Professional Documents
Culture Documents
C OATINGS
www.european-coatings.com journal 09 — 2020
10
WOOD
COATINGS
This issue comes with a full package on wood
coatings: a technical paper on the durability
of exterior coatings, a market report, a product
over view and exclusive expert voices.
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EDI T OR IAL 3
In our focus paper from page16 Gerhard Grüll and his team at Holzforschung
Austria give a summary of their last two decades of research into the durability
and service life of wood coatings and the conclusions for practice. The au-
thor will also present their findings in more details at the European Coatings
Live on 22 September at 15:00 CET. The web event is free of charge, you can
register at www.european-coatings.com/live.
Enjoy reading!
10
Source: Ilshat - stock.adobe.com
EXPERT
VOICES
Additives
modifying the
gloss level
12 16
WOOD COATINGS
Durability of exterior wood coatings
WOOD COATINGS
6 INDUSTRY NEWS 10 MARKET REPORT
The most important moves wiithin the coatings industry. Challenging market environment
12 EXPERT VOICES
Jos Kemp, PPG, and Claudia Schirp, Fraunhofer WKI
14 PRODUCT OVERVIEW
Additives modifying the gloss level
16 TECHNICAL PAPER
Two decades of research into the durability of exterior wood
coatings. Dr Gerhard Grüll, Dr Boris Forsthuber, Florian
Tscherne, Holzforschung Austria
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
C O NT E N T S 5
24
Source: Grispb - stock.adobe.com
LEGISLATION
Meeting the PIGMENT CONCENTRATES
reporting Colour pastes from the
requirement construction kit
30 32
30 LEGISLATION
Meeting the reporting requirement. Dr Dieter Reiml and Rupert
Scherer, TÜV Süd Industrie Service
32 PIGMENT CONCENTRATES
Colour pastes from the construction kit. Dr Jörg Horakh,
Heubach
MARKET MOVES
A short over view on the most important moves within the European
coatings industry. You can find more news on markets and companies,
raw materials and technologies at www.european-coatings.com.
“Penetrate markets
across the globe.“
Hubergroup bundles chemical expertise in a separate division
Lauren Pagano, Business Director Latex Binders
Strategy The printing ink manufacturer Huber-
Source: Hubergroup
CASE at Trinseo
group repositions itself: The production and mar-
Trinseo has been strengthening the CASE keting of raw materials for printing inks and coat-
unit. Please explain why? Trinseo is a global ings is now handled by the Chemicals Division. To
supplier of latex binders and a solutions provider diversify and divide the business into two divisions
to the CASE market. It is important for us to con- - Print Solutions and Chemicals - is a strategic cor-
tinue to focus on our CASE business unit as it is porate decision. Hubergroup is thus pursuing the
part of our strategy, to continue the diversifica- goal of making its technological expertise available
tion of our portfolio, especially regarding sus- to a wider range of customers.
tainability, and to continue to incorporate and
introduce new technologies. The CASE segment is www.hubergroup.com
a high growth market and therefore, highly at-
tractive. We continue to leverage ourselves, our
products, and chemistries into the market as it
supports our mission towards a specialty solu- Biesterfeld and Evonik expand cooperation
tions provider. CASE is an area of tremendous
opportunity, and that is why we are feeling confi- Distribution Biesterfeld is expanding its long-
Source: Saklakova - Fotolia
dent about growing in this market. term partnership with Evonik in the field of paint
and varnishes. With immediate effect, Biesterfeld
You acquired the vinyl pyridine (VP) latex will distribute matting agents, fumed silicas used
business from Synthomer. Why? This was a for rheology control in various applications, and
step to complement our portfolio and to grow special fillers from Evonik used as titanium dioxide
in the CASE business. This transaction helps us extenders in Poland, the Czech Republic, Slovakia,
to diversify ourselves into new markets and new Hungary, Romania, Serbia, Croatia, and Slovenia.
technologies by being able to offer VP latex for With this expansion, Biesterfeld intends to expand
coating tire cord fabrics, ensuring a strong bond its portfolio in a targeted manner.
between the tire cord and rubber during the tire
manufacturing process. We have gained exper- www.biesterfeld.com/en
tise in-house that we can integrate into our cur-
rent setup. This gives us strong technical leverage,
which we could bring to the tire industry. We will
continue to develop this business and penetrate
markets across the globe. “Quantum computing will enable us
You invested in an increased facility at the to take research and development to
Rheinmünster/Germany site. Will you shift
production to this site? Both acquisitions of
a completely new level.“
the Rheinmünster site and the VP latex business CEO Dr. Markus Steilemann, Covestro
align with our strategy to grow our latex binders
business in CASE, but they are not connected. The
Rheinmünster site helps us to support our growth
initiatives that we have in CASE and allows us to Epple: Aqcuisition of PCO Europe and new subsidiary
be more flexible and agile. It helps us as we con-
tinue our journey to diversify our chemistry base BeNeLux Epple Druckfarben increases ben Benelux has started its operations in
outside the core technologies. And the acquisition its shares in the Dutch printing chemi- Turnhout, Belgium. With the new subsidi-
of the VP latex business reinforces our position as cals manufacturer PCO Europe to 100 ary, Epple, manufacturer of sheet-fed off-
a solutions provider to the high-performance tire percent. As a manufacturer of sheet-fed set printing inks, wants to maintain more
segment. As part of the transaction, Trinseo has offset inks and varnishes, the company direct contact with printers and end cus-
established agreements with Synthomer for con- thus takes over a leading producer and tomers in Belgium, the Netherlands and
tract manufacturing the products at Synthomer’s supplier of printing chemicals for the Luxembourg.
production facility at Marl, Germany, where the offset printing industry. Additionally, the
products will continue to be produced. newly founded company Epple Druckfar- www.epple-druckfarben.com/en/
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
BYK Additives
Everything that wood needs
ANZEIGE
Sophisticated graining, a pleasant feel – elegant furniture or high-grade parquet flooring reveals wood in
its finest form. At the same time, these objects must withstand the tough everyday stresses and strains.
This demands the highest standards of the processing and protective properties of coatings. Whether
it’s waterborne or UV systems, BYK additives optimize important properties such as gloss, scratch
resistance, UV protection or durability. And consequently ensure that wood is not only good-looking
but remains that way.
www.byk.com
PRA’s 12th International
WOOD COATINGS
10 MARKET REPORT
Challenging market environment
12 EXPERT VOICES
Jos Kemp, PPG, and Claudia Schirp, Fraunhofer WKI
14 PRODUCT OVERVIEW
Additives modifying the gloss level
16 TECHNICAL PAPER
Two decades of research into the durability of exterior wood coatings.
Dr Gerhard Grüll, Dr Boris Forsthuber, Florian Tscherne. Holzforschung
Austria
As wood remains a popular building material, the forecasts the wood coatings market in the industrialised countries is saturated,
of the market research institute Markets and Markets for the so that it will probably grow more slowly. The market in the emerging
further development of the wood coatings market sound posi- countries, such as China and India, is expected to grow more strongly in
tive. The global volume should increase by 2024. Yet, the out- the next five years.
look of industry players sounds more cautious than that of the
market researchers, as the wood coatings manufacturers tend WOOD COATINGS MANUFACTURERS EXPECT STAGNATION
to assume stagnation.
The development forecasts of the industry players are more cautious.
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
MA R KE T R EP O R T 11
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
E XP ER T V OIC E S 13
shield
nomical enough to reach a high market share.
However, when you ask for renewable raw ma-
terials, recyclability and environment pollution
by micro plastics, there is still plenty of room for
research and development. Therefore, I rather
see needs in recycling systems and technolo-
gies instead of new functions of the material.
The challenge of the future will be to have ex-
cellent technical performance combined with
materials that can be handled in a closed and Claudia Schirp
sustainable circular economy with less energy Project manager
consumption and lower carbon footprint. The Fraunhofer-Institute for Wood Re- www.brb-international.com
group of customers who are interested in search, Wilhelm-Klauditz-Institut, WKI
green and sustainable products is increasing. claudia.schirp@wki.fraunhofer.de
MATT IS BEAUTIFUL
Wooden furniture and other wooden surfaces are widely
Source: Polat Alp - stock.adobe.com
Active Physical
Company Product name Chemical basis Particle size Application
content properties
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
P R O DU C T O V ER VIE W 15
Improved scratch resistance and anti-blocking properties, soft-feel-effect, Jorge Prieto et.al., 396 pages,ISBN: 9783866306080
transparent coatings. No effect on viscosity, surface slip and foam
Abrasion resistance
The service life of exterior wood coat- will not show unexpected weathering behav- ESTIMATED MAINTENANCE INTERVALS
ings has been a key issue in the research iour. Their customers can therefore expect
group on surfaces at Holzforschung high-quality products. However, it is often said In a research project on exterior wood clad-
Austria for about 20 years. It is worth that wood needs a lot of care and recoating dings about 20 years ago, a group of young
summarising the experience gathered to be durable and resist natural weathering. researchers endeavoured to estimate coat-
during this period and looking back on Coatings protect wood – they can reduce ing maintenance intervals. This proved chal-
the development of conclusions for moisture fluctuations, prevent cracking, re- lenging due to a lack of long-term experience
practice. Have early theories and rec- duce dimensional changes, they filter harm- and limited available literature. Nevertheless,
ommendations from a young research ful wavelengths of light and prevent fungal the results should be sound enough to give
team been proven in practice? growth. However, like all building products, recommendations for practice. An excellent
coatings themselves underlie degradation source of experience in this project was the
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
T E CHN I C A L PAP E R 17
RESULTS AT A GLANCE
űű A series of research projects vali-
dated guidance values for maintenance
72
intervals of exterior wood coatings.
66
lished in a practical booklet [1]. The guide Figure 2: Time to failure as a function of brightness of 26 out of 30 coating systems on
gave estimated maintenance intervals de- wood in natural weathering.
pending on the dry film thickness and opac-
ity of the coating along with practical proce-
dures for maintenance and renovation.
Based on the laboratory results from meas-
uring the physical properties of wood coat- 72
ings, such as water permeability and water 66
vapour or UV-light transmission, researchers 60
Natural weathering / months
was revised over the years [2] but the table of be clear when the end of a coating system’s ent opinions on when the end of a coating’s
maintenance intervals of coatings remained durability is reached. Therefore, we defined a service life is reached. So, it was important
virtually unchanged. series of limit states for exterior wood coat- to separate aesthetic aspects, which require
In a booklet on balconies and decking [3], ings [6] (Table 2). cleaning or refreshing surfaces, from techni-
the table was expanded to include near- At the beginning of this work it became clear cal reasons which require maintenance and
ly horizontal surfaces such as hand rails that even experts in the same field had differ- repair.
(Table 1) to take into account the influence
of inclination of a surface on durability. Re-
search work on balconies and decking veri- Figure 3: Time to failure of 26 out of 30 coating systems on wood in natural weathering
fied that nearly horizontal surfaces degraded compared to artificial weathering.
much faster than vertical ones. This extend-
ed table proved to be a relatively universal
tool for estimating the service life of exterior 84
wood coatings. International experts in the 78
European research project WoodExter [4] 72
discussed and confirmed the values in this
Natural weathering / months
66
table. All the maintenance recommendations R 2=0.80
60
from this research group were compiled in a 54
booklet [5]. 48
42
LIMIT STATES HELP WITH MAINTENANCE 36
DECISIONS 30
24
Traditional investigations into coating degra- 18
dation during weathering report results after 12
a defined period of weathering exposure. 6
In contrast, service life prediction is based
0
on the time of exposure or the dosage of 0 3 6 9 12 15 18 21 24 27 30 33 36 39
weathering impacts that is needed to reach
a limit state – which defines the service life Artificial weathering / weeks
of the product. This involves a different test
Systems 95% Confidence inter val
strategy with longer periods of weathering
Trend (linear) 95% Prognosis inter val
until failure occurs combined with short in-
spection intervals. At the same time, it must
Figure 4: The SERVOWOOD ser vice life prediction model gives results relative to a reference system; a web-based application to use
this model is under development.
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
T E CHN I C A L PAP E R 19
Technical defects determine durability be- ten the need for repair is only recognised by rely on sound test methods that imply safety
cause they impair the protective functions the time renovation is required. Maintenance factors or enable service life prediction. But
of coatings. The visual appearance of coated and renovation are the secret of durability can testing of exterior wood coatings replace
wood can become unacceptable when col- of wood buildings and wood components in long term experience?
our or gloss fade, when the surfaces become exterior use. The researchers used the defi- Development and testing of wood coatings
dirty or algae grow, but this has no technical nition of these limit states when investigat- for exterior use are closely related to weath-
consequences for the protection of the wood ing the durability of wood coatings and pub- ering tests. Natural weathering is the most
substrate. A significant loss of film thickness lished them to help with decision-making on accurate method of investigating the dura-
by chalking, as well as cracks, hail damage, the need of maintenance in practice. bility and characteristics of a coating as can
flaking, blistering or the growth of mould and be expected in real use on a building. Several
blue stain, however, have a negative effect on STANDARDISED TESTING TO ASCERTAIN methods and devices for artificial weather-
the tightness of the coating. These defects REAL-LIFE DURABILITY ing have been developed to accelerate the
must be repaired and it is of advantage that development and testing of wood coatings
this is done early after their occurence. The demand for long-term experience hin- with the aim of increasing reproducibility.
The maintenance interval is reached when ders innovation. The development of inno- The European standard EN 927-6 describes
coating adhesion is still good, and minor vative and improved products needs time, the method that is frequently used to assess
defects can be cured with a simple mainte- money and energy of researchers, which wood coatings using a device with fluores-
nance coat over the old coating. If the coating must be earned on the market with the new cent UVA 340 lamps, water spray and water
has degraded further and has lost adhesion, product making profit as soon as possible. condensation in a defined cycle. When inter-
it requires renovation, which needs much Institute researchers learn this very quickly preting the results of artificial weathering,
higher efforts compared to maintenance. But in direct collaboration with industry partners. a common question is how long a coating
in practice time passes quickly and very of- To sell a mature product, developers must will last in exterior use. What does a dura-
Table 1: Guidance values for maintenance inter vals of exterior wood coatings on cladding and balconies [5].
vertical 3 years
protected
horizontal 2 years
bright
vertical 1–2 years
unprotected
Impregnation, low build horizontal 1 year
stain 0 to approx. 30 µm vertical 3–4 years
protected
horizontal 2 years
dark
vertical 2 years
unprotected
horizontal 1–2 years
vertical 5 years
protected
horizontal 3 years
bright
vertical 2 years
unprotected
Medium build stain horizontal 1 year
approx. 30–60 µm vertical 7 years
protected
horizontal 4 years
dark
vertical 3 years
unprotected
horizontal 2 years
vertical up to 15 years
protected
horizontal 7 years
bright
vertical 10 years
unprotected
Opaque paint horizontal 5 years
approx. 30–60 µm vertical 12 years
protected
horizontal 6 years
dark
vertical 8 years
unprotected
horizontal 2–4 years
bility of 2,000 h artificial weathering mean tion that the laboratory test selected the best the research group (Table 1). With all tested
expressed in years of natural weathering? coatings. The results confirmed that coating systems we found reasonable conform-
Many experienced researchers know some film thickness and pigmentation of semi- ity between artificial and natural weather-
rules of thumb, and there have been several transparent systems strongly influenced the ing results (see Figure 3). This means that it
attempts to correlate the results of different time to failure during weathering. Figure 1 is possible to predict the durability of wood
artificial weathering cycles with natural expo- shows that coatings with a higher dry film coating systems using artificial weathering
sure. In 2014, we published a comparison of thickness had a clear tendency towards a tests in the laboratory. The prognosis interval
wood coating durability in natural weathering higher time to failure in natural weathering. illustrates the uncertainty of this correlation,
and artificial weathering using the methods While the linear correlation was poor for but this can be narrowed down by collecting
of EN 927 standards [7]. all systems because of their very different more data on coating materials from a sin-
formulation, a variation of the same coat- gle formulator, which would be a treasure
OPAQUE COATINGS PROVED MORE ing material in four dry film thicknesses re- for a coating developer. Standardised testing
DURABLE vealed an excellent correlation (dotted line). therefore makes sense and a collection of
Figure 2 shows the influence of pigmenta- data over the years is well-documented long-
After this publication the research group ex- tion. Although not as clear as for dry film term experience.
tended the same natural weathering trials, thickness, there was a trend of higher dura-
and so we now have long-term results from bility of varnishes with darker pigmentation, SERVICE LIFE PREDICTION MODEL
seven years’ natural weathering compared to which was probably caused by better light
10,080 hours (60 weeks) artificial weathering protection for the substrate and the coating. In recent years, service life prediction mod-
of 30 coating systems. Four opaque paints Opaque coatings had the best light protec- els for exterior wood coatings have been de-
have displayed the greatest durability to nat- tion and achieved the highest time to failure, veloped in the SERVOWOOD project [8] [9].
ural weathering and are still in good condi- i.e. maintenance intervals, of all systems. These are based on data from experiments
tion without needing maintenance. Three of These scientific data confirmed the assump- with 52 different model formulations of wood
these systems were durable over 60 weeks tions that were made when drafting the table coatings with known composition. The exper-
of artificial weathering, which is one indica- of maintenance intervals in the early work of iments included a unique dosage variation in
Limit state Film-forming coatings Non film-forming coatings State of coating Defects
Change of gloss
Aesthetic limit, Aesthetic limit, Only visual
L-E Change of colour
optical deficiency optical deficiency alteratioins
Growth of algae
Intensive chalking
Cracking
Blistering
Flaking
Discoloration
around cracks
Penetrating mould growth /
blue stain
L-D3 Decay of wood Decay of wood Onset of decay in wood White rot fungi
Wood-boring insects
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
T E CHN I C A L PAP E R 21
Figure 5: Schematic of hail damage and degradation of a coating on wood with moisture ingress, followed by growth of blue stain
fungi and flaking; maintenance can be possible until step 3.
1 4
2 5
3 6
Figure 6: Section through a hail impact on coated wood after nine months natural weathering; top: varnish without primer, strong
discoloration and fungal growth in the wood; bottom: varnish with primer, no fungal growth, hardly any discoloration.
natural weathering on multi-faceted expo- Extreme weather phenomena have become weathering in a standardised test or in prac-
sure rigs enabling the samples to be exposed more frequent and many thunderstorms tice on a building component [5]. This helps
to weathering in nine different directions. involve regional hailstorms. Hail impact can to decide whether a maintenance coat is suf-
This setup captured how much fungal growth destroy many building materials because the ficient or if it is necessary to remove the old
is pronounced on surfaces facing north and ice balls can be several centimetres in diame- coating and renovate the surface..
east while degradation was determined by ter and hit the surface with very high energy. After many projects like those described here
cracking and flaking on the south and west Coatings on wood are prone to damage even and excellent collaborations with renowned
faces. Results from statistical analysis of data from relatively small hailstones. The damage coating manufacturers and their R&D labs,
from four European laboratories were input caused by hail is characterised by barely vis- we see a good development in durability of
for a factor model according to ISO 15686-8. ible concentric cracks. At these cracks, mois- exterior wood coatings. This is also a result
This has the advantage that the model can ture can creep under the coating and even- of knowledge transfer in the sector including
be improved consequently when new data is tually lead to loss of adhesion and flaking as the wood industry and painters to ensure a
available. Natural weathering tests, started well as growth of blue stain fungi (Figure 5). In better quality coating application.
within the SERVOWOOD project, were pro- a recent project on hail resistance of wood
longed and will give input to the model in the coatings good progress was made in the im-
near future. provement of coating durability under these REFERENCES
The model will also be transferred into a extreme circumstances. This challenge can
web-based calculation tool for easy and be addressed on the one hand by specific [1] B
randstätter M et al., Holzfassaden. Vienna:
guided use (Figure 4). Within the model, coat- mechanical properties of the coating at rela- Holzforschung Austria, 2002.
ing properties that can be measured in the tively high dry film thicknesses, which was de- [2] S
chober K P et al. (2018): Fassaden aus
laboratory together with dosage factors will scribed in a multivariate model. On the other Holz: proHolz-Information. 3rd edition, Vienna:
provide an estimation of service life relative hand, proceeding damage after hail impacts proHolz Austria (ProHolz Information). ISBN
to a reference material. In the example in Fig- can be decelerated by using primers, which 978-3-902320-74-2
ure 4 an unpigmented system was chosen as avoid moisture ingress, ensure good wet ad- [3] S
chober K P, Auer C, Grüll G (2006):
the reference coating and the pigmentation hesion and include fungicides (Figure 6). Balkone und Terrassenbeläge aus Holz.
of the model system increased the service In natural weathering studies it was found Holzforschung Austria, Wien, ISBN 978-
life by the factor 1.5. A set of factors will be that the tolerance for the period after hail 3950252613
available for variations of dry film thickness, damage until application of a maintenance [4] D
earling T B, Suttie E D (2011): Maintenance
mechanical properties, wood species and coat can be as high as one year with high and renovation of exterior wood coatings. Cli-
growth ring angles as well as for parameters quality coating systems. This tolerance can ent report number 273427, Woodwisdom-Net
of exposure dosage, sheltering and detailing. be tested in natural or artificial weathering project WoodExter
As the reference material is usually a system with simulated hail damage. This is made [5] G
rüll G, Tscherne F (2020): Wartungsanleitung
well known to the user of the model, not only with a steel ball that is placed on a coated für Beschichtungen auf Holz im Außenbereich.
from laboratory testing but also in practise, wood panel when a mass piece falls from a 4th edition, Holzforschung Austria, Vienna,
this approach of the model combines long- defined height. This causes an impact very ISBN 978-3-9519933-0-0
term experience with the laboratory test re- similar to hail and the impact energy can be [6] G
rüll G et al. (2011): Maintenance procedures
sults of a new product. varied by the falling height and mass. A sim- and definition of limit states for exterior wood
ple tape test helps to check whether coating coatings. Eur. J. Wood Prod., 69, 443-450
HAIL RESISTANCE TO IMPROVE adhesion is still good at hail impacts during [7] G
rüll G et al. (2014): Comparison of wood
DURABILITY coating durability in natural weathering and
artificial weathering using fluorescent UV-
lamps and water. European Journal of Wood
and Wood Products, 72, 3, 367-376.
[8] F
orsthuber B, Ecker M, Grüll G (2017): Predict-
Dr Gerhard Grüll
Holzforschung Austria
g.gruell@holzforschung.at
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
CEP E C O R N E R 23
Visit our
digital
formulation
www.coating-additives.com assistant
For years, more and more customers have been attracted to additives to discuss the health risk of nail polishes, e.g. benzophenone,
natural alternatives for traditional cosmetics, which are often etocrylene, octocrylene or styrene, as a UV blocker or plasticizer [2].
harmful to health and the environment. The innovative pro- BioNails uses the innovative concept of “EMA” (enzyme mediated ad-
ject “BioNails” focuses this trend on nail polish: natural raw dressing). With this application technology, the coating layer is formed
materials and a new application concept define a new way of directly on the nail and with high specificity (Figure 1). The system is
sustainability. water-based and based on natural resources. For the application, the
user has to apply the enzyme directly to the nail, this can be done us-
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
B I O -B A SED C O AT I N G S 25
RESULTS AT A GLANCE
Nail polish made from wood, such as resorcinol, tannic acid
and lignin is possible with a new application concept.
cluding polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS) and groups (Figure 2a). Due to the antiseptic effect of diluted resorcinol solu-
poly(methyl methacrylate) (PMMA) [7]. The decomposition of hydrogen tions, it is used in dermatology. Tannic acid occurs in wood and in plant
peroxide activates the enzyme’s iron center, which can subsequently act parts, is soluble in water and has a non-uniform, polyphenolic structure.
as an oxidizing agent for phenolic species [8]. With this biological system, The basic building block is gallic acid (Figure 2b). Tannins occur in wine
phenols can be polymerised without the addition of aldehydes. and tea and are also used in cosmetic products such as deodorants.
Materials that can be obtained from wood or from wood components Lignin occurs in wood and in plant parts, is not soluble in water and
and have phenolic groups were chosen as monomers. Among them, has a non-uniform, polyphenolic structure. The basic building blocks
resorcinol, tannic acid and lignin provide promising results. Resorcinol are paracoumaryl, coniferyl and sinapyl alcohol (Figure 2c). The biopoly-
is obtained from natural resins, is soluble in water and has two hydroxyl mer is responsible for the strength and stability of trees and plants and
Figure 2: Structural formulas of (a) resorcinol, (b) gallic acid, (c) paracoumaryl, coniferyl and sinapyl alcohol.
a) b) c)
OH
HO O
OH
OH
HO
OH
OH HO
HO
HO O
O
O
OH
HO
Figure 3: Experimental setup for the coating according to “EMA”. can only be used technically if it has been broken down by the sulfate
or sulfite process. The sulfate process produces water-soluble alkaline
lignin and the sulfite process provides water-soluble lignin sulfonic acid.
Water-soluble dealkaline lignin can be produced by adjusting the pH of
alkaline lignin or by chemically modifying lignin sulfonic acid.
EXPERIMENTAL
Table 1: Results of the contact angle measurements of the coatings based on resorcinol, tannic acid and dealkaline lignin.
Θ [°] ± σ [mN/m] ±
Figure 4: Scanning electron microscopy images of the coatings based on (a) resorcinol and (b) tannic acid polymerized in water and
of (c) resorcinol, (d) tannic acid and (e) dealkaline lignin polymerized in an aqueous DMSO solution.
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
BIO-B A SE D C OAT I NG S 27
DISCUSSION
Resorcinol and tannic acid are soluble in water. Coatings on this basis
are hydrophilic. The measured contact angles are in the range of 10
to 15° (Table 1). In contrast, the dealkaline lignin coating has a higher
contact angle, with a value of Θ = 52°. Even as a raw material, lignin
is less hydrophilic than resorcinol and tannic acid, and the contact
angles reflect this trend. The results of the free surface energy also
confirm this trend: the wettability of the coating of resorcinol and tan-
nic acid is better than that of dealkaline lignin.
Scanning electron microscopy (SEM) enables nanometer-precise res-
olution and examination of the specifically polymerised films of resor-
cinol, tannic acid and dealkaline lignin with various solvent composi-
tions. The exclusive use of water is desirable for the target application.
In water, the polymer based on resorcinol forms a network that is very
close-meshed and porous (Figures 4 a–b). In contrast, tannic acid poly-
merises to a very smooth film that tends to blister. It was not possible
to deposit a polymer based on dealkaline lignin in water.
DMSO is classified as harmless to health and can be used safely as
a co-solvent (Figures 4 c–e). Aqueous DMSO solutions have only a
minor influence on the polymerisation of resorcinol, a network is
formed again, but due to the poorer solubility it is somewhat more
meshed than in the case of the polymerisation in water. However,
when tannic acid is deposited, the polar aprotic solvent causes a
major change: instead of a smooth, continuous film, a loose net-
work is formed. This is due to the reduced solubility of tannic acid in
DMSO-containing solutions. The tannic acid precipitates early out of
the reaction solution, i.e. before it can form long polymer chains and
therefore only forms particles and network structures. The reverse
effect can be observed with dealkaline lignin: the improved solubility
with DMSO-containing solutions has a positive effect, a smooth and
thick film is formed.
The coating process of all three monomers was also tested with oth-
er solvents, beyond the intended use. The protic solvents ethanol
and isopropanol, and the aprotic solvents dioxane and THF. In the
case of the two protic solvent mixtures, the SEM images of the re-
sorcinol-based coatings (Figure 5) show clear trends: the higher the
proportion of solvent, the higher the degree of filming. With a sol-
vent content of 25 %, resorcinol forms network structures and with
a content of 75 %, smooth films are formed. In contrast, no trend
can be observed in the case of aprotic solvents: resorcinol forms
network structures in aqueous dioxane solutions and a fibrous film-
ing in aqueous THF solutions. Deposition is no longer possible with
75 % dioxane and over 50 % THF mixtures. As with resorcinol, the
coatings based on tannic acid in protic solvent mixtures show a bet-
ter result than the coating tests in solutions containing dioxane and
THF (Figure 6). The polymerisation of tannic acid in ethanolic solu-
tions produces smooth and thick films. Depending on the ratio of
ethanol to water, the coatings tend to crack, blister and wrinkle. In
contrast, isopropanol solutions only produce smooth films at higher
concentrations, and the coating has holes at low concentrations
of isopropanol. The tendency to form bubbles is characteristic for
tannic acid and is therefore also found in these solvent mixtures,
particularly strongly in aprotic solvents. The polymerisation in the
dioxane solution produces a film network and in the THF solution a
holey film. With both solvents, coating with a solvent content of 50 %
or more is no longer possible. Dealkaline lignin shows a similar pro-
gression of the degree of film formation in ethanolic, isopropanolic
and dioxane-containing solutions (Figure 7). It was not possible to
polymerise dealkaline lignin in THF-containing solutions.
In general, the EMA process is interesting for specific coatings that have compositions. For real nail tests, resorcinol and tannic acid can be
to be applied locally and with nanometer precision. However, it is irrel- prepared in water and dealkaline lignin in an aqueous DMSO solu-
evant whether the raw materials are of natural origin or industrial poly- tion. The application is analogous to the experiments with the cover
mers (such as PP, PVC, PS, PMMA). Areas for coatings with EMA are: slip: the aqueous enzyme solution is placed directly on the nail and
ąą medicine dried at room temperature. Once the nails are dry, they can be put in
ąą wood the reaction mixture with the monomer and hydrogen peroxide. The
ąą paper physical adsorption of the enzyme is sufficient to start the specific
ąą sustainable synthesis of bio-polymers polymerisation and to initiate the deposition locally. The polymerisa-
tion is complete within a short time and the nails can be removed
OUTLOOK from the container after one to five minutes. Photographs are shown
in Figure 8. The resorcinol-based nail polish (Figure 8a) shows the best
This work shows that coatings made from different wood compo- properties in terms of uniformity and gloss. Due to the strong intrin-
nents are possible with the right selection of raw materials for en- sic colour, however, there are problems with pigmentation. This is
zyme-catalysed polymerisation and the correct setting of the solvent less relevant for tannic acid (Figure 8b) because tannic acid forms a
Figure 5: Scanning electron microscopy images of the coatings Figure 6: Scanning electron microscopy images of the coatings
of resorcinol polymerised in different solvent compositions. of tannic acid polymerised in different solvent compositions.
Tannic
acid
Resorcinol
Ethanol
Ethanol
Isopropanol
Isopropanol
Dioxane
Dioxane
THF
THF
Figure 7: Scanning electron microscopy images of the Figure 8: Application tests of the coatings based on (a) resor-
coatings of dealkaline lignin polymerised in different solvent cinol, (b) tannic acid and (c) dealkaline lignin according to the
compositions. “EMA” principle.
Dealkaline
lignin
Ethanol
Isopropanol
Dioxane
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
B I O -B A SED C O AT I N G S 29
Do you see any chance of eliminating the intrinsic colour of the raw materials? Lignin has
an intrinsic colour right from the start, but resorcinol does not. An aqueous resorcinol solution is
colourless and the deposited polymer only becomes darker as the degree of cross-linking increases.
This situation is comparable with the system of phenoplastics, where the colour is determined by the
degree of cross-linking. Anna Becker-Staines
University of Paderborn
Are there already ideas for producing pigmented coatings in this way? And in your opin- anna.becker@uni-paderborn.de
ion, do they also have to be of natural origin? Yes, this is planned for the future and for our
project pigments of natural origin are in focus. But theoretically also industrially produced pigments
could be incorporated into this system.
You write that coatings based on resorcinol and tannic acid are hydrophilic. Could these
wash off too easily in the daily life? Coatings of resorcinol and tannic acid are hydrophilic, but
not soluble in water because of the high cross-linking.
slightly beige, shiny coating during the polymerisation. However, the From a chemical point of view, recipe adjustments are necessary: The
coating based on tannic acid is inconsistent and thicker at the edge. main focus is on the exchange of hydrogen peroxide with a less ag-
Currently, the worst nail polish is formed by dealkaline lignin (Figure gressive mediator. A natural and sustainable origin should also be
8c). The reason for this is probably due to the non-uniform, polyphe- ensured when extracting the raw materials. From the point of view of
nolic structure of the monomer. the user, the pigmentation of the nail polishes is desirable. These can
Future work will focus on adhesion and mechanical stability of the be natural pigments or nanoscale melanin particles.
nail polishes. Good results would be a durability of one to two weeks.
REFERENCES
[1] https://www.umweltbundesamt.de/themen/mikroplastik-in-kosme-
MEETING THE
REPORTING REQUIREMENT
For this reason, those who place hazardous substances on the in the EU, depending on their area of application: For products for end
market in the EU are obliged to report their exact composi- consumers, the initial deadline was 1 January 2020 - but this deadline
tion to the poison control centres or the European Chemicals was extended by one year to 1 January 2021. The same applies to
Agency ECHA. Trustees such as TÜV Süd protect manufactur- commercially used products. For industrial use, the deadline is 1 Janu-
ers’ trade secrets when transmitting sensitive data. ary 2024. By 2025, all products must be notified, including products
that were previously on the market under national laws.
N ot only end users come into contact with paints and varnishes,
but these mixed products are also used in trade and industry.
The hazard potential ranges from physical hazards (e.g. fire hazard) to
KNOW-HOW
health hazards (acute and chronic poisoning) and environmental haz- Classification and labelling of products is not a simple matter. On the
ards (poisoning of water bodies). In medical emergencies, poison con- one hand, consumers have difficulty understanding the information
trol centres or ECHA offer advice by telephone: they provide informa- on product labels and, on the other hand, companies often do not
tion on necessary measures such as detoxification, examinations and know exactly how to label chemicals and classify their hazards. The
further steps. To ensure that doctors and experts from a wide range Federal Institute for Occupational Safety and Health (BAuA) in Germa-
of fields can provide this information, manufacturers and importers ny provides information on this. Detailed information and instructions
must classify and label the dangers arising before placing dangerous can also be found on the pages of the ECHA poison control centres.
products on the market in the EU and provide information on their Before hazardous substances are reported, however, they must first
chemical composition and toxicological properties. meet the requirements of the REACH Regulation. This further chemi-
In the past, there were no uniform rules for notifying poison control cals regulation primarily serves to protect human health and minimise
centres about chemical products. Now the EU has standardised the environmental risks.
notification to poison control centers with an amendment to the CLP Notifications to poison control centres are only made electronically
regulation (Classification, Labelling and Packaging). There are stag- via the harmonised PCN format (Poison Centre Notification) - in ac-
gered notification deadlines for those placing products on the market cordance with the CLP Regulation. Among other things, this format
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
LE G I SLAT IO N 31
“The advantage of a
UFI is that it ensures
WHEN AN EMERGENCY OCCURS data protection.“
In the German-speaking countries there are many names for
poison control centres. In Germany and Austria, for example,
“Giftnotruf”, “Vergiftunginformationszentrale” and “Giftinfor-
mationszentrum” are common, while in Switzerland a poison TRUSTEES PROTECT SENSITIVE PRODUCT DATA
emergency call is made to “Tox Info Suisse”.
Anyone wishing to place mixtures from manufacturers outside the EU
For poison emergency calls in Austria and Switzerland there is a on the EU market needs information on the chemical composition. As
single telephone number. Unfortunately, this is not yet the case there is no obligation to report outside the EU under the CLP Regula-
in Germany. At least you can reach most of the emergency call tion, manufacturers are usually reluctant to disclose their trade se-
centres with the respective area code under the number 19240. crets for reasons of business strategy. A trustee can be appointed to
counteract this problem. A manufacturer outside the EU entrusts the
Further information on the national helpdesks and emergency data to a trustee, who passes them on to the poison control centres
telephone numbers in all EU countries is available online from of all EU member states. In this way, business relationships can be
ECHA: https://poisoncentres.echa.europa.eu/appointed-bodies maintained without neglecting reporting obligations.
Trustees must treat all data with absolute confidentiality and must
never pass it on for their own purposes. This also includes keeping
data secure. Furthermore, trustees must be competent in the field of
chemistry as well as in the field of chemicals legislation. In order for
trustees to fulfil the task of notifying poison control centres of prod-
ensures that discrepancies between EU member states and the Euro- ucts to be imported, they must have the necessary computer skills to
pean Economic Area are reduced. Based on defined criteria, compa- handle the software instruments. Furthermore, reliability means that
nies determine hazardous properties of chemical products and assign trustees carry out their task with the utmost care and attention.
them to hazard categories. A European Product Categorisation Sys-
tem (EuPCS) has been established for this purpose. For classification, SENSE AND PURPOSE
companies can refer to the ECHA’s Classification and Labelling Inven-
tory (C&L Inventory) and consult already harmonised classifications of A uniform product notification system for hazardous mixtures in
substances or carry out a self-assessment of the expected hazards. Europe ensures that chemicals legislation is harmonised. A further
If substances are assigned to at least one hazard category, they are advantage is that all poison emergency call centres in the EU can be
considered hazardous and must be notified. Labelling is done using notified with a central notification. In medical emergencies, poison
standardised elements such as hazard statements, safety instructions control centres can also provide qualified assistance. At the same
and contact information. In addition, marketers must create a UFI time, companies protect their business secrets.
code (Unique Formula Identifier) and affix it to the product label. Trustees such as TÜV Süd help with questions relating to the noti-
fication obligation or the translation of the PCN into the respective
CONFIDENTIALITY AND TARGETED ASSISTANCE national language.
As customer requirements become more and more individual, REQUIREMENTS FOR PIGMENT PREPARATIONS
it is essential that products are developed specifically for each
customer and produced in ever smaller batch sizes. Modular Both do-it-yourself and industrial applications use water-borne pig-
production allows pigment concentrates to be adapted to reg- ment pastes to tint paints, coatings, plasters and glazes. This pro-
ulatory and technical requirements duction principle, which can be outsourced to the dealer, presents
the manufacturers of pigment preparations and base coats with nu-
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
P I G MEN T C O NCEN T R AT E S 33
Figure 1: Left: homogenised using a spatula; centre: 1,5 min; sible incorporation with commercially available mixers is required,
right: 3 min shaker. while at the same time being gentle on the material. Figure 1 shows
the effect of the wetting and dispersing agents migrating from the
color paste to the filler of the basecoat. Using dispersing additives,
the incorporation times and the required shear forces can be op-
timised.
While black, green and blue pigments absorb a wide range of visible
light, red, orange and especially yellow pigments only cover a nar-
row range. The resulting low hiding power of yellow and orange pig-
ments becomes a challenge when mixing brilliant full shades: Even
Figure 2: Green shade after weathering. Combination of pigments P.Y.3 / P.B.28 (right) and P.B.28 / P.Y.184 / P.Y.42 (left).
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
P I G MEN T C O NCEN T R AT E S 35
with maximum pigmentation levels, additional layers of paint often Table 1: Hiding power of various pigments: dE* on b/w-contrast
have to be applied to achieve sufficient coverage of the substrate. charts (2K-Acrylic, 5 % pigment conc., 500 µm NSD) [6].
For coatings with high hiding power, mostly inorganic pigments are COVERAGE OF THE COLOUR SPACE
used, although some organic pigments also achieve reasonable hid-
ing power. Table 1 shows the results for the same concentrations 60 % of all tinting pastes used in the European PoS market are
of solid pigments in the liquid paint. However, inorganic pigments based on eleven Color Indices (C.I.). The remaining 40 % of the tint-
usually have lower oil numbers and can therefore be used in pig- ing pastes are based on more than 100 different C.I. The goal for a
ment preparations in significantly higher concentrations. In order to tinting system is to achieve a maximum number of colour shades
compare the performance of organic and inorganic pigment pastes with as few pigment pastes as possible. For this purpose, as shown
in practice, we therefore measured the hiding power at 5 and 15 % in Figure 3, pigments are analysed together with brilliant RAL shades
paste addition to the liquid coating (Table 2). in the yellow-orange range of the colour space. The sufficiently high
chromas of the pigments P.Y.184, P.Y.74, P.Y.154 allow the brilliant areas of application thus lead to a large number of possible paste
RAL-colours to be realised [5]. combinations, the selection of which is individually optimised ac-
cording to technical and economic specifications.
REQUIREMENTS FOR TINTING SYSTEMS
ECONOMY OF TINTING SYSTEMS
The requirements in terms of economy, but also in terms of the
number of achievable colour shades, colour deviations, metamer- It is misleading to judge the economic efficiency of tinting systems
ism, opacity and light and weather fastness can vary greatly. only by comparing the costs of the pastes or even the pigments used.
A paste system that is suitable for the façade primarily requires Taking into account the parameters colour strength, hiding power
weather-resistant pastes. On the other hand, a system for interior and the total amounts of the individual pastes actually consumed
use will require more colourful organic pastes that are less expen- during tinting can lead to surprising results. Supposedly expensive
sive. Lime or silicate paints have special requirements. The different pigments can become practicable alternatives that generate compet-
itive advantages through their added value. A system with expensive
pigments can ultimately be cheaper if it offers advantages such as
Table 2: Hiding power (acc. DIN 55 987) of various pigment lower complexity, higher hiding power and higher UV stability.
preparations for 5 % and 15 % addition on paint (dE* on With brilliant shades in the yellow-orange-red range, the maximum
b/w-contrast charts; 2K-acrylic, 250 μm wet layer thickness). amounts of paste added are often not sufficient to ensure adequate
hiding of the substrate. Due to the resulting strong viscosity de-
Pigment Pigment Oil no. dE* dE*
%
paste C.I. type [ml/100g] (15%) (5%)
Table 3: Comparison of a tinting system with three alternatives
and their effects on the number of feasible of colour shades, UV-
P.Y.74 tr. Monoazo 40 45 17 34
stability and costs.
Pigment paste
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
P IG MENT C ONCE NTRATE S 37
COLOURISTIC PERFORMANCE
100
P.Y. 74
P.Y. 139 P.Y. 154 P.Y. 184
90
P.Y. 151
P.Y. 83
80
RAL1023
RAL1003
C*
70
P.Br.24
60
P.Y.53
50
40
50 60 70 80 90 100
h°
For which areas of application are they particularly suitable? So far we have developed wa-
ter-based and universal tinting systems that allow the problem-free tinting of solvent-based alkyd
paints up to silicate plasters. These paste systems are suitable for use in paint dosing systems at the
point-of-sales as well as for in-plant-tinting.
You mentioned the optimal particle size for effective scattering of visible light. What does
this look like for pigments in the yellow-orange range? To estimate the optimal particle size
for light scattering, half the wavelength can be divided by the difference in the refractive indices of the
pigment and binder. Since the difference in the refractive indices of organic and inorganic pigments
is very different, the optimal particle size for light scattering is 0.2-0.4 µm.
ACKNOWLEDGEMENT
E U R O P E AN CO AT I NGS J O UR N AL 09 – 2020
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THE SCIENCE OF DEFORMATION
AND FLOW BEHAVIOUR
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