 2813. The
60◦ reflectometer is now used worldwide as
9.2.2. Optical Properties the standard instrument for measuring specular
gloss because visual evaluation correlates well
The appearance of a coating involves not only with the reflectometer values. The directional-
color but also gloss, luster, and translucency. ity can also be recorded with this instrument as
the difference between the maximum and mini-
Gloss. The term gloss is commonly used mum readings when the instrument is rotated in
but is difficult to define [443]. The Commission its own plane [449].
Internationale de l’Éclairage (CIE) defines the The 60◦ reflectometer has been supple-
gloss of a surface as “the mode of appearance mented by the 20◦ and 85◦ reflectometers. The
by which reflected highlights of objects are per- 20◦ instrument provides better differentiation in
ceived as superimposed on the surface due to the high-gloss range, while the 85◦ instrument
the directionally selective properties of that sur- provides a better differentiation in the low-gloss
face.” range. However, values measured with these two
158 Paints and Coatings

reflectometer geometries do not always correlate change in color observed when the angle of ob-
satisfactorily with visual gloss evaluation. servance is varied. The tester should stand with
In order to measure the distinctness of image, his back to a north-facing window, hold the test
attempts were made to obtain a second reflec- panels in his outstretched arms at eye level, and
tometer value at a larger receiver-side aperture tilt them slowly to give observation angles of
angle and to combine the two reflectometer val- 15◦ , 45 ◦ , and 75◦ [453, 454].
ues in such a way that the measured values could Colors can be defined with the CIELAB color
be assigned to the relevant visual evaluations. space. All colors are arranged in a circle around
Sophisticated instruments are now available, in a central vertical lightness axis. The center of the
which the reflected image of a grating projected hue circle is considered to be neutral gray and
onto the surface is analyzed by means of Fourier saturation is quantified by the distance from the
transformations. axis. All colors can be defined in the color space
Goniophotometers are used for more detailed by color coordinates [455]. For further details,
laboratory investigations of the gloss indicatrix. see → Dyes, General Survey, Chap. 3.
A plane section is laid through the gloss indica- The three different color-response mecha-
trix and can be measured (ASTM E 167) [446– nisms in the human eye are the scientific basis for
452]. the measurement of color that is standardized in
the CIE Standard Observer (1931). This system
Color. See → Dyes, General Survey, specifies color according to X, Y, Z tristimulus
Chap. 2 and → Dyes, General Survey, Chap. 3 values and x, y, z chromaticity coordinates. Sev-
for a more detailed description of color. The im- eral alternative scales were subsequently devel-
pression of color is produced by the absorbance oped to provide a better adaptation to the color
of light by colorants (pigments) in the paint film. differentiation ability of the human eye [456].
To ensure that the color of the coating is not ISO 7724 describes methods for the instru-
altered by the color of the substrate, the coat- mental determination of the color coordinates
ing must “hide” the latter. Visual color evalu- and color differences. The standard is based on
ation involves comparison of a sample with a the CIE 1976 (L*, a*, b*) color space. ISO 7724
standard (ISO 3668). Visual comparison of the specifications are satisfied by many color mea-
color of paints requires an illumination of at suring devices: tristimulus colorimeters, spec-
least 2000 lx. The comparison should be made trophotometers, and abridged spectrophotome-
against a color-neutral (e.g., matt gray) back- ters. Spectrophotometric data are now pre-
ground and the samples should be illuminated ferred and have replaced tristimulus colorime-
by diffuse daylight. This may be achieved with ters. Measuring conditions 8/d or d/8 (with or
light falling onto the sample through a north- without gloss trap), or 45/0 or 0/45 are used [456,
facing window (in the northern hemisphere), or 457]. Metallic automotive finishes are measured
in a color-matching booth with a light source giv- with a sensor having a variable angle geometry
ing a power distribution approximating to that or with a two-angle instrument [45/0 for face
of CIE Standard Illuminant D 65. If the stan- tone (color observed when paints are observed
dard and test panels contain different pigment at an angle close to the perpendicular) and a sec-
mixtures, their colors may match under the stan- ond viewing angle to evaluate the flop tone (color
dard light source but not under another source observed near the grazing angle)].
(metamerism). Spectrophotometers can measure the spectral
Color comparison is most successful if the reflection of a sample and represent it graphi-
two paint films have the same or only slightly cally by means of computer peripherals. Spec-
different gloss, or if the panels are viewed at an trophotometers are a useful aid in the analysis
angle which minimizes gloss differences. Color and synthesis of color samples. All colorimeters
differences are conveniently described accord- enable calculation of the total color difference
ing to the criteria of lightness, chroma, and hue with the CIELAB color difference formula.
in conjunction with the rating schemes given in Color measuring instruments are superior to
ISO 4628/1. In the testing of coatings with spe- the human eye as regards the ability to differen-
cial optical effects (e.g., metallic finishes) the tiate between chroma and hue. The trained eye
flop effect also has to be included. Flop is the is, however, superior to color measuring instru-
 Paints and Coatings 159

ments in the evaluation of differences between Scratch Test. Many methods have been de-
full shade colors and dark colors. If paint has to veloped for testing scratch resistance. The
satisfy stringent color limits, final pass–fail deci- method standardized in ISO 1518 employs a
sions are made on the basis of visual inspection; scratching needle with a hardened steel hemi-
instrumental color measurement serves only as spherical tip of 1 mm diameter. The needle is
an aid [458]. moved along the surface of the coating under a
Color values are generally only measured at specified load either in a hand-operated or in a
one point on each sample panel. Colorimetric motor-driven apparatus.
evaluation can, however, be improved if several The coil coater method (ECCA-T 4, ASTM-
measurements are made at different points on the D 3363) uses pencils of different hardnesses
surface and the results are statistically evaluated which have a “squared tip” and a circular cross
[459]. section. The pencil is held at an angle of 45◦ to
the coating surface. The hardness of the coating
is equated with the hardness at which the pencil
9.2.3. Mechanical Properties can press into and penetrate the paint film. Pen-
cils that are too soft slip over the film without
Adhesion. The cross-cut test is the most scratching it.
commonly used procedure for assessing the re- Damping Test. Pendulums according to
sistance of a coating to separation from a sub- König [462] and Persoz (ISO 1522) or the
strate. A right-angle lattice pattern is cut into Sward Rocker (ASTM D 2134) are used in the
the coating and penetrates through to the sub- damping test. The damping time of a pendulum
strate. Cutting was previously performed with a oscillating on the surface is taken as a measure
single cutting tool or, on site, with a multiple cut- of the hardness of the coating. With air-drying
ting tool (DIN 53 151, ISO 2409). Sharp razor oil paints the hardness increases during drying.
blades were also used. These tools are now be- The pendulum oscillates for a longer time as
ing replaced by steel cutting blades which can be the paint hardens and the internal damping de-
broken into sections. The tool may be mounted creases. The behavior is not found in modern
on a motor-driven apparatus to ensure more uni- stoving finishes. Surface hardness may be high
form cutting. A piece of adhesive tape is placed but the internal damping may be large. A rela-
over the lattice pattern, firmly rubbed with a fin- tionship between surface hardness and internal
gertip, and removed. A six-step classification damping is no longer given in some synthetic
is used to evaluate the results. This procedure resin binders.
should not, however, be regarded as a means of Indentation Test. Indentation hardness is
measuring adhesion [460]. measured by two methods. A spherical or pyra-
The pull-off test for measuring adhesion is midal indentor is applied to the paint surface for
described in ISO 4624. Adhesion is assessed by a specified period. The penetration depth under
measuring the minimum tensile stress necessary load is measured (ISO 6441, ASTM D 1474,
to detach or to rupture the coating in a direction Pfund hardness number). In the other method
perpendicular to the substrate. The result gives an indentor with a specified load is applied for
the minimum tensile stress required to break the a specified period to the paint surface and then
weakest interface (adhesive failure) or the weak- removed. The depth of the impression is then
est compound (cohesive failure) of the test as- measured.
sembly. Mixed adhesive–cohesive failure may According to ASTM D 1474 the Knoop hard-
also occur. ness number is measured with the pyramidal
Knoop diamond. According to ISO 2815 the
Hardness. The hardness of a coating is ex- Buchholz instrument is used. This method can-
amined by three types of test: the scratch test, not detect elastic deformation of the coating
the damping test, and the indentation test with that disappears immediately after the load is re-
a penetrating body. The results of one of these moved.
tests do not allow conclusions to be drawn as The Wallace microindentation tester employs
regards the behavior in another test [461]. a Vickers diamond pyramid indentor and elec-
160 Paints and Coatings

trical measurement of capacitance to determine ISO 7784), and Gardner wet abrasion method
the depth of indentation under load. (used with emulsion paints in DIN 53 778 T 2)
In modern instruments the load on the inden- are commonly used.
tor is applied in very small steps and at varying The stone impact resistance is an impor-
rates, with the simultaneous measurement of the tant property of automotive finishes. Several in-
depth of penetration. The results are plotted as struments (gravelometers) have been developed
a curve showing the depth of penetration. The for testing this parameter. One or more projec-
measurement can be continued with stepwise re- tiles are hurled or shot in the direction of the
moval of the load [463]. painted surface at a defined velocity [Verband
der Automobilindustrie (VDA) Guideline 621–
Flexibility. Viscoelastic properties are 427] [468, 469].
sometimes measured on free paint films [464,
465]. However, the degree to which the coating
allows bending of a substrate without cracking 9.2.4. Chemical Properties
or peeling is more important. Flexibility depends
on ambient temperature and humidity, as well Since coatings are generally used to protect sub-
as on the bending rate of the substrate. Both strates against corrosion, two factors must al-
cylindrical and conical mandrels are quite of- ways be considered:
ten used to evaluate the flexibility of coatings in
1) Are the coatings themselves resistant to ag-
bending tests (ISO 1519, ISO 6860). Slow de-
gressive media?
formation tests such as the Erichsen cupping test
2) Can the coatings protect the substrate?
(ISO 1520) also exist.
Rapid deformations are produced in impact It should always be borne in mind that chemicals
tests (falling weight tests). A metal sheet coated may have different effects depending on whether
on one side is deformed by a falling weight that they are in liquid or vapor form.
has a hemispherical indentor. Deformation oc-
curs directly or indirectly, i.e., the coated or the Water Vapor and Water Resistance. The
uncoated side of the sample is struck by the rate of water vapor transmission of free paint
falling body and deformed (ISO 6272). films is measured according to ISO 7783. The
The viscoelastic properties of coatings de- resistance of coated substrates to water conden-
pend on structural factors, particularly on the sation is, however, generally measured (e.g., ac-
degree of chemical cross-linking, and can be ac- cording to DIN 50 017). Water vapor condenses
curately measured by monitoring the bending on coated substrates in airtight cabinets (ca-
vibrations of thin, coated steel bars. The bars pacity ca. 300 L) or in walk-in chambers. The
are subjected to forced oscillations whose reso- coated substrates are subjected to 100 % relative
nance curves are evaluated with a computerized humidity at 40 ◦ C for 8 h, followed by a 16-h
measuring system. The device can provide data period at 23 ◦ C and 50 % relative humidity.
on the flexibility of coatings after different cur- The resistance to humid atmospheres con-
ing processes. The method can be used to de- taining sulfur dioxide is measured according to
termine the optimum conditions for curing with ISO 3231 in a 300-L cabinet, to which 0.2 or
heat [466, 467]. 1.0 L of sulfur dioxide is added before the cab-
inet is heated to 40 ◦ C.
Abrasion Resistance. Abrasion (wear) re- Resistance to humidity (continuous conden-
sistance is a basic factor in the durability of a sation) is measured according to ISO 6270 in
coating, and is determined by the interaction the Cleveland condensation cabinet, in which the
of the abrasive medium and the coating. Many specimens form the roof of the cabinet. The cab-
types of abrasive media and treatment are used inet contains a water bath set at 40 ◦ C. The water
for testing e.g., fast and slow movement, small or vapor condenses on the coatings that are backed
large load, high and low temperature, constant or by porous or nonporous substrates which are
intermittent contact. The falling sand (abrasive) maintained at 23 ◦ C and 50 % relative humid-
method, abrasive blast method, rotating disk ity. The water vapor diffuses through the porous
method, rotating wheel method (Taber abraser, substrate [470].
 Paints and Coatings 161

Corrosion Resistance. The determination evaluated at the liquid–air interface. Disks of ab-
of the resistance to neutral salt spray fog accord- sorbent material are immersed in the test liquid
ing to ISO 7253 has been adopted from ASTM and placed on the coating. The test liquid or test
B 117. This widely used method is regarded as paste is also dropped directly onto the coating.
the classic corrosion test. The specimen panels If the test medium is to be prevented from evap-
are artificially damaged with a scratch that ex- orating, the test surface is covered with a glass
poses the substrate. The salt mist acts continu- dish. Elevated temperature generally increases
ously on the specimen panels during the test. the aggressiveness of the test medium.
In filiform corrosion on steel and aluminum, ISO 4628 describes a general system for
thread-like infiltrations of the coatings start from evaluating the decomposition of coatings. The
edges or damaged sites. This phenomenon can intensity, quantity, and size of common defects
be tested according to ISO 4623 on steel sheets are classified on a numerical scale ranging from
by damaging a specimen with a scratch and im- 0 to 5.
mersing the specimen in salt solution or expos-
ing it to a neutral salt spray fog in a test cabinet
maintained at 40 ± 2 ◦ C and 80 ± 5 % relative 9.2.5. Weathering Tests
humidity.
Comparisons of the results of laboratory cor- Coatings that are exposed to weathering undergo
rosion tests with damage sustained in use have aging. Aging is defined as the sum of all irre-
revealed differences in corrosion and corrosion versible chemical and physical processes that
products. For example, the constant salt spray occur in the coating over the course of time. Ag-
fog test leads to a different type of rust forma- ing is mainly caused by radiation, temperature,
tion than that produced by natural weathering, and moisture (rain and atmospheric humidity).
with its alternating damp and dry periods. Test Solar radiation (λ = 290–3000 nm) is the
cycles have therefore been developed in which primary cause of aging. Solar radiation causes
the individual stresses are applied in sequence. heating of the coating that depends on the color
A good correlation with natural corrosion in au- of the surface. UV radiation initiates photo-
tomobiles was demonstrated in the VDA alter- chemical aging. Weathering produces changes
nating test. The sample is subjected to salt spray in gloss and color, cracking, blistering, loss
fog for 24 h, followed by four 24-h cycles each of adhesion, and loss of flexibility; these pa-
consisting of 8 h at 40 ◦ C and 100 % relative rameters are used to evaluate aging [473–478].
humidity, followed by 16 h at 23 ◦ C and 50 % ISO 2810 gives guidelines on how to perform
relative humidity, and two days of ambient con- natural weathering tests. The manner and loca-
ditions (VDA Guideline 621–415). tion in which the coating is exposed must be
Since atmospheric corrosion is an electro- appropriate for the end use of the product under
chemical process, attempts have been made to test. Flat specimen panels or structures are fas-
develop electrochemical test methods that can tened to exposure racks at a defined angle. The
predict the corrosion resistance of the coating– exposure period should be one or more years.
substrate system [471, 472]. The intensity, quantity, and magnitude of defects
The specimens are damaged with a scratch (e.g., blistering, chalking, cracking) caused by
that exposes the metallic substrate, and are ca- natural weathering can be classified according
thodically polarized. After several hours a loss of to ISO 4628 (evaluation of degradation of paint
adhesion at the scratch can be observed, which coatings). Measurement of degradation of gloss
can be correlated with natural corrosion. and color is described in Section 8.2.2.
Commercial test institutes in Florida are often
Resistance to Liquids. Various methods commissioned to carry out natural weathering
are used to test the resistance of coatings to the tests. The weather conditions in Florida are pre-
action of liquids and pastes (e.g., mustard, soap ferred because the same aging phenomena occur
solutions, ketchup). Standard methods are de- as in other locations but more quickly. Exposure
fined in ISO 2812. Coated specimen panels are time can be reduced by a factor of two to four
partially immersed in the test liquid so that the when compared with other locations. The test
changes in gloss, color, and swelling can also be institutes in Florida also offer accelerated aging
162 Paints and Coatings

by means of exposure on black boxes and on FATIPEC, International Conference on Organic

heated black boxes. Coatings, Science and Technology in Athens,
In laboratories, coatings are artificially Waterborne and Higher-Solids Coatings Sym-
weathered in specially designed apparatus to posium, the conference of the ACS Polymeric
simulate or measure the aging processes that oc- Materials Division, and ASTM meetings) are
cur during natural weathering. Artificial weath- particularly important because they describe the
ering involves a smaller number of parameters use of analytical methods from the point of view
than natural weathering but can be controlled of their suitability for investigating coating ma-
more uniformly and allows accelerated test con- terials. Periodic literature reviews on the analy-
ditions [479–481]. sis of coating materials are also published in the
Generally valid correlations between aging journal Analytical Chemistry.
processes during artificial and natural weather- The analysis of coating materials is often em-
ing cannot be expected because they are influ- ployed in the investigation of complaints and
enced by many factors. Clearly defined relation- substandard batches, or to evaluate competing
ships can only be expected if the most important products. Analysis also plays an important role
parameters are the same or their influence on in the assessment of raw materials, occupational
the coatings is known [482, 483]. ISO 4892 and safety and hygiene, and the emission of solvents
11 341 specify filtered xenon arc radiation and and decomposition products during paint curing.
other conditions used for the artificial weather- In the case of complaints, the binder and pig-
ing of coatings. The optical radiation source and ment (extender) composition of the individual
its filter system is specified so as to produce a layers have to be established to determine the
spectral distribution of the irradiance sufficiently origin of the paint material in doubtful cases.
similar to the global solar radiation defined in Establishing the cause of coating defects (e.g.,
CIE Publication No. 85. The irradiance is mea- inclusions, delamination, peeling) is also im-
sured inside the apparatus with a radiation meter. portant. These and other analytical investiga-
The temperature is measured with a black stan- tions are time-consuming and expensive. Opti-
dard thermometer. The test panels are wetted by mal utilization of analytical resources therefore
spraying or flooding with water. ISO 2809 and requires a clear definition of the problem in hand.
787/15 also provide information on how to sim-
ulate aging processes occurring during natural
weathering under a glass cover. 10.1. Analysis of Coating Materials
ASTM D 822 describes a standard procedure
for operating light- and water-exposure appara- 10.1.1. Separation of the Coating Material
tus (carbon-arc type) for testing coatings. ASTM into Individual Components
G 53 and DIN 53 384 describe similar standard
procedures for the light exposure or light and For a complete analysis it is advantageous to
water exposure (fluorescent UV type) of non- separate the coating material into its compo-
metallic materials [484]. nents. The binder and pigment (extender) frac-
tions can only be investigated in detail after
separation and isolation. The solvent compo-
10. Analysis sition can usually be determined by gas chro-
matographic analysis of the complete coating
Modern coating materials are complex mixtures material. In conventional, solventborne systems,
of binders, solvents, pigments, extenders, and the pigment (extender) fraction is centrifuged
additives. Most of these components consist of off after diluting the coating material with a
several constituents. Complete analysis of coat- suitable, volatile solvent (ethyl acetate, tetra-
ing materials therefore requires comprehensive hydrofuran, methyl ethyl ketone) [486]. Cen-
knowledge and the use of various analytical trifuge speeds of 5000 min−1 are generally suf-
methods. ficient, however if finely divided pigments (ex-
Surveys of the analysis of coating materi- tenders) or soot are present, a low-density, low-
als are given in [485–487]. The proceedings of viscosity solvent (e.g., acetone) should be used
conferences devoted specifically to paints (e.g., and the rotational speed should be increased
 Paints and Coatings 163

to 20 000 min−1 [488]. To achieve quantitative employed to obtain an overview of the binders
separation the pigment sediment is repeatedly and binder classes. A common procedure is to
shaken with solvent and recentrifuged. Prior to pour a few drops of the binder-containing su-
analysis the combined binder containing super- pernatant from the separation (centrifugation)
natant fractions are dried in a drying cabinet. onto a NaCl or KBr crystal. A thin binder film is
The centrifuged pigment is also dried in a dry- obtained after drying in the drying cabinet and
ing cabinet before being analyzed. IR absorption is then measured. The IR spec-
Problems are often encountered if centrifu- tra provide qualitative and semiquantitative in-
gation is applied to waterborne systems, par- formation about the binder composition. Com-
ticularly if the binder is insoluble or only spar- prehensive spectra catalogs of organic polymers
ingly soluble in organic solvents. In these cases [493] and commercially available coating ma-
the coating material should be carefully dried terials [494] are available for comparison pur-
(vacuum drying cabinet, freeze drying). A re- poses. Modern IR spectrometers, particularly
presentative binder fraction is then obtained by the Fourier transform infrared (FTIR) spectrom-
exhaustive extraction with a suitable solvent eters, offer further possibilities. These instru-
(e.g., 1,2-dichlorobenzene, dimethylformamide, ments have short measurement times and high
and/or tetrahydrofuran) [489, 490]. wavelength reproducibility; they can therefore
accumulate data and provide a considerably bet-
ter signal to noise ratio than conventional grat-
10.1.2. Analysis of Binders ing or prism instruments. IR spectroscopy can
then be used to analyze extremely small sam-
Modern coatings are expected to provide per- ple amounts. Examples are diffuse reflectance
manent protective action, outstanding mechan- FTIR spectroscopy (DRIFTS), investigations of
ical–technological properties, and an attractive sample surfaces by measurement with attenu-
surface appearance. This requires binders con- ated total reflection (ATR), or the analysis of
sisting of special resin combinations (Chap. 2) local defects using an IR microscope [495]. A
and selected additives (Chap. 5). further advantage of FT spectrometers is the
Preliminary tests, color reactions, and spot fact that the data are available in digital form.
tests [491] were formerly used to identify in- Spectroscopic data banks can therefore be com-
dividual resins but are no longer important be- piled either on the spectrometer computer or on
cause they are not sufficiently specific and they an external computer. Commercial data banks
do not provide quantitative results. They have (e.g., Sadtler) and in-house, laboratory-specific
been largely replaced by modern spectroscopic data collections can be installed, the latter are
and chromatographic methods, which often re- often better suited to the particular interests of
quire preliminary chemical workup of the sam- the laboratory. Data banks facilitate archiving,
ple. and also allow quick comparisons of measured
Infrared and nuclear magnetic resonance and library spectra. Quantitative evaluations are
spectroscopy are the most important spectro- also facilitated after appropriate calibration. The
scopic methods for analyzing coating materials. theoretical aspects of FTIR spectroscopy and
Near infrared Fourier transform (NIRFT) Ra- analysis are described in [496]. The use of FT
man spectroscopy [492] also has great poten- and conventional IR spectroscopy to investigate
tial, particularly for aqueous systems. UV/VIS coatings and coating materials is described in
spectroscopy is used only in exceptional cases, [497–499].
e.g., to determine light protection agents (UV
absorbers). Nuclear Magnetic Resonance Spec-
troscopy. Like IR spectroscopy, NMR spec-
Infrared spectroscopy has the advantage troscopy requires little sample preparation, and
of simple sample preparation and measurement; provides extremely detailed information on the
practically all types of samples (both as regards composition of many resins. The only limita-
the state of aggregation and solubility) can be tion is that the sample must be soluble in a
investigated with the aid of special measuring deuterated solvent (e.g., deuterated chloroform,
techniques. Infrared spectroscopy is frequently
164 Paints and Coatings

tetrahydrofuran, dimethylformamide). Com- molecules according to their partition coeffi-

mercial pulse Fourier transform NMR spec- cients. It is particularly suitable for characteriz-
trometers with superconducting magnets (field ing relatively low molecular mass resins (e.g.,
strength 4–14 Tesla) allow routine measurement epoxy, phenolic, and melamine resins).
of high-resolution 1 H- and 13 C-NMR spectra. The high resolution of modern columns and
Two-dimensional NMR techniques and other the high sensitivity of UV detection allow indi-
multipulse techniques (e.g., distortionless en- vidual oligomers (including positional isomers
hancement of polarization transfer, DEPT) can and secondary compounds) to be separated and
also be used [500]. These methods are em- identified. The peak distribution pattern often
ployed to analyze complicated structures. 13 C- permits identification of commercial products.
NMR spectroscopy is particularly suitable for Detailed HPLC investigations have been carried
the qualitative analysis of individual resins in out on epoxy resins [512]. HPLC can also be
binders, quantiative evaluations are more read- applied to resins without UV-active groups by
ily obtained by 1 H-NMR spectroscopy. Com- using mass detectors [513].
prehensive information on NMR measurements On-line coupling of pyrolysis, gas chro-
and the assignment of the resonance lines are matography, and mass spectrometry is a quick
given in the literature, e.g., for branched poly- and elegant method for the qualitative detec-
esters [501], alkyd resins [502], polyacrylates tion of monomer units in many resins (e.g.,
[503], polyurethane elastomers [504], fatty acids polyesters, polyurethanes, phenolic resins, and
[505], cycloaliphatic diisocyanates [506], and polyacrylates). Identification of comonomers of
epoxy resins [507]. polyacrylates, including hydroxy-functional and
carboxy-functional monomers, is facilitated if
Chromatography. Liquid chromatography the sample is silylated before pyrolysis [514].
is the most important chromatographic method
for the investigation of binders and resins. Spe- Chemical Workup. Chemical decomposi-
cial applications are also opening up for su- tion of resins followed by qualitative and quan-
percritical fluid chromatography (SFC) [508]. titative analysis is still an important technique
Methods of particular importance are size ex- because, apart from NMR spectroscopy, none
clusion chromatrography (SEC) (also termed gel of the instrumental analytical methods provides
permeation chromatography, GPC) and reverse- reliable quantitative values. Chemical workup
phase high performance liquid chromatography is also essential for low concentrations of resin
(HPLC). building blocks that are often unknown; it sim-
Gel permeation chromatography separates plifies and enables the desired substances to be
molecules according to their size. This tech- concentrated. Qualitative and quantitative deter-
nique is used to determine the molecular mass mination is carried out by instrumental methods.
distribution of resins. A review of modern GPC Well-established methods of chemical
methods for analyzing coating materials is given workup are available for alkyd resins based on
in [509]. Combination of GPC with modern o-phthalic acid. Alkaline hydrolysis can be used
spectroscopic techniques (in particular FTIR for the quantitative determination of the dicar-
spectroscopy) is a valuable aid for identifying in- boxylic acid, fatty acid, and polyol fractions
dividual resins in binder systems; in some cases [515]. In the IUPAC method the carboxylic acids
additives can also be identified, because their are determined by gas chromatography after
molecular mass is often substantially lower than transesterification with lithium methoxide; the
that of the resin constituents. The coupling of polyols are determined by gas chromatography
liquid chromatography and FTIR spectroscopy after aminolysis and acetylation [516]. Chemical
is described in [510]. Off-line investigations of workup methods (e.g., hydrolysis with alcoholic
fractions from an analytical GPC run of a binder alkali, alkali fusion, aminolysis with hydrazine,
by FTIR measurements under diffuse reflection and transesterification with sodium methoxide)
provide detailed information on the composition for various resins are described in [517]. Al-
of the binder [511]. kaline hydrolysis has the disadvantage that it
Reverse-phase HPLC (mainly octyl- or results in low fractions for polyunsaturated fatty
octadecyl-modified silica gels) separates acids and lower polyols. Transesterification with
 Paints and Coatings 165

methanol or trimethylsulfonium hydroxide pro- therefore be used to identify the source of supply
vides substantially better results for unsaturated when investigating coating materials [521].
fatty acids. This transesterification process was For many inorganic and organic substances,
originally proposed for determining fatty acids X-ray diffraction spectra recorded on powdered
in triglycerides [518] but can also be applied to materials are commercially available on a data
alkyd resins and polyesters. After evaporation carrier (CD-ROM) [522].
of methanol and silylation, the polyols from The pigmentation of monochrome coat-
the reaction mixtures can then be determined ing materials usually comprises several con-
by gas chromatography. This procedure yields stituents: organic and/or inorganic pigments, ti-
more accurate values than with the previously tanium dioxide to improve the hiding power, and
mentioned methods, particularly for the lower other inorganic extenders. The inorganic frac-
polyols. tion is generally dissolved with acid and can then
be analyzed by conventional chemical methods.
The organic pigments remain undissolved and
10.1.3. Analysis of Pigments and Extenders are investigated by IR spectroscopy, photometry,
X-ray diffraction, and separation methods such
The separated pigment (extender) is usually used as thin layer chromatography (TLC) or HPLC.
as starting material for analysis (see Section Modern FTIR spectroscopic methods including
10.1.1). If quantitative separation is not possible library searches; further developments in TLC
(e.g., in emulsion paints) the inorganic pigment and HPLC are discussed in [523]. A separation
(extender) fraction can be obtained by ashing the process for organic pigments has been developed
nonvolatile fraction; for further details see [489]. which exploits solubility differences in various
The isolated pigment (extender) fraction is solvents (ranging from n-hexane to sulfuric acid)
analyzed by various chemical and instrumen- [524]. The extracted pigments are identified by
tal methods. Methods of elemental analysis their VIS spectra in the range 400–900 nm. The
are used for inorganic pigments (extenders). advantages and limitations of X-ray diffractom-
These include traditional chemical methods in- etry in the analysis of organic pigments are dis-
volving separation and gravimetric, tritrimet- cussed in [525].
ric, or polarographic determination of the el- The increasing use of special-effect paints,
ements. These methods are being replaced by particularly in automobile finishes, places new
instrumental methods such as atomic absorp- requirements on analytical techniques. The pre-
tion spectroscopy (AAS), atomic emission spec- viously described methods are largely unsuit-
troscopy (AES), and X-ray fluorescence analy- able for identifying substances used to produce
sis (XFA). A further valuable tool is IR spec- special effects. Aluminum pigments in metal-
troscopy, which provides characteristic spectra lic paints can be roughly classified by light mi-
for many inorganic extenders and pigments (e.g., croscopy. Since these pigments are often sub-
chalk, dolomite, kaolin, talc, and barium sul- jected to special pretreatment, the determination
fate). The most elegant and informative method, of foreign elements with X-ray microprobes or
but the most expensive as regards equipment, the determination of an organic agent used for
is X-ray diffraction [519, 520]. Sample prepa- surface treatment may be necessary for more ac-
ration is simple and the method can be used curate characterization. Light microscopy can
on hardened coating materials; problems asso- also be used for initial characterization of nacre-
ciated with isolating the extender–pigment frac- ous pigments, more detailed information can be
tion can therefore be avoided. The principal ad- obtained with a microscope spectral photometer
vantage, however, is that the substances (e.g., (e.g., UMSP 80, Zeiss) or transmission electron
BaSO4 ) can be identified directly and not indi- microscopy [526].
rectly via their elements (e.g., Ba and S). This is
particularly advantageous if both silica and sil-
icates (kaolin, talc) are present. Minerals such 10.1.4. Analysis of Solvents
as dolomite, chalk, talc, and kaolin originating
from different geographical locations have spe- The solvent composition of coating materials
cific elemental compositions. Their spectra can can be determined in two ways. In the first
166 Paints and Coatings

method, the coating material is subjected di- These factors require special sample prepara-
rectly to gas chromatography, if necessary after tion and analytical methods, for a detailed dis-
dilution with a suitable solvent. In the second cussion see [530]. The separation of binder and
method, the solvent fraction is separated from pigment (extender) fractions for further inves-
the coating material by vacuum distillation and tigation is only possible with non-cross-linked
then analyzed by gas chromatography or, in spe- (physically drying) binders. The coating film is
cial cases, by IR spectroscopy. ASTM methods soaked in a suitable solvent and the pigment is
(D 3271 and D 3272) exist for both processes. centrifuged off after dissolving the binder. Pro-
The advantages and disadvantages of the two vided sufficient material is available, the isolated
methods in the analysis of solventborne and wa- components can be analyzed by the methods de-
terborne systems are discussed in [486]. scribed in Section 10.1. The above method can-
Direct gas chromatographic analysis with not be used with cross-linked binders (e.g., two-
modern capillary column technology and repro- pack systems, stoving finishes). The binder and
ducibly operating injection systems (e.g., mod- pigment (extender) fractions in coating layers
ern autosamplers) gives highly reproducible, ac- are most simply analyzed by means of IR spec-
curate results. This method is therefore used troscopy. Different measurement techniques are
most widely. With complex solvent mixtures, available for this purpose, which require various
unambiguous identification of the peaks is facil- degrees of preparative effort. The most impor-
itated by simultaneously analyzing the sample tant techniques are measurements on KBr pellets
on two columns with different polarities or by prepared from scratched off paint material, mea-
using GC–MS. For further information on gas surement of the coated surface with the method
chromatography, see [527]. of attenuated total reflection (ATR), and mea-
surements on cross sections of the coating with
FTIR microspectroscopy [531].
10.1.5. Analysis of Additives Further methods for determining the binder
structure of cross-linked systems include the
Qualitative and, in particular, quantitative anal- use of pyrolysis gas chromatography or alkaline
ysis of coating additives is difficult due to their hydrolysis followed by analysis of the degrada-
low concentrations and chemical diversity. A tion products by gas chromatography. In multi-
general outline for their investigation cannot be layer coatings this may prove difficult because
given, isolation and analysis depend on chem- the materials have to be prepared from individ-
ical structure. The liquid or hardened coating ual layers.
material is often extracted with a suitable sol- The inorganic pigment (extender) fraction
vent, followed by spectroscopic or chromato- can be obtained by ashing the isolated paint ma-
graphic analysis. For example, plasticizers can terial and analyzing it by the methods described
be extracted very efficiently with pentane and in Section 10.1.3.
detected by IR spectroscopy or gas chromatog- The question of the cause of coating de-
raphy. Supercritical fluid chromatography (SFC) fects often arises in the investigation of coat-
is being increasingly used for the analysis of ings. Defects may be found at localized sites
polymer additives [528]. Especially in combina- (specks, craters) and impair the appearance of
tion with supercritical fluid extraction (SFE) as the coating. They may also occur as planar de-
a relatively fast and efficient sample preparation fects that for example reduce adhesion to the
method [529], it may prove to be of interest for substrate or between the individual layers. De-
the analysis of many additives used in coating fects are investigated with light microscopy,
materials. FTIR microspectroscopy, X-ray methods [532],
and modern surface analysis methods such as
time-of-flight secondary ion mass spectrome-
10.2. Analysis of Coatings try (TOF-SIMS) [533], laser-microprobe mass
analysis (LAMMA) [534], and X-ray photoelec-
Coatings are practically free of solvents and the tron spectroscopy (XPS) [535].
binder is generally cross-linked (i.e., insoluble).
 Paints and Coatings 167

11. Uses to maintain their proper function. Such construc-

tions include road and railroad bridges, electric
The application of paints to various substrates pylon lines, radio and radar antennae, gas tanks,
(e.g., metals, wood, plastics, and concrete) is storage tanks (e.g., for oils, chemicals, cement,
the most widely used method of protecting ma- and grain), loading equipment (e.g., cranes, con-
terials against corrosion and degradation. It is veyors), mining and drilling constructions, as
also used to obtain properties that include gloss, well as steelworks and chemical plants. Al-
color, completely smooth or textured surfaces, though these constructions are sometimes pro-
abrasion resistance, mar resistance, chemical re- tected by inorganic coatings, about 90 % are
sistance, and weather resistance. Normally, a coated with paints based on organic binders.
combination of properties is required. Paint sys- Appropriate surface preparation is of ut-
tems are therefore applied that generally con- most importance for a long service life. Best
sist of a primer, an intermediate coat, and a top- results are achieved by blasting, using grade
coat. These coats of paint together with the sub- 2 1/2 or 3 according to the Swedish Standard
strate surface and surface layers resulting from SIS 055 900 (equivalent to DIN 55 928, part
substrate preparation and pretreatment form the 4, FRG; BS 7079, part A 1, 1989, UK; SSPC-
coating system. Only this complete coating sys- SP 5-SP 6, ASTM, USA; ISO 8501–8503). Al-
tem can provide the combination of properties though mill scale and old paint are sometimes
required for the wide range of uses of organic removed by flame descaling, this method is
coatings. less effective. Residues of rust and corrosion-
Most paints are supplied as liquids that are ap- promoting chemicals (e.g., salts) on the prepared
plied by different methods, using various types surface lead to early rusting under the new paint
of equipment (see Chap. 8). The properties and must therefore be removed completely.
and uses of powder coatings are described in In galvanized steel constructions, blasting is
Section 3.4. Once applied, the wet paint film also necessary to provide a coatable surface. The
must dry to a hard solid film. Paints that dry sweep-blasting method is used in which the zinc
at ambient temperature (air-drying paints) may surface is roughened without removing a signif-
be force-dried at temperatures up to 100 ◦ C. icant amount of the zinc layer. When construc-
Other types of paints require higher tempera- tions made of aluminum alloys are coated, their
tures (120–220 ◦ C) for film formation that in- surfaces must be blasted with iron-free blasting
volves reaction of two and more binder compo- materials.
nents. Thus, the paint formulator has to consider Heavy-duty coating systems generally com-
both the properties of the liquid film and those prise two primer coats and two topcoats, mod-
of the final dry film. Liquid film properties have ern system sometimes consist of one primer coat
to be considered during storage, application, and and two topcoats. The total dry film thickness
curing. (DFT) of such anticorrosive paint systems is
To obtain a properly formulated paint, testing 150–200 µm, each layer has a minimum DFT of
has to be carried out in different stages (Chaps. 40–50 µm. Due to their excellent adhesion, the
9 and 10): weathering and corrosion tests, appli- first and second primers prevent corrosion of the
cation tests, field trials that test in-use behavior, metal surface. The pigments and extenders allow
and durability. The paints can only be used com- the primers to react with ions (Cl− and SO2− 4 )
mercially when they have passed these tests. that diffuse into the film from the atmosphere.
The pigmented organic film also forms a barrier
against humidity that may otherwise initiate a
11.1. Coating Systems for Corrosion corrosive process.
Protection of Large Steel Constructions Heavy-metal pigments (mainly lead pig-
ments) and zinc chromates were used succes-
(Heavy-Duty Coatings)
fully in earlier decades. These pigments are now
being replaced by nontoxic pigments (see Sec-
[536, 537]
tion 11.3.1, and → Pigments, Inorganic).
Large steel constructions have vast metal sur-
The first and second topcoats build up the
faces which must be protected against corrosion
necessary dry film thickness and protect the en-
168 Paints and Coatings

tire coated construction against the adverse in- coats are available as one- or two-pack prod-
fluence of the atmosphere. ucts. Zinc-rich ethyl silicate paints dry to form
Binders based on linseed oil and other oils inorganic films that are very durable even under
have been used for many years in anticorrosive adverse atmospheric conditions, (e.g., onshore
primers. Alkyd binders, especially those with and at sea). These coatings have excellent re-
high fatty acid contents, perform similarly. The sistance to oil, solvents, and mechanical impact,
main disadvantages of these binders is their lim- and are therefore used on drilling stations, oil
ited chemical resistance and their slow drying. rigs, and ships. Since zinc-rich silicate coatings
Chlorinated rubber and poly(vinyl chloride) are heat resistant, they are also used in hot areas
(PVC) resins allow the formulation of coatings of iron works, coal mines, and coking plants.
with good chemical resistance. They are there- Heavy-duty coatings are often still applied
fore used for steel constructions in chemical manually with brushes or rollers that completely
plants. Since they are not resistant to many or- wet the metal surface; holes and pores are filled
ganic solvents, they should not be used in oil with paint. This is especially important when
refineries or plants handling solvents. The unde- old, partially rusted constructions are repainted
sirable fact that these binders contain halogens after sanding. Brushing and rolling, however,
in high amounts is responsible for their decreas- only allow a slow working speed. Larger sur-
ing use. Overspray of chlorinated rubber and face areas must be painted with airless spraying
PVC paints and contaminated blasting materials equipment.
produced after removing old paint cause severe
problems in waste incineration plants (genera-
tion of hydrochloric acid), as well as in waste 11.2. Automotive Paints
disposal areas (pollution of soil and water).
Epoxy resins cured with aminoamide resins 11.2.1. Car Body Paints
or amine adducts are often used for large metal
constructions. Paints based on these resins are Cars are coated to achieve maximum, long-
normally applied in four layers. Epoxy coatings lasting corrosion resistance. Cars must also be
form films that are resistant to organic solvents given an optimum appearance that lasts for many
and a wide range of chemicals. Epoxy coat- years. Long-lasting color and gloss retention as
ings are used for the majority of steel and alu- well as resistance against cracking (especially
minum constructions, but are also suitable for in clearcoats of two-coat metallics) are there-
use on other construction materials (e.g., con- fore necessary. Topcoats of automobiles must
crete). They can protect buildings in chemical withstand solar radiation and atmospheric pol-
plants and nuclear power plants. Epoxy coatings lution (e.g., acid rain and soot from oil com-
are less susceptible to deterioration by radiation bustion). Aggressive chemicals (e.g., road salts
than other organic films, and are also resistant and cleaning agents containing detergents) can
to decontaminating chemicals (usually aqueous damage the coating if they come into contact
detergent solutions) used to remove radioactive with the car surface. Furthermore, small stones
dust from walls and other surfaces in nuclear cause heavy impact on automobile surfaces and
power plants. corrosion via chipping.
Heat-resistant coatings have silicone-resin Large numbers of cars are manufactured on
binders. Pigments for such paints are zinc dust, fast-running assembly lines. The paints must
flakes of aluminum or stainless steel, titanium therefore be applied with highly efficient equip-
dioxide, or silicon carbide. Such paints can with- ment, and must dry very quickly. The paint prod-
stand temperatures up to 600 ◦ C. ucts are classified as primers, intermediate coats
Paints with inorganic binders are also used (also called fillers or surfacers), and topcoats (or
for corrosion protection of steel constructions. finish). The primers and fillers are designated as
These paints are based on organic silicates which the undercoating system.
are soluble in mixtures of alcohols or other Car paints are cured with heat in special oven
water-miscible solvents (see Section 2.15.2). lines. Electrodeposition coatings (used as anti-
Ethyl silicate is often used and mostly pigmented corrosive primers) contain only small amounts
with zinc dust. Zinc-rich primers and single of volatile organic compounds (VOC), whereas
 Paints and Coatings 169

intermediate and topcoats release considerable Electrocoating produces a homogeneous film

amounts of VOCs. Intermediate coats based on that covers the entire car body surface, including
waterborne resins have been developed to de- recesses and cavities.
crease VOC emission and are already being used Although the dry film thickness on the metal
in some automotive plants. Basecoats, as part of edges is somewhat lower, these areas are still ef-
base–clear topcoat systems, contain very high ficiently protected against corrosion. The ultra-
amounts of volatile organic solvents. Water- filtration technique results in a very high transfer
borne basecoats were developed more recently effect and a uniform coating: paint solids from
to lower this source of solvent emission. Some the bath are deposited on the metal surface with-
car manufacturers are operating pilot lines with out loss. Since electrodeposition paints have a
the aim of introducing waterborne basecoats into low organic solvent content, air pollution is low.
their production processes. Many car producers The dip tank contents are not flammable, which
in the United States and Europe have already reduces insurance costs [540].
switched their topcoat lines over to waterborne
basecoats [538]. Intermediate Coats. Intermediate coats
(fillers) are applied between the anticorrosive
Pretreatment. Various metals are used for primers and the topcoat systems. They provide
manufacturing car body shells: steel, galvanized good filling and flowing layers which are nor-
steel, aluminum alloys, and zinc-rich precoated mally smoothed by sanding. Oil-free polyesters
steel. The surfaces of these metals are routinely are used as binders for fillers. They react with
contaminated with oils, drawing lubricants, dirt, blocked isocyanates in 20 min at 165 ◦ C. Their
and assembly residues (e.g., welding fumes). high flexibility gives the whole coating system
The body shells are pretreated to remove these a highly effective mechanical (stone chip) resis-
contaminants and to obtain a well-defined, ho- tance.
mogeneous surface that has the necessary prop- Fillers are applied with electrostatic spray-
erties for adhesion of primers. Pretreatment in- ing devices (fast-rotating bells) to give dry
cludes surface cleaning and formation of a phos- film thicknesses of about 40 µm. Waterborne
phate conversion coat on the shell surface (see fillers with polyester–melamine binders (primer
Section 8.2.1); six to nine discrete steps are in- surfacers) have been developed to reduce the
volved using either spraying devices or baths. volatile organic content. They yield a film thick-
Continuous control of phosphating solutions en- ness of 30 µm after a prereaction time of 10 min
sures good results [536, 539]. at 100 ◦ C and a reaction time of 20 min at
165 ◦ C. The properties of the films are similar to
Anticorrosive Primers. Anticorrosive those formed by solventborne paints. More re-
primers are applied in dip tanks so that they cently, waterborne fillers based on blocked iso-
reach all parts of the car body; dipping is a fast cyanates have been developed. Field trials have
method of application. The standard method for shown that their mechanical resistance is very
application of primers is electrodeposition. An- good.
odic electrodeposition paints were used when
the electrocoating technique was first applied, Topcoat Systems. Topcoats form an impor-
but cathodic electrodeposition is now predom- tant part of the protection system of the car body
inant because it provides better corrosion pro- surface, but are much more important for deco-
tection. ration. The basic requirements for a car topcoat
The binders for cathodic electrodeposition are:
are epoxy resin combinations dispersed in water
(see Section 3.8). Advantages of anticorrosive 1) Full, deep gloss (wet-look)
electrocoatings include excellent corrosion re- 2) Highly brilliant metallic effects
sistance at a dry film thickness of ca. 20–30 µm. 3) Long-lasting resistance against weather and
Electrocoats are stoved at 165–185 ◦ C to obtain chemical influences
films with the desired properties. The paint in- 4) Easy to polish and repair
dustry is now developing electrocoats that can Topcoats based on nitrocellulose combina-
be cured at lower temperatures (140–150 ◦ C). tions with plasticizers and alkyd resins were
170 Paints and Coatings

used in the first decades of industrial car man- absorbing agents to prevent deterioration in ex-
ufacturing. These were followed by thermo- treme climates.
setting alkyd–melamine combinations, and later Some car manufacturers use clearcoats with
by thermosetting acrylics. The use of stoving acrylic binders that are cured with aliphatic iso-
enamels as thermosetting paints also accelerated cyanates. Their chemical and mechanical prop-
production significantly. Although the proper- erties are better than those of alkyd–melamine
ties of these coatings during application and in clearcoats. Solid contents are as high as 58 %.
use were very good, their high content of volatile
organic solvents had to be lowered to comply Car Repair Paints [536]. Repair paints are
with legal restrictions. used in considerable amounts for refinishing
The basecoat–clearcoat system is presently cars. Since repair shops cannot provide the same
the most commonly used type of topcoat for cars facilities as those of car manufacturers, repair
because it is the standard application system for paints are dried at ambient temperature or ele-
metallic colors. Today, about 70 % of all cars vated temperature up to 80 ◦ C (metal temper-
have metallic topcoats. The basecoat–clearcoat ature). Alkyd repair paints and nitrocellulose
system consists of a colored layer (basecoat) paints were standard materials, but two-pack
which is overcoated after a short flash-off time acrylate–isocyanate refinish paints are now more
with a protective layer of clearcoat. Both coats common. Their properties are similar to those of
are cured together at 120–140 ◦ C. The basecoat the original car coatings (long-lasting gloss and
contains pigments which provide two types of color, mechanical and fuel resistance). Car refin-
finish: solid (straight) colors or metallic. ish paints are available in a wide range of colors,
Solventborne metallic basecoats contain ca. solids as well as metallics. They are often sup-
15 % solids and ca. 85 % volatile organic sol- plied to shops and retailers as mixing schemes.
vents. These solvents are not released into the at- Paint systems for car repair comprise anticor-
mosphere, but are converted to combustion gases rosive primers, putties, intermediate coats, and
in afterburners. To reduce emission of organic topcoats; repair coatings applied to refinished
solvents from this source, waterborne basecoats cars have similar durabilities to those of the orig-
have been developed. inally manufactured coating systems.
Waterborne basecoats with higher solids con-
tents are now available: metallic basecoats con-
tain about 18 wt % solids and solid (straight) 11.2.2. Other Automotive Coatings
color basecoats 25–40 wt %. The solvent in wa-
terborne paints is not pure water; about 15 % of The properties of coating systems used for car
organic solvents is still needed as a cosolvent for components differ considerably from those of
proper film formation. Metallic basecoats are ap- systems used for exterior car surfaces. Color is
plied at a DFT of 15 µm, solid color basecoats not important (and is mainly black or gray), but
at a DFT of 20–25 µm. anticorrosive properties similar to those of car
Basecoats are sprayed in two layers. The body coatings are required. Since car compo-
first layer is sprayed electrostatically with high- nents are produced in large numbers, coatings
speed rotation bells, the second layer is sprayed are commonly baked at high temperature to en-
with compressed air to achieve proper orienta- sure a high reaction rate and rapid film forma-
tion of the aluminum particles in metallic paints. tion.
The basecoat is then dried for 3–5 min in a warm Wheels are electrocoated; engine blocks are
air zone at 40–60 ◦ C. coated with heat-resistant, usually waterborne
A final layer of clearcoat is applied with elec- materials. Other parts (e.g., steering equipment
trostatic high-speed rotation bells [538, 542] to and shock absorbers) are painted with two-pack,
protect the system against atmospheric influ- one-coat epoxy systems that are usually solvent-
ences, including wear and tear during use. borne; use of waterborne systems is, however,
Alkyd–melamine clearcoats with an approx- increasing.
imate solids content of 50 % contain UV-
 Paints and Coatings 171

11.3. Paints Used for Commercial Normally, however, two-pack polyurethane top-
Transport Vehicles coats are applied to the dried filler. These top-
coats with aliphatic isocyanate hardeners have
11.3.1. Railroad Rolling Stock excellent gloss and color retention. The DFT of
topcoats is 40–80 µm, depending on the hiding
Large numbers of railroad electric and diesel en- power of the topcoat.
gines, passenger cars, and freight cars are in ser- Red, orange, and yellow pigments used in
vice. They are designed to function for at least topcoats are now free of toxic lead and heavy
30 years with minimum maintenance of their metals to protect workers and the environment.
coatings. Railroad companies expect a service life of 15
Coating systems for railroad rolling stock are years before the topcoat has to be replaced (pro-
used under severe working conditions. Engines vided that spot repair is carried out when neces-
and passenger cars are run at high speeds in many sary). The whole coating system should not need
types of climates. They are frequently cleaned to be renewed before a minimum service life of
with strong chemical solutions to remove the 30 years.
heavy dirt adhering to the coating. Freight cars Although two-pack epoxy primers and
are also exposed to additional stress as a re- polyurethane intermediate coats have high
sult of impact from mechanical handling during solids contents, they still contain significant
loading and unloading. Many transported goods amounts (20–30 wt %) of organic solvents. In
(chemicals, fuels) attack the coating of freight polyurethane topcoats, the VOC is even higher.
cars. Coating systems for railroad rolling stock Anticorrosive, waterborne primers based on
must be highly resistant in all respects. This aqueous dispersions of two-pack epoxy resins
is achieved by using two-pack coating systems and one-pack acrylic resins have been developed
(mainly epoxy but also polyurethane) and, more to decrease solvent emission. Waterborne, one-
recently, coatings of acrylic resins which are ap- pack acrylic topcoats are also used. All of these
plied as one-pack, waterborne dispersions. waterborne paints contain 2–5 % organic cosol-
Before applying the coatings, surfaces are vents that are required for film formation.
pretreated by blasting. Longlife coatings re- Field trials have shown that the expected
quire surface pretreatment according to Swedish durability of the new waterborne coating sys-
Standard SIS 055 900, grade 2 1/2 (equivalent tems is equal to that of conventional solvent-
to DIN 55 928, part 4, FRG; BS 7079, part borne paints. As a further advantage, the number
A 1, 1989, UK; SSPC-SP 5-SP 6, ASTM, USA; of single coats can be reduced from three to two.
ISO 8501–8503). Standard freight cars are painted with a three-
coat alkyd system consisting of an anticorrosive
Engines and Passenger Cars. The exteri- primer, an intermediate coat, and a topcoat, to-
ors of engines, passenger cars, and similar vehi- tal DFT is ca. 150 µm. Such systems are being
cles (subway coaches) are normally painted in replaced by single-coat systems of waterborne
a three-coat system. An anticorrosive, two-pack acrylic resins and acrylic copolymers to reduce
epoxy primer is applied at a DFT of 80 µm. The solvent emission.
curing agent is either an amine adduct or an ami-
noamide resin. Zinc chromate was used for many Freight Cars. Special freight cars transport
years as an effective anticorrosive pigment but dry and liquid goods that can contain aggressive
has now been replaced by chromate-free pig- chemicals which would destroy alkyd coatings.
ments (e.g., zinc phosphates, barium metabo- An exterior coating system based on two-pack
rate, calcium borosilicates, and zinc phospho- epoxy resins is therefore used. It consists of the
molybdates) to avoid the risk of carcinogenicity. same anticorrosive primer employed for engines
Anticorrosive primers are followed by a 40– and passenger cars. This two-pack epoxy primer
50 µm intermediate coat, based on two-pack is applied to blasted steel, sometimes also stain-
polyurethane resins. This coat is sanded to yield less steel. The next layer is a two-pack interme-
a smooth surface. diate epoxy coating with chemically inert pig-
Sometimes, the intermediate coat is over- mentation, DFT 40–60 µm.
coated with the topcoat in a wet-in-wet system.
172 Paints and Coatings

Topcoats are also based on epoxy resins, their a chromate-free, two-pack epoxy primer. Top-
DFT is 40–50 µm. Chemical resistance requires coats based on PVC copolymerisates, chlori-
pigments that are not affected by the transported nated rubber, silicone-reinforced epoxy esters,
goods; the available color range is therefore lim- or alkyds were used for many years. Now, the
ited. standard European topcoat is based on acrylic
Although epoxy topcoats show chalking and resins with terminal epoxy groups that are
loss of gloss after a short period of outdoor use, cross-linked with amine adducts or aminoamide
this does not affect their chemical resistance. resins.
Chalking does not cause a significant reduction
of film thickness.
When goods such as salts or fertilizers are 11.3.3. Road Transport Vehicles
transported, the interior coatings must be chem- Coatings on road transport vehicles are expected
ically resistant. Chemical resistance is obtained to have a minimum service life of ten years. Paint
by using the same system that is used for exte- systems must therefore be of high quality.
rior coating. In the case of food transport (e.g.,
flour, sugar, or grain) the coating must also com- Trucks. Drivers’ cabins are coated in the
ply with relevant legal regulations; thresholds same way as cars (see Section 11.2.1). Truck
are stipulated to limit migration of coating in- chassis are especially prone to corrosion caused
gredients into the transported goods. The same by stone impact and road salts. Chassis parts are
resin system as for the exterior coating may be supplied by special manufacturers who normally
used, but there are strong limitations for the use provide an anticorrosive prime coating.
of pigments, plasticizers, and additives. Side and cross members are pretreated by
In the case of abrasive freight goods, the blasting and phosphating. An electrodeposited
interior of the car must be lined with a thick primer coating follows and is sometimes imme-
coat system consisting of solvent-free two- diately overcoated with a topcoat based on an
pack polyurethane or epoxy material. Toughness air-drying alkyd or epoxy ester, or on an oven-
combined with flexibility results in a film that is drying alkyd–melamine resin combination. Af-
highly resistant to abrasion. ter assembly of the truck, a third layer (i.e., a
second topcoat) is applied that serves as a sup-
Application. The standard application ply finish. These finishes are mostly two-pack
method for most paints used on railroad vehi- acrylic –aliphatic isocyanate topcoats.
cles is airless spraying. A combination of airless
and compressed air spraying has been recently Trailers. Trailer chassis are generally
introduced, it is mainly used for applying water- coated in the same way as truck chassis but with
borne topcoats. a two-coat system. The primer is either a one-
pack alkyd paint or a two-pack epoxy paint that
are cured at ambient temperature with amine
11.3.2. Freight Containers adducts or isocyanates.
Truck bodies are often constructed of steel
Hundreds of thousands of freight containers frames with aluminum side walls. The alu-
have been built worldwide since the early 1960s. minum alloys are pretreated by application of
They are exposed to many types of climate and 5–8 µm of a chromate-containing wash primer.
are heavily stressed by wear and tear. Freight The topcoat is a two-pack acrylic resin bear-
containers consist of steel or aluminum alloy ing hydroxyl groups and is cross-linked with
frames, clad with sidewalls and roofs made of aliphatic isocyanates.
steel, stainless steel, or aluminum alloys. The
walls and roofs may be coil-coated. Container Buses have a profiled steel framework that
frames are usually blasted to grade 2 1/2 of the is clad on the sidewalls and roof with steel, gal-
Swedish Standard SIS 055 900. vanized steel, and aluminum alloys. The anti-
Prime coating is either a two-pack, zinc-rich corrosive primer must therefore adhere well to
epoxy primer with a DFT of ca. 30–40 µm, or all of these metals, and to glass-fiber-reinforced
plastics.
 Paints and Coatings 173

Two-pack epoxy primers with chromate-free Aircraft coatings normally consist of two
pigments show the best performance. They are coats. The topcoat used for civil aircraft is
applied with a DFT of ca. 80 µm, and simul- a high-gloss two-pack polyurethane product,
taneously form the anticorrosive primer and a cured with aliphatic isocyanates. Single-coat
sandable filler. They can protect the metal sub- systems based on thermoplastic acrylic resins
strates against corrosion. have been used for military aircraft, but are be-
The metals are joined by spot welds and riv- ing replaced by polyurethane topcoats [545].
ets that may cause electric currents in the joining
areas. Specially designed epoxy primers prevent
corrosion in these areas. At ambient tempera- 11.4. Marine Coatings [546–548]
ture epoxy primer fillers dry thoroughly in about
16 h. Since this is too long for assembly lines, The requirements of any coating system are
they are normally cured in ovens (80 ◦ C metal determined by its in-use environment (service,
temperature). construction, or maintenance). The sea is wet,
Bus topcoats are mainly two-pack acrylic – salty, usually oxygenated, sometimes anaerobic,
isocyanate paints which dry very rapidly at am- and full of living organisms which may colonize
bient temperature or under low baking condi- the surface of a vessel or platform [546].
tions. This is important because many buses, es- During construction and maintenance cycles,
pecially luxury coaches, are painted in multi- coatings have to adapt to the environment with-
stripe color designs. The resulting coatings have out disrupting time schedules and productiv-
excellent color and gloss retention under service ity. They must also conform to increasingly
conditions. This is not only important for long- stringent considerations of occupational safety
lasting corrosion protection, but also for the im- and health, and to environmental constraints.
age desired by the owners. While construction to the “block-stage” (stage
at which the prefabricated block is transferred
to the building dock) frequently takes place un-
11.3.4. Aircraft Coatings der cover, final assembly and painting take place
under ambient conditions (−10 to + 40 ◦ C,
Aircraft coating systems have an extremely high and 40–100 % relative humidity). Marine paints
quality. Corrosion must be prevented to guar- must be able to tolerate this range of climate as
antee safe functioning of the aircraft. Aircraft well as application methods and skills. For main-
manufacturers issue very comprehensive speci- tenance, the advent of larger vessels, smaller and
fications to ensure the required coating proper- more specialized crews, and increased vessel ac-
ties. This demands extensive development work tivity, means fewer or no opportunities for in-
and careful paint formulation, because the coat- service maintenance. Improved plant reliability
ing properties must be obtained with a minimum means longer intervals between drydocking.
dry film thickness to minimize weight. Aircraft The requirements of marine coatings may
coating systems must also be resistant to hot hy- therefore be considered under the following
draulic fluids. headings:
The aluminum alloys used for aircraft con- 1) Substrate: usually hot-rolled mild steel, high-
struction are pretreated by anodizing, chromat- tensile steel, or aluminum
ing, application of wash primer (6–8 µm), or 2) Surface preparation: usually centrifugal or
pickling. pneumatic blasting with recycled shot or ex-
Anticorrosive primer formulations are based pendable grit blasting media
on epoxy resins that react at ambient temperature 3) Priming: the dominant consideration is the
with amine adducts, aminoamide resins, or iso- effect on the efficiency and quality of new
cyanates (two-pack primers). Zinc or strontium construction
chromates are used as anticorrosive pigments. 4) Design requirements: examples are anticor-
These electrolytically active pigments prevent rosive, antifouling, chemical resistance, im-
dangerous filiform corrosion. Extensive devel- pact and abrasion resistance, cosmetic qual-
opment work is being carried out on chromate- ities, friction and camouflage at various
free aircraft primers [543, 544]. acoustic and electromagnetic wavelengths
174 Paints and Coatings

11.4.1. Substrate, Surface Preparation, and shop primers that form inorganic films (zinc
Priming silicate) are now mainly used.
4) Lifetime. Ship construction times have
Substrate. In marine construction the sub- dropped and much prefabrication is done
strate is generally hot-rolled mild steel, with undercover, so that anticorrosive protection
some high-tensile steel in highly stressed ar- (weathering) during construction may only
eas (apertures in container ships), and aluminum be required for 3–9 months.
where there are weight penalties (e.g., topsides 5) Burning and Weld Spatter. Limiting degra-
of passenger liners, ferries, and naval vessels). dation of the primer in the heated zone and
nonadhesion of weld spatter are important
Surface Preparation. Steel hot rolled at considerations for subsequent coating oper-
800–900 ◦ C acquires a tenacious oxide layer ations.
(mill scale) that is cathodic with respect to the The above constraints mean that only a limited
steel to the extent of about 300 mV. In the pres- range of coating materials is suitable for marine
ence of an electrolyte (seawater containing 3.5 % construction:
salts, mainly sodium chloride) the steel would
1) Wash or etch primers based on poly(vinyl
corrode and pit and roughen severely. The first
butyral) and phenolic resins pigmented with
process in new construction and refurbishment
zinc tetroxychromate
is therefore the complete removal of mill scale.
2) Epoxy primers cured with amine adducts
A small amount of very light-gauge steel is pre-
or polyamides, pigmented with zinc, zinc
pared by acid pickling, but most steel for ship
chromate and potassium chromate, strontium
and off-shore construction is centrifugally or
chromate, or, more recently zinc phosphate
pneumatically blasted with steel shot that can be
and calcium phosphate
recycled or with expendable abrasive grit. Free-
3) Epoxy primers cured with amine adducts,
dom from scale and soluble salt contamination
containing inert pigments (usually iron ox-
are the main requirements, texture and profile
ide)
are less important [548].
4) Epoxy primers, zinc-rich, cured with
polyamines or polyamides
Priming. In new construction the freshly 5) Epoxy primers cured with amine adducts,
blasted steel surface is highly reactive and re- containing leafing aluminum flake pigmen-
quires corrosion protection during construction. tation
It immediately passes through an automatic shop
or blast priming plant. The design criteria for These organic primers have, however, largely
shop primers are set principally by the ship- been discarded in favor of the “organic zinc sil-
builder, with the consequence that their “fitness icate” shop primers (see also Section 2.15.2).
for purpose” is compromised. The main criteria These are low-zinc versions of zinc silicate anti-
are: corrosive primers. Low zinc concentrations are
used to minimize volatilization of zinc metal and
1) Speed of Drying. The primer is applied to the formation of zinc oxide aerosols at welding tem-
substrate on a horizontal moving conveyor; peratures.
the plate must dry quickly to allow handling Dilution of the zinc with other pigments (ex-
and stacking within a few minutes. tenders) requires careful compromise: the pro-
2) Speed and Quality of Welding. The primed tective qualities of a conductive zinc film with
plates are cut and welded by a number of continuous contact should be retained without
techniques (plasma, submerged arc, inert gas, increasing the emission of toxic vapors. Dilu-
manual metal arc, laser). The primers must ent pigments are therefore chosen for their heat
not interfere with the speed and quality of resistance and contribution to the impermeabil-
welding. The principal defects of the previ- ity of the films; they include titanium dioxide,
ous generation of materials was their high or- iron(III) oxide, talc, mica, and china clay.
ganic content, which yielded porous welds. Limitations in performance are several. Zinc
3) Occupational Safety and Health. Emission is volatilized at weld lines and cut edges, re-
of toxic vapors must be minimized; hence, ducing anticorrosive protection. In areas of ma-
 Paints and Coatings 175

rine and industrial pollution, thorough wash- ions. The use of toxic anticorrosive pigments
ing and/or grit sweeping is necessary to remove such as red lead, white lead, lead silicochro-
water-soluble corrosion products of zinc (sul- mate, and zinc chromate has declined for safety
fate, chloride, and ammonium salts) before over- and health reasons. Zinc (or calcium) phos-
coating. Performance is also reduced if the com- phate is one of the few anticorrosive pigments
plete paint system requires chemical or impact still in common use. There has also been a
and abrasion resistance. In such cases reblast- move away from medium oil alkyds and tung
ing is necessary (particularly in chemical tanks, oil/phenolic drying oils for primers and under-
but also in ballast spaces and on the external coats, and long oil alkyds for finishing. They
hull) to completely remove the shop primer. Grit are convenient maintenance materials, but re-
sweeping may also be used but is not as efficient. duced maintenance requirements have meant a
Maximum primer thickness must be strictly con- move towards nonconvertible (chemically dry-
trolled to about 25 µm. ing) epoxy and polyurethane coatings, and a de-
cline in the use of convertible (physically drying)
acrylic, vinyl, or chlorinated rubber coatings for
11.4.2. Ship Paint Systems topsides and boottoppings. Retention of color
and gloss have been improved with rust-hiding,
The painting areas of a ship are shown in Figure
antistaining additives (e.g., calcium etidronate
33. The main requirement of marine coating sys-
or other iron(III) sequestering agents).
tems is corrosion prevention. Detailed require-
For similar reasons in the boottopping area
ments vary with the particular internal or exter-
and on decks, where the most severe mechan-
nal area (e.g., chemical resistance in cargo tanks;
ical and corrosive problems occur, traditional
resistance to seawater in ballast spaces; heat re-
drying oil–red lead compositions are being re-
sistance in engine rooms; impact and abrasion
placed by solvent-free or high-solids, impact-
resistance on boottoppings, external hulls, and
and abrasion-resistant epoxies with outstand-
decks; cosmetic qualities on superstructure and
ing mechanical properties. External underwa-
topsides).
ter hull coatings have changed more slowly.
They originally consisted of mixtures of coal tar
pitch, modified with natural bituminous materi-
als (e.g., asphaltums and gilsonite) by cooking
with lead and drying oils, pigmented with leaf-
ing aluminum flake. They had a high water and
oxygen impermeability but deficient mechanical
properties. Furthermore they are not resistant to
cathodic protection, either by impressed current
or sacrificial zinc or aluminum anodes.
Coal tar pitches are less readily avialable
than they used to be; their content of polynu-
clear aromatic hydrocarbons makes their safe
use suspect. They have been replaced to some
extent by the less effective petroleum bitumens
Figure 33. End-on view of a ship’s hull showing painting whose mechanical properties are improved by
areas
a) Topsides; b) Boottopping or “wind and water line” (may combination with poly(vinyl chloride) and other
be exposed or immersed); c) Lower sides (always im- chlorinated polymers as one-pack, nonconvert-
mersed); d) Superstructure; e) Decks; f) Bottom; g) Water ible coatings, or by combination with epoxy
level (heavy load); h) Water level (light load) or polyurethanes in high-performance two-pack
convertible coatings. Similar materials are pre-
Although still referred to as anticorrosives, ferred for coating ballast spaces and double bot-
marine coatings are technically barrier coatings toms in vessels, where economical systems are
that depend on ohmic resistance for their pro- required that do not have to be attended through-
tective qualities. The ohmic resistance is main- out the lifetime of the vessel (15–25 years). Mul-
tained by impermeability to water and hydroxyl
176 Paints and Coatings

tiple coats with a total thickness of 250–400 µm cation. The paints are generally applied by air-
are usually employed. less spraying. Difficult geometrically complex
The environment in chemical tanks is areas and welds are usually cleaned, smoothed
amongst the severest to which marine coatings by mechanical abrasion, and coated with a brush
are subjected. Each tank may have to trans- [549–552].
port some 1500 bulk, liquid cargoes that in-
clude crude oil, refined gasoline, aviation spirit,
diesel oil, solvents, vegetable oils, or wine. In- 11.4.3. Fouling and Antifouling
organic cargoes are also carried in solution (e.g.,
alkalis and acids). New demands also appear Fouling and antifouling are unique to the ma-
such as methanol as a fuel and feedstock, and rine industry. In contrast to other coatings whose
methyl tert-butyl ether as an additive for lead- primary function is structural, preservation, the
free petrol. outer hull surface of a ship also has to be
No single type of coating is universally ap- smooth to maximize ship speed and reduce fuel
plicable, and nonpaint alternatives may also be consumption [553]. Fouling with marine or-
used (e.g., rubber linings and stainless steel). ganisms, considered as biological roughness,
Vessels that are not dedicated to a single type can be immediate and drastically increase fuel
of cargo (parcel tankers) usually have a number consumption or reduce speed. Some 630×106
of coating systems. deadweight (tonnes) of marine transport burns
The tank coating has three purposes: 184×106 t of fuel at a cost of $ 18.4×109 /a.
Physical roughness would increase this by 10 %,
1) To prevent corrosion of the steel fouling by 30–40 %. The improvement in foul-
2) To prevent contamination of the cargo ing control and roughness of ships made since
3) To facilitate cleaning and avoid cross- 1974 has been calculated to have led to world-
contamination of one cargo by another wide annual fuel savings of $ 720×106 ; the ex-
Variants of six main paint systems are used tension of drydocking from 21 to 28 months has
(Table 30). been calculated to have saved $ 800×106 .
Zinc silicates are outstanding for nonreac- Much effort has been directed to the pre-
tive hydrocarbon cargoes. The remaining sys- vention of fouling [547, 554]. The major con-
tems are all highly cross-linked and their ad- cern on wooden ships was the attack of wood-
vantages are generally a function of the cross- boring mollusks (Teredo and Martesia) or crus-
linking density and their specific chemical sta- tacea. Almost any sessile marine organism may
bility. Heat is of great advantage in achieving be found as a fouling organism. Seriousness
adequate cross-linking density. Some systems depends on size and frequency of occurrence;
require the carriage of heated cargo (e.g., palm severity of settlement depends on geography
oil) for up to six months after application. Heat- and vessel itinerary. Because of the wide range
ing, ventilation, and film thickness all need to be of organisms (e.g., bacteria, diatoms, algae,
closely controlled during application. The steel barnacles, hydroids, mollusks, ascidians, and
surface temperature has to be maintained at a sponges) methods of prevention have to be ex-
constant level. In Northern latitudes the outside tremely general. All antifoulings have so far de-
of the vessel may be lagged with polyurethane pended on a small range of organic, metallic,
foam and the tanks are ventilated with hot dehu- or organometallic biocides. They include cop-
midified air. Certain sequences of cargo have to per, water-soluble or water-reactive compounds,
be avoided since the coating systems swell and organoarsenical, organomercurial, organolead,
are stressed; for example, permeability to water and organotin compounds. The biocides func-
(from damp cargo or steam cleaning) may in- tion by slowly dissolving (leaching) in the sea-
crease following carriage of methanol or contact water adjacent to the hull and killing the organ-
with tank-cleanning chemicals. Chemical tank ism in question. There is a critical leaching rate
coating is thus one of the most critical coating for each biocide and for each organism. The
processes requiring careful coordination of coat- objective of antifouling design is to select an
ing formulation, testing, manufacture, surface optimum biocide or mixture of biocides and to
preparation, and control and inspection of appli- control the release rate at just above the criti-
 Paints and Coatings 177
Table 30. The most important paint systems for marine tank coatings

cal leaching rate for macrofouling (i.e., fouling the physics and chemistry of bioadhesion. Hy-
that affects ship performance). Ideally the leach- drophobic fluoropolymers have proved ineffec-
ing rate should be linear or zero order. Because tive as marine antiadhesive coatings. Silicone
leaching has to continue for 3–5 years under ad- elastomers are adequate for most release pur-
verse environments only the most potent bio- poses and physiologically benign, they have
cides have been found useful (LD50 against tar- shown the most promise. Claims have also been
get organisms may be 3 ng/mL). Control of re- made for nonadhesion with hydrophilic agents,
lease was at first poor because the choice of ma- but much work remains to be done in this area
trix or vehicle was limited to a small number of [563].
natural oils and resins with the appropriate per-
meability. Controlled-release media have, how-
ever, since been developed. Stable film-forming 11.5. Coil Coating [536, 537]
resins composed of trialkyl- and triaryltin esters
Coil coating is a special application method in
of acrylic copolymers are used [555–557]. When
which coiled metal strips are unwound and then
exposed to water the film dissolves with zero-
passed through pretreating, coating, and drying
order kinetics and the surface becomes smoother
equipment before being finally rewound (see
in turbulent flow [558]. Self-polishing or ablat-
Section 8.3.4). The coated metal strips (0.2 –
ing antifoulings based on tributyltin and cop-
2 mm thick) are supplied as coils, and are used
per(I) oxide can have antifouling lives of five
to manufacture a wide variety of metal construc-
years or more. Trade names include Intersmooth
tions, ranging from flat panels to complex geo-
(International Paint, UK); Nautic (Hempel, Den-
metrical forms. The organic coating film must
mark); Seaflo (Chugoku, Japan); and Seamate
have a high elasticity to allow the metal to be
(Jotun, Norway).
shaped without damaging the film at the edges.
For reasons of safety, health, and environ-
Coil coating allows very efficient coating of
mental protection, organolead, -arsenic, and -
large surface areas in a short time, the coated sur-
mercury compounds are no longer used [559].
faces have a very high quality. The metal sheets
Use of organotin compounds is restricted to
are shaped to the required form after coating.
commercial vessels. Although nontoxic, non-
Coating coils of strips in a large coating fa-
polluting, and nonhazardous solutions to the
cility instead of in many small ones results in
fouling problem are needed, alternative com-
optimization of the coating process and reduces
pounds to the tributyltin acrylates have proved
pollution of the environment (lower emission of
extremely difficult to find. However, apart from
volatile organic solvents) [536].
their susceptibility to biocides one of the com-
Prior to coating, the metal surfaces must be
mon features of all fouling organisms is ad-
cleaned and pretreated with aqueous solutions to
hesion. Prevention of adhesion with antiadhe-
form conversion coatings. The following metal
sive coatings has been successful [560–562].
surfaces can be coil-coated:
This approach requires an understanding of
1) Steel strips with a width up to 1850 mm
178 Paints and Coatings

2) Electrolytically galvanized metal bands where weather resistance is required (e.g., exte-
3) Hot-dipped galvanized steel bands (using the rior panels on buildings).
Sendzimir method)
4) Strips from aluminum alloys with a width up
to 1650 mm 11.6. Coatings for Domestic Appliances
Coil coatings are normally applied by roller [536]
coating machines, but are sometimes sprayed.
The topside of the metal band is normally Domestic appliances (e.g., refrigerators, deep-
painted with a primer (DFT ca. 5 µm) and a top- freezers, dishwashers, washing machines, and
coat (DFT 20–22 µm). Zinc-rich coil coatings laundry dryers) are mainly made from blank
are applied with a DFT of 5–20 µm, plastisol sheet iron, or electrolytically or hot dip galva-
films have a DFT of 80–400 µm. The reverse nized steel. Coatings must protect these con-
side of the coils is coated with backing coats struction materials against corrosion caused by
based on binders, such as alkyd, polyester, and food ingredients, household chemicals, and the
epoxy resins (DFT 8–10 µm). humid atmosphere in a kitchen or laundry.
After a very short flash-off time (3–10 s), Domestic appliances are manufactured in
the coated metal passes through a drying oven, large numbers necessitating adequate applica-
which can be up to 50 m long. Drying time is tion and drying facilities and fast production
20–60 s at 180–260 ◦ C, depending on the coat- lines. Stoving materials are used that cure in
ing type. a short time at comparatively high tempera-
Epoxy primers are used as general-purpose tures (10 min at 160 ◦ C or 30 min at 120 ◦ C).
primers on steel, galvanized steel, and alu- Binders for these stoving paints are mainly self-
minum, and under all types of finishes. These cross-linking acrylic resins that cure by polycon-
primers give excellent corrosion resistance on densation to give a smooth homogeneous film
steel. Acrylic primers have a corrosion resis- with excellent mechanical and chemical resis-
tance similar to that of epoxy primers, and are tance.
used primarily under fluorocarbon finishes be- Stoved acrylic resin films are generally ap-
cause of their superior intercoat adhesion. plied as single coats which requires careful pre-
Polyester primers are widely used in West- treatment of the metal surfaces by cleaning and
ern Europe. Although their corrosion resistance phosphating. The paints are applied by electro-
(salt spray test) is not as good as that of the other static spraying using rotating bells or disks.
primer types, their mechanical properties are su- Certain components of domestic appliances
perior. are also coated with electrodeposition paints.
The choice of binders for the topcoat depends Two-pack polyurethanes are applied if the di-
on the end use of the coil-coated metals. Acrylic mensions of the parts are too large for the elec-
topcoats were developed earliest, and are widely trodeposition bath. These paints dry at ambient
used indoors for surfaces that are not exposed to temperature to give films with similar properties
water, chemicals, or mechanical stress. Polyester to stoving acrylic enamels. Solvent-free powder
coil coatings provide a good general-purpose coatings are also used to coat domestic appli-
finish, and can be used for a wide range of ap- ances.
plications (e.g., car interiors and accessories,
caravan exteriors, domestic appliances). Tough,
abrasion-resistant, and durable general-purpose 11.7. Coatings for Packaging (Can
finishes can be formulated with polyurethane or Coatings) [536]
polyester resins.
Topcoats based on fluorocarbon resins About 100×109 cans are produced annu-
[poly(vinylidene fluoride)] produce extremely ally worldwide for packing perishable food
durable coatings (life to first maintenance > 20 (→ Foods, 2. Food Technology, Chap. 4.3).
years under most climatic conditions) with ex- Cans can be considered as a single material, con-
cellent color and gloss retention. Like silicone- sisting of a metal substrate with an organic lac-
modified resins they are used for applications quer.
 Paints and Coatings 179

The interior coating of cans is very impor- their taste. Components of coating films are not
tant because it prevents the metal from reacting allowed to migrate into food, beverages, or other
with the ingredients of the filling goods. The filling goods. In most countries, food packaging
can exterior is painted to prevent corrosion, but is subjected to legal regulations. The raw materi-
also for decorative reasons. Coatings based on als used to produce can coatings and the coatings
combinations of polyester or acrylic resins with themselves are strictly limited.
melamine resins are used for can exteriors. Lac-
quers based on phenolic resins are especially re-
sistant against aggressive can contents. Curing 11.8. Furniture Coatings [536]
at 200 ◦ C produces densely cross-linked films
with high chemical resistance, but poor flexibil- See also → Wood, → Wood, Surface Treat-
ity. ment, and → Wood, Preservation
Combining phenolic resins with epoxy resins The long-term value of furniture depends to
results in films with good chemical resistance a high degree on its surface characteristics. Un-
and flexibility. Interior coatings based on these treated or uncoated surfaces very quickly lose
resin combinations are applied with a solids con- their good appearance and deteriorate under con-
tent of 33–43 % and cured at 200 ◦ C in 80 s. ditions of use. Different forms of wood are used
Epoxy–phenolic resin lacquers are used in high for furniture (e.g., solid wood, veneer, plywood,
amounts for can coating. particle board, and chipboard). Solid wood and
Interior can coatings based on PVC veneer may originate from different types of
organosols are highly flexible and resistant. trees with a wide range of properties partly due
They are used mainly for cans which are heavily to their contents of resins and essential oils.
shaped during the manufacturing process. The natural humidity content of fresh wood
Three-piece (body and two lids) cans are now has to be lowered to a maximum level of 10–
welded instead of soldered. The welding seam 15 % before it is coated. Continuously varying
is coated separately with epoxy–phenolic resins atmospheric humidity in air leads to changes in
or PVC organosols that are cured at 260 ◦ C for the volume of the furniture wood. Furniture coat-
10–20 s. The PVC organosols result in higher ings must therefore have excellent film flexibil-
dry film thicknesses, whereas the epoxy–phe- ity as well as film hardness, and resistance to
nolic welding seam coatings have better chemi- abrasion and fluids (e.g., alcohols). Prior to coat-
cal resistance. ing, wood surfaces usually have to be smoothed
Special filling goods and a long shelf life by sanding, using putty, patinating, staining, or
sometimes require an extremely high dry film pore filling.
thickness for the welding seam coating. Powder Resins and essential oils are often extracted
paints are then applied electrostatically to give a with organic solvents to prevent the coating from
dry film thickness of ca. 50 µm. cracking, discoloring, and developing other
Beverage cans are two-piece (body and lid) faults.
cans produced by the drawn and wall iron- Automatic spraying, machine roller coating,
ing (DWI) process. They require highly flexi- and curtain coating are used for industrial appli-
ble coatings based on epoxy resins cross-linked cation of furniture coatings. Drying is acceler-
with aminoplast resins. ated by air circulation and/or increased temper-
For many years, paints used to coat cans ature up to 80 ◦ C. IR drying ovens and tunnels
contained considerable amounts of volatile or- are also used.
ganic solvents. Waterborne can coatings were Furniture coatings can be clear or pigmented
developed to reduce solvent emissions and are with many different color shades. The surface
used worldwide. Binders used in waterborne can can be high gloss, semigloss, matt, or textured.
coatings are modified epoxy resins (see Section Some coatings leave the wood pores open to give
2.10). Acidic acrylate chains are grafted onto the wood surface a more natural appearance; the
an epoxy molecule. After partially neutralizing “bottom” of the pores must, however, be coated
with amines, the resins can be dispersed in water. evenly to protect the wood surface completely.
Both waterborne and solventborne can coat- Application of a film that fills the wood pores
ings must not affect the can contents, especially results in a completely smooth surface coating.
180 Paints and Coatings

For many years, nitrocellulose coating sys- or acrylic polymers and copolymers (e.g., with
tems were preferred for indoor furniture and styrene). Gloss is between matt and silk-glossy.
other wood parts. These systems are still used Architectural paints are applied in situ with
on low-price furniture, but are gradually being brushes or rollers in Europe, but spray applica-
replaced by coatings based on polyurethanes and tion is widely used in the USA on concrete and
unsaturated polyesters. Most modern wood and wooden buildings. Paints on windows and doors
furniture coatings are based on special acrylic are brush applied. Structural components (e.g.,
resins and unsaturated polyester resins, cured by doors, windows, radiators) that receive primers
UV or electron-beam radiation [565, 566]. or complete coating systems during production
The properties of furniture coatings can be or in the workshop are dipped or sprayed.
summarized as follows: Since the decorative effect is a very important
factor in architectural paints a large number of
1) Nitrocellulose Paints. Cheap, high content
shades in various gloss gradations are available.
of organic solvents, low solids content, dry
Manufacturers’ color cards, the German RAL-
at ambient temperature, not very resistant to
register (Deutsches Institut für Gütesicherung
chemicals or mechanical stress, dried film is
und Kennzeichnung), and the Swedish NCS
soluble in organic solvents.
(Natural Color System) shade charts provide a
2) Polyester Paints. Binder based on unsatu-
survey of available shades.
rated polyester resins (copolymerized with
styrene), low emission of organic solvents,
catalytic curing by organic peroxides or UV 11.9.1. Exterior-Use Coatings
radiation, highly resistant to abrasion, alco-
hols, and other chemicals (cleaning agents). Exterior-use coatings must be weather-resistant:
3) Polyurethane Paints. Polyester, polyether, or they must adhere to a wide range of substrates
acrylic resins containing hydroxyl groups are and retain their gloss and shade fastness for a
cured with isocyanate hardeners, medium to number of years. Suitable binders and pigments
high solids contents, best overall properties must therefore be chosen [568].
in terms of mechanical and chemical resis-
tance [567]. Coatings for Mineral Substrates. The
binders must be particularly resistant to al-
kali because otherwise hydrolysis can occur
11.9. Coatings for Buildings in the presence of moisture due to the high
pH of the substrate. Aqueous systems such as
Coatings for buildings are solvent- or water- silicate paints and vinyl or acrylic emulsion
borne. They include coatings that can protect paints with silicone resin additives are suit-
all materials used in building and construction able for opaque and semitransparent coatings.
work (e.g., wood, steel, light metals and alloys, Solventborne systems are based on synthetic
plastics, concrete, plaster) against corrosion and resins (e.g., styrene–acrylate polymers). Two-
decomposition; they can also give a decorative pack polyurethane coating materials with an
appearance. aliphatic isocyanate as hardener can also be
Solventborne paints are mainly alkyd paints used. Colorless, water-repellent impregnations
with mineral spirit as solvent. Paints based on are obtained with silicone resins or siloxanes in
synthetic resins and two-pack paints with hydro- solvent and silicates in water [569].
carbon, ester, or ketone solvents are, however,
also used. Gloss ranges from silk-matt to high Coatings for Wood. Wooden structures can
gloss. receive colorless, semitransparent, or opaque
Waterborne systems are formulated with pure coatings. The binder and pigment of the sys-
acrylates and have a solvent content below 10 %, tems must be formulated such that a sufficient
preferably glycols. The gloss is between silk- film thickness reduces exchange of moisture and
matt and full gloss. thus swelling and shrinkage of the wood.
Emulsion paints (see also Section 3.5) with The UV transparency of the coating has to
a solvent content below 4 % are based on vinyl be low to prevent depolymerization of the wood
 Paints and Coatings 181

lignin. This is achieved by using UV absorbers 11.9.2. Interior-Use Coatings

in varnishes and transparent iron oxides in stains
[570]. Wall coatings for mineral substrates are
Long oil alkyd resins are used as binders largely formulated as dispersions. Cleanabil-
for solventborne products; acrylic resin disper- ity (wipefastness, washfastness, abrasion resis-
sions alone or mixed with alkyd resin emulsions tance) rather than weather resistance is, however,
are used for waterborne products. Stains may the prime concern (DIN 53 778). Fungal con-
be of the impregnating or coating type. Low- tamination can easily occur in damp, moist ar-
build stains (solids content < 30 %) are used on eas and is prevented by adding fungicides (e.g.,
non-dimensionally stable wooden surfaces and carbamates or imidazoles).
on dimensionally stable structural parts as prim- Various surface effects can be produced by
ing coats only. High-build stains (solids content varying the viscosity and adding coarse, possibly
> 40 %) are used as intermediate- and topcoats colored extenders or fibers. Two-pack systems
to protect dimensionally stable structural parts based on polyurethane resins or epoxy resins are
against direct weathering [571]. used for wall coatings that require a good resis-
tance to agents used for chemical cleaning and
Coating for Metals. Steel, zinc, and light decontamination.
metals are largely topcoated with alkyd resin
systems. Choice of an appropriate surface treat- Floor Coatings. Concrete floors are coated
ment and a suitable primer are important, partic- with low-solvent or solvent-free epoxy or acrylic
ularly with galvanized surfaces and light metals, resin materials that may be applied in any desired
because adhesion to these substrates presents thickness. They are extremely resistant to abra-
difficulties [572]. sion, can be made slip resistant with sand, sili-
Primers based on modified alkyd resins or con carbide, or high-grade steel granulate, and
two-pack epoxy resins for derusted ferrous met- are also resistant to mineral or vegetable oils and
als mainly contain zinc phosphate and zinc ox- gasoline (used for warehouses and factory halls).
ide as a corrosion protection pigment. Nonfer- Pigmented, two-pack, waterborne epoxy
rous metals are first washed with an ammonia- resin coatings (garages) or one-pack waterborne
cal wetting agent before applying the primer that acrylic resin emulsion paints are used for areas
contains a binder based on synthetic resins (e.g., that receive less wear (e.g., cellars). Wooden
PVC copolymers, chlorinated rubber) which en- parquet floors are coated with one- or two-
sure good adhesion to the substrate. The same pack polyurethane varnishes that can be applied
primers must be used on zinc or galvanized sur- by spraying or brushing. Acrylate-based water-
faces because the use of alkyd resins causes em- borne parquet varnishes are also used because
brittlement [573]. they are environmentally friendly.

Coatings for Plastics. The use of plastics Radiator coatings are intended to protect
in building and construction (e.g., glass-fiber- radiators against corrosion without, however,
reinforced resins, rigid PVC) is constantly in- affecting their heating effects (DIN 55 900).
creasing, as is the trend towards renovating such Primers based on special alkyd resins are gener-
surfaces. The surface is first cleaned and, if nec- ally applied industrially. They have to satisfy the
essary, roughened. A one-pack primer based on usual requirements for preventing radiator cor-
chlorinated rubber or chlorosulfonated polyeth- rosion during transportation and at the building
ylene (as is conventional with galvanized sur- site. The topcoats applied on site by rolling or
faces) or a two-pack epoxy primer is then ap- inundation are based on medium oil alkyd resins.
plied. The primer can then be coated with a
topcoat system that is usually formulated with Heating oil storage premises must be
medium or long oil alkyd resins [574]. equipped with a collection trap so that any heat-
ing oil leaking from the tank cannot contaminate
the soil. The interior of these premises must be
painted with an officially approved coating ma-
terial that is not dissolved or penetrated by heat-
182 Paints and Coatings

ing oil. The coating must also cover cracks in regarded as the tracer for photooxidants. Even
the substrate. Multilayer systems based on wa- low concentrations of photooxidants harm plant
terborne acrylic resin dispersions are suitable for life and may damage the human respiratory tract.
this purpose. Atmospheric pollution caused by photooxidants
can occur particularly in the summer (summer
Fire Retardant Coatings. The flammabil- smog), and was first observed in Los Angeles,
ity of combustible wood structures can be re- where measures were adopted at an early stage
duced in accordance with DIN 4102 by ap- to reduce pollution.
plying a fire retarding paint that forms an in- Solvent emissions can be reduced in three
sulating layer [572]. Dispersion paints based ways:
on poly(vinyl acetate) with addition of ammo- 1) Use of low-solvent or solvent-free products
nium phosphate, a nitrogen compound (e.g., 2) Application methods with low solvent emis-
melamine), and a carbon-forming agent (e.g., sions
pentaerythritol) are suitable for this purpose. 3) Implementation of waste air treatment as a
The thermal insulation is so good that ignition secondary measure in paint application fa-
can be delayed by at least 10 min. cilities
In painting work performed by tradesmen,
emissions can only be lowered by using low-
12. Environmental Protection and
solvent products.
Toxicology
Low-Solvent Coating Materials. A great
Paints and coating materials frequently contain deal of progress has been made in the devel-
substances that may be a hazard both to hu- opment of low-solvent paints [575]. The use of
man health and to the environment. This applies water as a replacement for organic solvents is
particularly to organic solvents, to certain reac- particularly important in this respect, although
tive binder constituents, to pigments containing alternatives such as powder coatings or one-pack
heavy metals, and to some additives. Evaluation and two-pack high-solids paints have also led
of the environmental properties of paints must to significant improvements. Solvent emissions
take into consideration their effects on the atmo- can be drastically reduced by using low-solvent
sphere, water, and the soil, the potential danger coating materials. This is particularly apparent
to the user, the use of low-residue application in automobile finishes: in a metallic effect fin-
techniques, and the suitability for use. The pri- ish based on conventional coating materials and
mary concern is to minimize adverse effects in solvent contents of up to 85 %, the specific emis-
all sectors. sion is ca. 180 g of solvent per square meter of
car body. With an average car body surface of
90 m2 , ca. 16 kg of solvents are released per au-
12.1. Clean Air Measures tomobile. By using low-solvent coating materi-
als (electrodeposition paints, waterborne primer
Organic solvents in paints constitute significant surfacers, waterborne metallic basecoats, and
sources of atmospheric pollution. The direct ef- a conventional solventborne clearcoat) solvent
fects of these substances and their mixtures (see emissions in modern plants are now only 30–
Section 12.4), particularly the odor nuisance, 45 g/m2 . Waterborne clearcoats are under devel-
should be taken into account in the vicinity of opment, but the use of powder clearcoats is also
sources of solvent emissions. In the atmosphere under discussion. Use of these systems should
the solvents gradually decompose or participate allow solvent emissions to be reduced further to
in chemical reactions under the influence of sun- ca. 20 g/m2 .
light or traces of other substances present in the In other industrial application sectors there is
air. Photochemical decomposition in the pres- an increasing tendency to employ low-solvent
ence of nitrogen oxides leads to formation of paints. In furniture production, for example,
intermediates which are termed photooxidants waterborne, UV-curing paints are superceding
on account of their oxidizing action. Ozone is high-solvent nitrocellulose lacquers.
 Paints and Coatings 183

Stringent coating stability requirements on ing with compressed air the application effi-
metal surfaces can be met by using powder coat- ciency is particularly low (20–65 %, depending
ings. Use of powder coatings is therefore in- on the shape of the part being coated). Higher
creasing in new areas of application (e.g., for application efficiencies are achieved with air-
the colored coating of sanitary ware [576] and less and electrostatic spraying methods, and may
corrosion protection of truck tanks [577]). reach 90 % in the case of electrostatic spray-
The need for waste air treatment can gener- ing. The overspray of coating powders can be
ally be avoided by replacing conventional, high- largely recovered and reused directly. Problems
solvent paints by low-solvent coatings. In some arise with changes in color which can, however,
cases smaller waste air treatment plants may be largely be solved. The highest application effi-
necessary for specific demarcated areas where, ciencies for wet paints (nearly 100 wt %) are ob-
for example, a solventborne layer is applied. tained with brushing, rolling, and pouring meth-
In the architectural paints sector, conven- ods, which, however, can only be used on flat
tional, high-solvent paints based on alkyd and surfaces. Parts with hidden areas can be effec-
synthetic resins can largely be replaced by tively coated by dipping methods.
waterborne dispersions of acrylate polymers
and copolymers, aqueous alkyd resin emulsion Waste Air Treatment. Two main methods
paints, and oil-based high-solids paints. Mod- are used for treating waste air in coating and
ern low-solvent coating materials not only de- paint shops: afterburning with heat recovery and
crease environmental pollution, but have also adsorption with solvent recovery. In order to
improved paint quality (e.g., resistance to weath- reduce expenditure on waste air treatment, the
ering). In some countries low-solvent architec- amount of waste gas should be minimized by
tural paints are clearly labeled as such to as- enclosing the paint application area and recy-
sist workers and users. In the Federal Republic cling circulating air. Water washers (scrubbers),
of Germany waterborne emulsion gloss paints fabric filters, and electrical separators are used
containing ≤ 10 wt % solvent and high-solids to remove paint aerosols from the atmosphere.
paints containing ≤ 15 wt % solvent are iden- Recycling of circulating air is already common
tified by an “environment label”, a symbol cre- practice in modern automated paint shops (e.g.,
ated for products having a favorable environ- in the automobile industry). If the workforce is
mental compatibility. In Switzerland paints con- protected against relatively high solvent concen-
taining ≤ 5 wt % of solvents may be labeled trations by respirators equipped with a fresh air
as “solvent-free”, and with ≤ 30 wt % as “low- supply, manual spraying zones can also be op-
solvent”. Some states of the United States (e.g., erated with recycled air. If such a concentration
California) stipulate maximum solvent limits for procedure is not possible, large-volume waste
individual product groups. air streams with a low solvent content can be
concentrated with a continuously operating ad-
Application Methods with Low Solvent sorption wheel (e.g., with special activated car-
Emission. The method used to apply the coat- bon) and then treated [578]. The solvent from the
ing material also influences the level of solvent waste air is adsorbed on one side of the rotating
emissions as well as the amount of waste and wheel and desorbed with a small air stream on
water pollution. Application efficiency depends the other side. The concentrated waste air (10 %
on the application method and shape of the ar- of the original waste air stream) can then be pu-
ticle being coated. Application methods are de- rified either by an adsorption unit with solvent
scribed in Chapter 8. Spraying and dipping are recovery, or by afterburning. The heat from the
most commonly employed for industrial coat- afterburning plant should be utilized; if this is
ing. Spraying methods have the highest solvent not possible, newly developed thermal methods
emissions because overspray losses are unavoid- with internal heat utilization may be used [579].
able, and low-viscosity paints generally have Biological waste gas treatment methods are
to be applied. With conventional high-solvent also suitable for purifying solvent-containing
paints the solvent content at the ready-to-spray waste gases, especially slightly contaminated,
viscosity value may be as high as 90 wt % but large-volume waste gas streams; they have al-
is usually 50–70 wt %. In conventional spray- ready been tested [580]. In biological methods
184 Paints and Coatings

organic substances are degraded by microorgan- culation, neutralization, and filtration. With cer-
isms on the surface of a wet filter layer or in a tain water-soluble toxic substances (e.g., heavy-
scrubber. metal compounds), organic solvents, and addi-
In various countries (e.g., the Federal Re- tives, further purification steps may be neces-
public of Germany, the United States, Scandi- sary. Heavy metals can be precipitated. Meth-
navia, and Switzerland) regulations exist con- ods used for organic solvents depend on their
cerning the treatment of waste air from paint nature and concentration in the water; they in-
shops. Large paint shops (e.g., in the automobile clude ultrafiltration, reverse osmosis, adsorption
industry) are covered by these regulations. In the (e.g., on activated charcoal), biological purifi-
Federal Republic of Germany the maximum per- cation, and, with high solvent concentrations,
missible emissions from automobile paint shops distillation [581]. The concentration of organic
are limited by the amount of solvent used per substances in the wastewater is described by the
square meter of car body (see page 182). For au- chemical oxygen demand (COD) and the bio-
tomated spraying zones in other paint shops the logical oxygen demand within 5 days (BOD5 ).
emission of organic substances in the waste gas Statutory requirements governing the prelimi-
is restricted to a maximum of 150 mg/m3 . nary purification of the wastewater can vary
widely. They depend on purification facilities
in the existing wastewater treatment plants. The
12.2. Wastewater effort and expense involved in wastewater pre-
treatment can be considerably reduced by avoid-
In industrial paint application the principal ing the use of toxic substances (e.g., heavy met-
sources of wastewater are spraying cabins, wet als). With waterborne paints particular attention
filters, and scrubbers. Further sources of waste- should be paid to adequate removal of water-
water are the cleaning of apparatus, equipment, soluble organic substances (e.g., solvents) from
vessels, tanks, and working areas, as well as the wastewater.
the retentate produced in the ultrafiltration of
electrodeposition paints. To reduce environmen-
tal pollution, attempts should be made to min- 12.3. Solid Residues and Waste
imize the amount of wastewater. Wastewater
from spraying cabins may be treated by coag- Considerable amounts of solid residues and
ulating the overspray and continuously extract- other waste are produced when paints are ap-
ing the paint slurry, as well as by reducing the plied, particularly by spraying. The overspray
amount of water used. Continuous methods for is collected as a coagulated residue from the
cleaning the circulating water are used both for spray cabin water. Articles such as contami-
solventborne and waterborne paints. Products nated filters, paint residues, and empty con-
based on alumina, metal hydroxides, and organic tainers also have to be disposed of. For eco-
fatty acid derivatives are used as coagulating logical reasons minimization of waste produc-
agents. These auxiliaries coat and envelop the tion and reutilization should take precedence
paint particles. over disposal methods (incineration, landfill).
With waterborne paints, stable dispersions or In the Federal Republic of Germany, for exam-
emulsions are sometimes formed in the circu- ple, this principle is laid down in waste control
lating water. The coagulating agent also has to and emission legislation (Abfallgesetz, Bundes-
“break” these disperse systems. A very fine floc- Immissionsschutzgesetz). Up to now paint slur-
culant coagulate is often formed which has to ries were mainly disposed of in special landfills.
be separated with special filters or a centrifuge, On account of increasingly stringent require-
or converted into larger, more easily removable ments to prevent pollution of soil and groundwa-
flakes by using a further coagulating agent. If ter, paint slurries will have to be disposed of in
the circulating water from the spray cabin has to special refuse incinerators. This will inevitably
be drained off due to high levels of contamina- lead to higher disposal costs; avoidance of waste
tion, it must be treated before being discharged and recycling will therefore be of economic ad-
into the sewage system or wastewater treat- vantage.
ment plant. Treatment usually comprises floc-
 Paints and Coatings 185

The production of paint residues and waste linked and can be ground into a powder. The
can be prevented or reduced by using coating powder is used as a filler for plastics dispersions
methods with high application efficiencies (dip- (e.g., for underbody protection in automobiles
ping, brushing, rolling, and pouring). Compared and in sealing materials).
with the spraying technique, these methods gen-
erally also result in lower solvent emissions (see
page 183). The amount of overspray produced 12.4. Toxicology
in spraying methods can be lowered by using
electrostatic application procedures. In powder Many different substances are used in paints and
coating the overspray is trapped and separated coating materials as binders, pigments, solvents,
in a dust-removal filter; it can then be directly and additives. Workers involved in painting and
recycled, if necessary after purification. coating work are regularly exposed to volatile or-
In the spray application of wet paints the ganic compounds, especially solvents. In spray-
overspray can also be recovered and recycled ing application methods the inhalation of all
by various methods which have not, however, paint constituents in the form of aerosols should
all been tested industrially [582]. The overspray be borne in mind even if they are nonvolatile or of
can be recovered with rotating disks or circu- low volatility. Contact with the skin represents a
lating belts. Stable paints can be reused directly further source of exposure to paint constituents,
after conditioning (e.g., viscosity adjustment). many of which can be absorbed through the skin.
In solventborne paints the disk or belt often With manual application by brushing or
has to be wetted with solvents, the waste air rolling the health hazards due to solvent expo-
should therefore be treated to prevent high sol- sure (aliphatic and aromatic hydrocarbons, es-
vent emission. Some waterborne paints can also ters, ketones, alcohols, and glycol ethers) are
be recovered by this method. In paint recycling a major factor. Solvents are predominantly ab-
the overspray should not be entrained with the sorbed via the respiratory tract. Their toxic ef-
waste air from the spray cabin; certain precondi- fects depend on the nature of the solvent, its
tions should therefore be observed: airless spray- concentration, and the length of exposure. De-
ing guns are most suitable and the parts to be pending on the concentration, symptoms after
coated should not be too large or have a com- acute exposure include irradiation of the mucous
plex three-dimensional structure (e.g., car bod- membranes (eyes and respiratory tract), vertigo,
ies). The overspray can be recovered from the nausea, and vomiting; narcosis symptoms are
cabin circulation water if it can be coagulated also observed which are attributed to distur-
without destroying its chemical structure. After bances of the central nervous system. Chronic
mechanical dewatering with kneaders or mixers, poisoning is initially undetectable, but may sub-
purification, and work-up, small amounts of this sequently produce damage to organs that is spe-
material can be added to the new paint. If direct cific for the solvent concerned.
recycling is not possible, the material can be sep- The neurotoxic effects found in painters and
arated by centrifugation into a binder solution coaters exposed to solvents are the subject of
and pigment concentrate that can be used as raw controversy. Some studies describe subjective
materials for paint production. Physically dry- symptoms such as fatigue, difficulty in con-
ing paints and stoving finishes are particularly centrating, and short-term memory problems
suitable for recovery. in workers employed in industrial paint and
Paint coagulates can also be used as a binder coatings application. These symptoms have not,
constituent in the production of molded plas- however, been observed in painters employed in
tics and as a filler replacement in plastics disper- the architectural and exterior-use paints sectors
sions. If used as a binder for molded plastics, the who mainly use waterborne paints [583].
material must not be cross-linked; the coagulate During surface treatment prior to paint ap-
is worked up into an aqueous dispersion which plication, abrasive dust and pyrolysis products
is used to wet or impregnate fiber mats that are produced during the removal of paints and sol-
then compressed. In order to produce fillers the vents may also be inhaled. The dust produced
paint coagulate first has to be dehydrated and from corrosion protection agents and some older
dried, the material becomes completely cross- colored paints is often contaminated with heavy
186 Paints and Coatings

metals. Chlorinated hydrocarbons are still used 13. Economic Aspects

in paint strippers.
Frequent skin contact with paints and coating [586, 587]
materials can cause skin disorders, particularly Paints and varnishes (coatings) have two
on the hands, in painters and coaters. The lipid- primary functions: protection and decoration.
solubilizing properties of the organic solvents Other objectives include information, identifi-
may cause or at least promote contact eczema. In cation, safety, insulation, vapor barrier, nonskid
particular, paints based on reactive resins (e.g., surface, and control of temperature, light, and
epoxy and polyester resins) may cause allergic dust. A range of product categories with a wide
skin disorders. Skin-sensitizing substances in- variety of application is therefore available:
clude residual monomers and reactive diluents 1) Architectural (decorative) coatings include
(e.g., acrylates and epoxides) and paint additives exterior and interior house paints which
(e.g., acid anhydrides, peroxides, amines, as well are normally distributed through wholesale-
as cobalt and zirconium in driers, and formalde- retail channels and purchased by the general
hyde and isothiazolinone in biocides). Some of public, painters, building contractors, gov-
these paint constituents are also skin irritants. ernment agencies, etc.
In spraying methods often employed for in- 2) Product finishes are coatings formulated
dustrial paint application, workers are not only specifically for original equipment manufac-
exposed to solvents, they may also inhale paint ture (OEM) to satisfy application conditions
constituents in the form of aerosols. On account and manufacturing requirements for a wide
of their very small size, some aerosol compo- variety of industrial and consumer products,
nents can reach and penetrate the lung virtually e.g., wood and metal furniture and fixtures;
unhindered. Substances that have a particularly automotive and nonautomotive transporta-
sensitizing and irritant action on the skin can tion, aircraft, machinery and equipment, ap-
thus also affect the respiratory tract. Isocyanates pliances, electrical insulation, film, paper,
can have a sensitizing effect even at very low foil, toys, and sports goods.
concentrations (1 µL/m3 ) and can cause chronic 3) Special-purpose coatings are formulated for
bronchial asthma in particularly susceptible per- special applications or extreme environ-
sons. A literature study carried out by a working ments and include automotive and machinery
group of the International Agency for Research refinishing, high-performance maintenance,
on Cancer came to the conclusion that there is road markings, marine (bridge) maintenance,
sufficient evidence for carcinogenicity due to the crafts, metallic and multicolored coatings.
occupational exposure of painters [584]. Occu- The number of coatings producers worldwide
pational exposure in paint manufacture cannot was estimated at about 10 000 in 1988. The total
be assessed however. world coatings market was estimated to be ca.
Depending on the application method (brush- $ 36×109 ; the product market sectors were as
ing, spraying) and the paint used, technical follows:
and personal work safety measures should be
adopted when applying paints and coatings. Decorative 52 %
Technical measures include adequate supply of Auto OEM 6%
Refinishes 5%
fresh air and removal of waste air (e.g., in spe- Can coatings 3%
cial hoods), as well as the replacement of “haz- Others including
ardous” paints with less dangerous ones [585]. industrial paints 34 %
Many hazardous dangerous substances have Total production 12×109 L

maximum workplace concentrations (threshold

World paint markets by region were
limit values) which should be strictly observed
and monitored. Adequate facial and skin protec-
North America 32 %
tion must also be ensured (e.g., with masks and Western Europe 30 %
gloves). Japan 13 %
Rest of Asia-Pacific 10.5 %
Rest of world 14.5 %
Total production 12×109 L
 Paints and Coatings 187

In 1989 the top ten paint companies ac- coating can also avoid the classical painting pro-
counted for about a third of the total world mar- cess.
ket, by the year 2000 they could well account
for up to half. This development is expected be-
cause of permanent streamlining of activities by 14. References
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