Quelle/Publication: European Coatings Journal

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Seite/Page: 22

Defended from the sun

some air-drying alkyd systems. Therefore, the non-basic
Optimised use of UV absorbers and HALS in the aminoether function N-OR, e.g. HALS-2 with R = OC8H17
weathering protection of wood substrates. (its pKb of ~ 10 denotes a much weaker base) has gained
A major drawback in the use of wood materials for wide acceptance in the paint industry, as it has the major
construction and decorative applications is its sensitivity to advantage of non-interaction with biocides, acidic media and
light. Coatings are usually used to prevent deterioration of the drying process of acid-catalysed or air-drying systems.
the wood surface. The protection effect depends strongly on In contrast to HALS, which trap radicals at the surface, UVA
the opacity of the coatings, and is particularly difficult for filter out the harmful wavelengths of the light spectrum
coatings of low opacity, which transmit most radiation. before photochemical reactions can take place, and
However, optimised use of UV absorbers and HALS both in therefore reduce the rate of radical generation [2]. Today,
the coating system and also in a direct wood impregnation UVA based on 2-(2-hydroxy-phenyl)-benzotriazole (BTZ)
step can improve the light stability considerably. chemistry are considered to be the most important class for
Christian Schaller *, Daniel Rogez. the stabilisation of clear coats. Commonly used UVA are
* Corresponding author. Contact: Dr. Christian Schaller, BTZ-1 for solventborne and BTZ-2 for waterborne
Ciba Specialty Chemicals Inc., CH-4002 Basel, Switzerland, applications.
Tel: +41 61 6366812, Fax +41 61 6365116, Some limitations of benzotriazole-based UVA have pushed
[Link]@[Link] the paint industry to adopt a new UVA class based on 2-
The popularity of natural wood as an exterior design and hydroxyphenyl-s-triazine (HPT) chemistry [3]. This new
construction material would be even greater if significant class of UVA can be fine-tuned by selective choice of
improvements could be achieved in extending its durability substituent, allowing tailor-made additives to be created for
with reduced maintenance work. But under outdoor powder [4], high performance automotive, industrial and
conditions, weathering causes deterioration of the surface, wood coating applications [5].
due to a complex set of reactions induced by factors such as For wood, a UVA based on substituted tris-resorcinol
solar radiation, water, temperature and oxygen. triazine (Figure 1, HPT-1) with exceptional
photo-permanence and a more pronounced red-shifted
How light degrades wood absorption was introduced for UV curable systems [6], high
Many researchers have shown that ultraviolet (UV) and performance solventborne [7, 8] and, in encapsulated form,
elements of the visible (VIS) spectrum of solar radiation for waterborne wood coating applications [9, 10].
cause most of the chemical modification and mechanical
breakdown of exposed wood. To understand these effects, it Direct wood pretreatment based on special HALS
is important to understand wood biology and the related As both UV and visible light up to 500 nm causes lignin
mechanisms of photo-oxidation and degradation. degradation [11], wood has to be protected from parts of the
Chemically, wood is a complex biopolymer composed of visible light spectrum. Therefore a new two-step protection
structural polysaccharides, essentially cellulose as a strategy was introduced, in which a lignin stabiliser is
structural substance, hemicelluloses as a kind of glue and applied as a dilute pre-treatment solution or in an existing
lignin as strength provider. Lignin contains chromophores primer formulation directly onto wood and selected UVA (for
with aromatic conjugated bond systems and carbonyl indoor applications) or UVA/HALS (for outdoors) are used
groups, and this is why its interaction with light (UV/VIS) in either in the same treatment stage (internal UV filter effect)
the presence of oxygen is the main cause of wood or preferably in a subsequently applied top coat (external
photo-oxidation. filter effect).
The lignin undergoes chemical modifications resulting in Such lignin stabilising treatments, which improve colour
radical formation and finally decomposition, producing stability in interior applications and long term durability in low
coloured and hydrophilic by-products. The resulting surface opacity exterior wood coatings [12] are based on a special
property changes lead to discolouration and increased water HALS. This traps the radicals formed by visible light at the
sensitivity followed by hydrolysis, leaching of the wood surface, which have not been screened by organic
chromophores, and finally erosion and greying of the wood. UVA (> 400 nm) [13, 14]. This approach finally allows the
Today the photo-oxidation of lignin is well understood and at use of clear or low-pigmented coatings even in high
least four degradation pathways have been identified [1]. performance, high durability outdoor applications, e.g.
The key to increasing the service life of wood with wooden window frames.
film-forming finishes is the optimisation of light protection of Today most of the paints used are semi-transparent
the wood surface and the coating. Since the early 1970s it finishes, where the pigments may act as partial VIS light
has therefore been common practice to combine UV protectors. This protection can be increased by combination
absorbers (UVA) with hindered amine light stabilizers with organic UVA for substrate protection and HALS for
(HALS). coating protection as well as the lignin stabiliser. It is well
known that such combinations of organic and inorganic
The chemistry of HALS and UVA UV/VIS light screeners show good performance in certain
HALS are mainly derivatives of 2,2,6,6-tetramethylpiperidine ratios.
and help to prevent surface defects such as gloss loss, The knowledge of how to use this two-step protection
chalking in pigmented systems and cracking in clear coats. strategy is still limited and has to be improved to obtain
Figure 1 shows the chemical structures of some commercial efficient and economic use of light stabilisers for film-forming
UVA and HALS products. wood coating systems according to the shade of the coating,
The most important HALS compounds are difunctional i.e. the degree of pigmentation. It is evident that clear,
piperidine derivatives, as shown in Figure 1. Here the semi-transparent and opaque coatings behave differently
substituent on the nitrogen atom determines the properties during weathering and therefore require different light
of the HALS due to basicity. For instance, HALS-1 with R = stabiliser packages.
CH3 is basic (pKb ~ 5) and interferes with acid catalysed and

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Experimental use of UVA nor the use of lignin stabiliser shows any
The effectiveness of various light-protective treatments was significant benefit in terms of colour retention.
evaluated using the following conditions: Hence UVA use can be significantly reduced or eliminated in
dark and opaque paints. As an initial recommendation,
Wood samples 1.0%, for clears, 0.5% for low to medium opacity and no
Pine (pinus radiata) 200 x 90 x 10 mm with back and end UVA for dark or opaque coatings are suggested.
grain sealing with an automotive 2K-PUR clear coat.
Dark and opaque systems require HALS
Paint system However, it is well known that colour retention is not the
Linseed long oil alkyd (LOA) with different amounts of main problem for dark and opaque pigmented systems.
transparent black, red and yellow iron oxides plus a white Earlier studies showed that these tend to suffer more from
pigmented system (2 x 120 g/m2 applied by brush) chalking and then complete erosion of the paint and the
wooden surface, whereas clear and low pigmented systems
Stabilisers primarily show cracking. In this case higher amounts of
HPT-1 as UVA, HALS-2 (decanedioic acid, HALS are necessary to protect the binder against
bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester) and photo-oxidation and avoid surface defects such as gloss
a lignin stabiliser pre-treatment (2% aqueous solution; 1x 80 loss, chalking and subsequent flaking [15].
g/m2 brush applied).
Direct lignin stabilisation yields best performance
Artificial weathering The effect of the lignin stabiliser on colour and coating
Atlas "Weather-Ometer Ci-65 A", Xenon light according to protection of pine with a clear UVA containing top coat after
the Xe-WOM CAM 7 cycle for exterior applications (inner & 1 year outdoor exposure is shown in Figure 4. Here LOA-1
outer borosilicate filter) according to DIN EN ISO 11341 A was applied without (A), with 1% HPT-1 and 0.5% HALS-2
(0.35 W/m2 / 340 nm: 102 min light and 18 min light and on total paint (B) and the second coating was applied over
spray). 2% aqueous solution of the lignin stabiliser (C). System (A)
shows gloss loss, cracking, and erosion with greying of the
Colour difference measurement wood surface. The use of HPT-1 and HALS-2 obviously
Minolta "CM-3600d" device (gloss included) and calculation improves the coating properties but some colour deviation
of L*, a*, b*, C*, h and ∆E* with "CGREC" software with darkening and yellowing can be seen.
according to DIN 6174. The lignin stabiliser further improves the colour retention to
almost retain the initial colour of the wood. In general, this
Gloss measurement approach shows excellent results in colour retention as well
60° gloss with Byk/Gardner "Micro-Tri-Gloss" equipment as mechanical properties of the paint film for all common
according to DIN 67530. pale wood species like pine, fir and ash.

Cracking Natural weathering tests

Visually according to DIN EN ISO 4628-4. The effect of HALS on the 60° gloss of LOA paints with
different degrees of pigmentation after 12 months 45° south
exposure in Pfeffingen, Switzerland is shown in Figure 5.
UV-VIS spectroscopy
The initial 60° gloss was around 30 for all paints. After
Integrated transmission spectra of 20 µm dry film thickness
exposure, paints without HALS had a 60° gloss of around
(DFT) on glass 200 to 800 nm with 1 nm resolution (Perkin
15. The use of UVA shows only slight improvement for all
Elmer "Lambda 900" UV/VIS/NIR spectrophotometer).
the paints.
Artificial weathering
HALS are always beneficial
The integrated transmission spectra (i.e. their light
The use of HALS is beneficial, regardless of whether UVA is
protection capacity) of different test coatings are shown in
used. For the low and medium pigmented paints (LOA-3,
Figure 2. Based on the transmission value at 500 nm they
LOA-5) the higher levels of HALS have little advantage over
can be classified as
the 0.5% addition.
- clear: >90% transmission (LOA-1)
For the dark LOA-6 and the opaque LOA-8, obvious
- low pigmented: 90% - 60% (LOA-2, -3)
improvements in performance are only obtained by using
- medium pigmented: 60% - 30% (LOA-4, -5)
1.0% or even 2.0% HALS. These results indicate that the
- dark pigmented: 30% - 0% (LOA-6, -7) and
use of higher amounts of HALS is necessary with increasing
- opaque pigmented: 0% (LOA-8).
pigmentation in the paint.
Organic light stabilisers, i.e. HPT-1 and HALS-2 and lignin
stabiliser pre-treatments were compared. The colour
deviation of pine with LOA stabilised with UVA/HALS (0.5% There is no single optimal light stabiliser package
and 1.0% / 0.5% on total paint) with and without lignin These results show the value of light stabilisers in retaining
stabiliser pre-treatment (2% in aqueous solution) after 1000 the mechanical and aesthetic properties of outdoor wood
h Xe-WOM CAM 7 exposure is shown in Figure 3. coatings. Unfortunately a single light stabiliser package is
not equally suitable for all shades from clear to opaque
pigmented systems. But it is possible to give rough
Adapting UVA use to the opacity
guidelines based on the transmission profile of the
In the clear, low and medium pigmented finishes the use of
pigmented paints. In general the concentration of UVA can
UVA alone reduces the colour deviation on pale wood
be reduced and the concentration of HALS should be
species to a certain extent, with better results for a higher
increased with increasing pigmentation.
UVA concentration. The visible light screening of the
For clear paints, higher amounts of an optimum UVA (0.5%
pigment evidently also improves performance. In all cases,
to 1% on total paint) have to be used to protect the
the lignin stabiliser system has the best performance.
substrate, with HALS added (0.5%) to protect the coating
The dark LOA-6/7 and white opaque LOA-8 show lowest
from surface defects. In addition a solution of 1% to 2%
colour deviation of the non-stabilised paints and neither the

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lignin stabiliser, preferably used in aqueous solution or an - The degradation of wood surfaces on exposure to light is
existing primer formulation helps to retain aesthetic and mainly due to breakdown of the lignin component, which
mechanical properties discolours and becomes more hydrophilic.
For light and medium pigmented systems the amount of - Hindered amine light stabilisers (HALS) protect the coating
UVA can be reduced to 0.5% as the pigment itself protects surface by blocking radical reactions initiated by light, while
against light, but the amount of HALS should be increased UV absorbers prevent UV light from reaching the substrate.
(0.5% to 1.0%). The lignin stabiliser again improves results. - A wood pretreatment system which uses a special HALS
In dark and opaque pigmented systems the UVA and lignin has been developed to protect lignin from photodegradation
stabiliser add no real benefit to the overall performance of due to VIS light. It is shown to have considerable benefits
the system as long as sufficient amounts of HALS (1% to when using low-opacity coatings.
2%) are used to avoid surface defects. - The most effective means of protecting wood from light
This has to be seen as a basic general guideline for starting damage depends on the opacity of the coating.
point formulations. The benefits may differ according to the - For opaque and dark pigmented coatings, HALS addition
quality of the binder system, the solids content of the paint, must be increased to protect the coating itself from light
the quantity and type of the pigments used, the final damage, while for clear, low and medium pigmented
application and the local weather conditions. Ultimately, it is systems, high UV absorber levels with lower HALS and
always the real experiment that tells us the final answer. lignin stabiliser pre-treament are more effective.

ACKNOWLEDGEMENTS The authors:

The authors would like to thank Nadja Brugger and Raphael -> Dr. Christian Schaller received his Diploma degree in
Meyer from Ciba Specialty Chemicals Technical Service, chemistry from the University of Stuttgart, Germany, in
wood coatings laboratory, for their contributions to this work. 1998. After obtaining his PhD at the Research Institute of
Pigments and Coatings (FPL), Stuttgart, Germany he
REFERENCES continued academic research at the FPL. He joined Ciba
[1] G. J. Leary, Journal of Pulp and Paper Science 20 (1994) Specialty Chemicals in 2002. Since 2003 he is Application
6 Head for light stabilizers and additives in the Technical
[2] A. Valet, Light Stabilizers for Paints, C. R. Vincentz Service
Verlag Hannover 1997 -> Dr. Daniel Rogez (PhD in Polymer Chemistry from the
[3] A. Stährfeld, A. Braig, Advanced UV protection of University of Haute Alsace, France) joined the former
automotive clear coatings, XXVI FATIPEC Congress, Ciba-Geigy company in 1979. Working initially in the paints
Dresden, Germany 2002 and inks additives development laboratories, he specialised
[4] S. Zeren, UV Stabilization of powder clear coats, XXVI in antioxidants, light stabilisers and photoinitiators for the
FATIPEC Congress, Dresden, Germany 2002 European market. He is currently Global Marketing Manager
[5] C. Schaller, D. Rogez, A. Braig, for Additives and Colorants for Decorative and Industrial
Hydroxyphenyl-s-triazines: advanced multi-purpose Paints at Ciba Specialty Chemicals, Basle, dealing
UV-absorbers for coatings, XXVIII FATIPEC Congress, particularly with the wood coatings market.
Budapest, Hungary 2006
[6] D. Rogez, P. Hayoz, W. Peter, UV-curing and light
stabilization of parquet coatings, European Coatings
Conference on Parquet Coatings II, Berlin, Germany 2002
[7] P. Hayoz, W. Peter, D. Rogez, Asia Pacific Coatings
Journal (2003) 16 (2) 14
[8] P. Hayoz, W. Peter, D. Rogez, Asia Pacific Coatings
Journal (2003) 16 (3) 28
[9] W. Peter, C. Schellenberg, D. Rogez, C. Schaller, G.
Kalscheur, New concepts for improved durability of
waterborne wood coatings, Coating Wood and Wood
Composites Conference, Charlotte, NC, USA 2005
[10] W. Peter, C. Schaller, C. Schellenberg, D. Rogez, A
new concept of aqueous additive preparations for
waterborne coatings, Waterborne and High Solids Coatings
Conference, Brussels, Belgium 2006
[11] C. Schaller, D. Rogez, W. Peter, New approaches for
wood coating stabilization, 5th International Wood Coatings
Congress, Prague, Czech Republic 2006
[12] D. Rogez, Color stabilization of wood and durability
improvement of wood coatings, 2nd Wood Coatings
Congress, The Hague, Netherlands 2000
[13] P. Hayoz, W. Peter, D. Rogez, Improved
photo-protection of wood and durability improvement of
wood coatings, 3rd Wood Coatings Congress, The Hague,
Netherlands 2002
[14] P. Hayoz, W. Peter, D. Rogez, Farbe + Lack 109(7)
(2003) 26
[15] C. Schaller, D. Rogez, New concepts for light
stabilization of wood, 18th SLF Congress, Elsinore,
Denmark 2006

Results at a glance

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Figure 1: Chemical structure of some commercial UVA and HALS products.

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Figure 2: Integrated transmission spectra of the LOA paints tested.

Figure 3: Colour deviation of pine with LOA with HPT-1/HALS-2 with and without lignin
stabiliser after 1000 h Xe-WOM CAM 7 exposure.

Figure 4: Pine with LOA (A: no additive; B: 1% HPT-1 + 0.5% HALS-2; C: 2% lignin
stabiliser pre-treatment / 1% HPT-1 + 0.5% HALS-2) after 1 year 45° south open rack
exposure in Pfeffingen, Switzerland.

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Figure 5: Effect of the HALS-2 concentration on 60° gloss of LOA paints after 12
months 45° south exposure in Pfeffingen.

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