The EC Dossier Additives! PDF

European
C OATINGS
www.european-coatings.com dossier 2016
Additives
The best technical papers on additives for
coatings published in the European Coatings
Journal within the past three years.
Presented by
12 Dispersants 96 Fluorosurfactants
Core/shell structures with encapsulated aminic Combining good eco toxicological behaviour
pigment-affine groups with technical performance
2 e d i t or ial
Join our Group

“European Coatings Industry”
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Tiny amount, huge effect!
Additives are indispensable ingredients of each and every formulation. They

are used in tiny amounts to help modify the performance spectrum of coat-
ings systems. Development work on additives never ceases and there are
countless products on the market.. As a formulator, you are continually called
on to be au fait with the latest advances in research and development.. Such
knowledge is rarely to be found in a single package. European Coatings Jour-
nal is about to change that. This thematic dossier is bursting with information
Dr. Sonja Schulte
Editor-in-Chief on additives that we have compiled for you. In it you will find all the relevant
T +49 511 9910-216 technical papers on additives that have been published in European Coatings
sonja.schulte@vincentz.net
Journal over the last three years. Now there’s a welcome development! 
e u r op e a n co at i ngs J OURNA L 2016

p o r t rai t 3
BYK ADDITIVEs: BYK Additives & Instruments is one of the world’s leading suppliers
in the field of additives and measuring instruments.
Improving product characteristics Additives are chemical substances which, when used in small
quantities, improve product properties such as scratch resistance or
and production processes. surface gloss. Manufacturing processes are also optimized by the
Small quantities, big properties. addition of additives.
The coatings, inks and plastics industries are among the main
consumers
of BYK additives. Yet with exploration technology
oil/gas, the manufacture of care products, the production of adhe-
sives and sealants, and construction chemistry, too, BYK additives
improve the product characteristics and production processes.
Testing and measuring instruments from BYK can effectively evalu-

ate the quality of color, gloss and appearance as well as the physi-
cal properties of paint, plastic and paper products and are an impor-
tant part of quality control.
As a globally operating specialty chemicals company, BYK has

production sites in Wesel, Kempen, Moosburg, Schkopau and
Geretsried (Germany), Deventer and Denekamp (Netherlands),

Widnes (UK), Wallingford, Chester, Gonzales, Louisville (USA) and
Tongling (China).
Today the company employs around 2,000 people worldwide and

forms part of the ALTANA Group.
BYK-Chemie GmbH · Abelstrasse 45 · 46483 Wesel · Germany

Telephone +49 281 670-0 · Fax +49 281 65735
Info@byk.com · www.byk.com
e u r op e an coat i n gs J OURNA L 2016

4 contents
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Source: Evonik
Dispersants
Maximizing
Dispersion
stability
12
Claude Beaubien - Fotolia.com
Corrosion
protection
New dispersing addi-
tives help to protect
aqueous coatings
against corrosion.
Surfactants
20 32
New superwetting additives solve
adhesion problems in waterborne
coatings
European Coatings Journal 2016
6 Dispersants 32 Surfactants
Designed for selective adsorption New superwetting additives
By A. Rudolfi, M. Krohen, solve adhesion problems
F. Piestert and S. Mößmer, Byk-Chemie By R. Reinartz, J. M. Snyder and Y. Dai, Air Products
12 Dispersants 38 Nanotechnology
Maximizing dispersion stability Nano-additive for toughening water-borne elasto-
By V. Kilpeläinen, a. Gutierrez, S. v.d. Loon, VLCI meric roof coatings
By D. Burgard and M.Herold, Bühler Partec GmbH
16 Corrosion protection
How dispersants affect corrosion resistance 42 Nanotechnology
By M.Muth, A. Freytag and M. Conrad, Byk-Chemie Addition of nanoparticles can enhance performance
of water-borne coatings
20 Corrosion Protection By D. Burgard and M. Herold, Bühler Partec GmbH
Dispersants help to protect aqueous coatings
46 Smart Coatings
By Ph. Favresse, F.Kleinsteinberg,
Permanent hydrophobic and easy-to-clean effects
K. Roland and P. Glöckner, Evonik Industries
By C. Dechamps, L. Bermert, H.Gibbs and M. Gro-
24 Waterborne Coatings teklaes, OMG Borcher and Univeristy of Applied
New dispersant provides enhanced stabilisation Sciences Krefeld
By S. Onclin, H. Frommelius, 50 Crosslinkers
P. Gómez, E. Martinez and S.Shah, BASF The best of two worlds
28 High Solids By T. Unkelhäußer, M.Mallack, H. Görlitzer and R.
Additive optimises bot colour stability and visosity Lomölder, Evonik Industries
By K. Schulz, Evonik Industries

c on t e n t s 5
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Source: Scanrail - Fotolia.com

Crosslinkers
Silane-urethane
hybrid crosslink-
ers create
scratch-resistant
clearcoats
50
Source: Yvonne Prancl - Fotolia.com
Hardeners
Getting on Emulsifier
with acrylics Getting more with less
72 86
56 Hardener 80 Emulsifier
Water-borne hardener for zero New chemistry
VOC self-leveling floors. By C. F. Palmer, Jr., Ethox Chemicals
By S. Liu and T. Trivedi, Incorez
86 Rheology Modifier
60 Levelling Agent New bio-based rheology additive
Hydrophilic agent enhances levelling for low-temperature process
and intercoat adhesion By G. Fauquet and Y. Trang, Arkema
By M.Bessel, G. Jaunky and M. Heekeren,
Byk-Chemie 90 Radiation Curing
Novel approaches to gloss reduction
66 Slip Additives
By B. Tiede, Lubrizol
Performance of structually different
slip agents compared
96 Surfactant
By C. Cocucera, K. Quackenbush and O. Arseven,
Fluorosurfactant flourish
Dow Corning Europe
By R. Friedrich, E. Höner and F. Schooren,
72 Hardeners Merck KGaA
Getting on with acrylics
100 Driers
By M. Ursai, S.A.P.I.C.I. Spa
Encapsulated driers minimise
skinning of air-drying paints
76 Crosslinkers
By J. Horakh, H. Gibbs, F. Gol and G. Kiepe,
Bio building blocks
OMG Borchers
By P. Engel, Evonik Industries

6 D i s p e r s ant s
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Designed for
selective adsorption
Dispersants based on core/shell structures stabilize pigments in reactive systems
By Astrid Rudolfi, Marcel Krohnen, Frederik Piestert and Stefan Mößmer
Dispersing additives with a hyperbranched core/shell struc- based on a primary resin and a crosslinking resin (usually melamine
ture have been developed with encapsulated aminic pigment- or phenolic resins), which crosslink at higher temperatures with an
affinitive groups. These can be used in solvent-borne and acidic catalyst [2].
solvent-free coating systems. They provide highly effective
stabilisation of various types of pigment while avoiding any The nature of pigment dispersants
undesirable interactions with reactive coating systems.
Polymeric dispersing additives are now widely used in order to meet
T he property profile and the associated fields of application of a

coating material are essentially determined by the resin that is
used. The origins of these resins are diverse and can basically be di-
the demand for high-quality visual properties such as high transpar-
ency or hiding power, to ensure that colours have long-term shade
stability with enhanced gloss and minimum haze, and to meet the
vided into natural substances, modified natural substances and syn- mechanical and chemical requirements in pigmented reactive coating
thetics [1]. materials. These amphiphilic surface-active additives use either steric
In modern coating systems, synthetically produced oligomeric sub- or electrostatic hindrance to stabilise the pigments and fillers that
stances used as resins play a primary role in satisfying the consider- have been used in the coating material [3].
able mechanical requirements and providing the necessary chemical Generally speaking, all dispersing additives are composed of low-
and physical resistance of high-performance coating materials. Reac- molecular to high-molecular weight chain segments that have a sta-
tive multicomponent resins, which crosslink through chemical reac- bilising effect, combined with at least one pigment-affinitive anchor-
tions, are of special importance. ing group. The interactions with the pigments enable the additive to
These include, in particular, the classic two-component systems (2- be adsorbed onto the pigment surface by means of these anchoring
pack epoxy and 2-pack polyurethane systems), which crosslink by a groups. This is the prerequisite for effective and long-lasting stabilisa-
polyaddition reaction at room temperature, as well as stoving systems tion of a pigment.

Di sp e r s an t s 7
undesirable side-effects, leading to adverse effects on the property

profile of the formulated systems. Table 1 provides an overview of the
possible interactions between the aminic additives and various reac-
tive coating systems.
Results at a glance
Three structurally different additives compared
űű Hyperbranched core/shell structures with aminic pigment- This application technology study compares innovative aminic dispers-
affinitive anchoring groups were used as the basis for new dis- ing additives based on the hyperbranched core/shell structures shown
persing additives for solvent-borne and solvent-free reactive in Figure 1 with established structural types to investigate whether a high
systems. degree of pigment stabilisation can be achieved in representative reactive
systems, while at the same time preventing possible interactions between
űű The specially designed hyperbranched core/shell structure the coating system and the additive.
can prevent undesirable interactions between reactive coating Three structure types were compared in this study. In each case, these
systems and the additive. possess both aminic pigment-affinitive groups of a similar chemical
nature and basicity as well as polymeric side chains of a similar polar-
űű Practical tests confirmed that the use of this type of addi- ity. As shown in Figure 2, these structure types differ in terms of their
tive gave effective viscosity reduction and improved stability on basic skeleton:
storage in both epoxy and 2-pack polyurethane systems. ąą Structure type 1: linear copolymer with freely accessible aminic
anchoring groups;
űű Tests in a stoving system showed that the new structure ąą Structure type 2: branched polymer with sterically shielded aminic
performed well, whereas a linear copolymer dispersant ap- anchoring groups;
peared to interfere with the curing mechanism. ąą Structure type 3: core/shell polymer with sterically encapsulated
aminic core. 
Figure 2: Comparison of structural types of dispersants tested
As most pigments used in coating applications carry an acidic surface

treatment, dispersing additives with aminic pigment-affinitive groups, in
particular, are considered to be very effective additive structures because
they can undergo stable acid/base interactions with the pigment surface.
These aminic dispersing additives significantly improve pigment sta-
bilisation; however, in various reactive systems they can cause some
Figure 1: Schematic representation of dispersing

additives based on hyperbranched core/shell structures

 Three different coating chemistries studied sessing the transparency, colour strength and colour shift under both
transmitted and incident lighting conditions.
These three differently structured dispersing additives were first used In addition to this, measurements were made with respect to the in-
to produce solvent-borne pigment concentrates based on a universal fluence of the different structure types on the undesirable interac-
grinding resin and different pigments (Colour Index references P.R. tions (listed in Table 1) with each coating system. In the case of the
122; P.R.170; P.G.7; P.B.15:4, and P.Bl.7, fine-sized). The same pigment 2-pack epoxy system, the pigmented base coating (epoxy component)
concentrates without the dispersing additive served as a reference. was stored for twelve weeks at 50 °C (122 °F) and the flow time was
After 24 hours, the viscosity of the individual pigment concentrates measured at regular intervals.
was measured (cone/plate geometry, cone diameter = 25 mm, angle = For the pigmented 2-pack polyurethane system, the resulting flow
1 °, temperature = 23 °C (73 °F), shear rate = 1 s-1). times were measured during the curing reaction between the acrylate
In a second step, these pigment concentrates were used in differ- and the aliphatic-aromatic and/or pure aliphatic polyisocyanate cur-
ent solvent-borne reactive coating systems. A 2-pack epoxy sys- ing agent. In the case of the acid-catalysed stoving systems, the influ-
tem (bisphenol A/polyamide curing agent), a 2-pack polyurethane ence of the various structure types on the mechanical properties was
system (OH-functionalised acrylate with aliphatic-aromatic and/or determined by the König pendulum hardness test (in accordance with
pure aliphatic polyisocyanate), and an acid-catalysed stoving system DIN EN ISO 1522).
(acrylate/melamine) served as let-down systems.
The test systems formulated in this manner were poured onto a Poly- Two dispersants effectively reduce viscosity
ester foil which was fixed at a 65 ° angle. The qualities of the pigment
stabilisation in terms of optical properties were then established by The reduction of the millbase viscosity by the different dispersing ad-
measuring the gloss (at a 20 ° angle) and haze, and by visually as- ditives gives a rough indication of their efficiency. As shown in Fig-
Figure 4: Influence of the different structure types on the gloss

Figure 3: Influence of the various structural types of dispersant of the pigmented 2-pack polyurethane system (OH-functional-
on the viscosity of the pigment concentrates ised acrylate/pure aliphatic polyisocyanate)
Figure 5: Influence of the different structure types on the Figure 6: Influence of the structure types on the storage stability
transparency of the pigmented 2-pack polyurethane system of the epoxy base component
(OH-functionalised acrylate/pure aliphatic polyisocyanate),
here using P.G. 7

Di sp e r s an t s 9
ure 3, when compared with the reference, all three structural types on the hyperbranched core/shell structure (type 3 structure) gave the
significantly reduced the viscosity, regardless of which pigment was best results. For all pigments tested, these two structural types pro-
dispersed. duced a significant increase in gloss compared with the reference.
Structure types 2 and 3 in particular showed a significant reduction in Structural type 1 also tended to significantly improve the gloss; how-
the paste viscosities, for which structure type 2 was especially good ever, this did not always occur, particularly for stabilisation of P.R.170
with P.R.122, P.R.170 and P.G.7, whereas structure type 3 gave the and P.B.15:4.
best results with P.R.170, P.B.15:4 and P.Bl.7. For all pigments tested, This trend in results is also evident in the transparency of the pigment-
these two structure types gave higher efficiency than structure type ed coating systems. For example, in the 2-pack polyurethane system
1 – quite considerably in some cases. coloured with the pigment concentrate based on P.G. 7, structure
types 2 and 3 produced an outstanding transparency in conjunction
Gloss and transparency differences are considerable with a bluish/greenish colour shade (Figure 5), which is yet another
indicator of very effective pigment stabilisation. In this case, structure
In addition to the viscosity reduction of the pigment concentrates, the type 1 with a more yellowish/greenish colour shade did not match the
three structural types were also tested in terms of their influence on good results of the other two dispersing additives.
the visual properties of the selected coating systems. Figure 4 shows The results shown for the example of the 2-pack polyurethane system
the influence of the three structural types on the gloss of the 2-pack were also confirmed in the tests with the 2-pack epoxy and the acid-
polyurethane system based on the pure aliphatic polyisocyanate cur- catalysed stoving system. They can therefore be considered essentially
ing agent. representative for the performance specification of the three different
In this case again, both the branched polymer with sterically shielded structure types.
aminic anchoring groups (type 2 structure) and the additive based
How structure correlates to viscosity stability
Table 1: Possible interactions bet ween the coating Figure 6 provides an even clearer picture of the influence of the three
system and the aminic dispersing additive types of structure on the storage stability of the epoxy base component.
After just a few days, the epoxy base component containing the addi-
System Component Component Possible system/ Effect on coating tive with structure type 1, which has freely accessible aminic anchoring
reference A B additive interactions properties groups, showed a drastically increased flow time, finally resulting in a
gelling of the system.
1 Epoxy Poly(amido) Interaction with Major effect on Structure type 2, which has sterically shielded aminic anchoring
amine epoxy part storage stability groups, had no medium-term influence on the storage stability of the
epoxy base component. However, the viscosity did start to increase
2 Polyol
Polyisocy-
Catalysis of curing Shorter pot-life after a storage period of six weeks.
anate Only structure type 3, which has an encapsulated core, showed no
3 Alkyd Oxygen Complexation of Longer drying viscosity increase across the entire storage period of twelve weeks.
metallic dryers time Indeed, it provided the same storage stability as the system that did
not contain any wetting and dispersing additives.
4.1 Acrylate/ Acid Partial catalyst Incomplete In the case of the 2-pack polyurethane system, the influence of the
melamine catalyst deactivation curing reaction
structures on the pot-life (period of time until the initial viscosity has
4.2 Polyester/ Acid Partial catalyst Incomplete doubled after the two components have been mixed) the results were
melamine catalyst deactivation curing reaction more variable, depending on the curing agent that was used.
As shown in Figure 7, none of the additives shortened the pot-life of 
Figure 7: Influence of the structure types on the pot-life of the 2-pack polyurethane system. Left: OH-functionalised acrylate +
aliphatic-aromatic polyisocyanate. Right: OH-functionalised acrylate + pure aiphatic polyisocyanate

 the pure aliphatic polyisocyanate. However, compared to a system surfaces, and the minimised interactions with reactive coating sys-
with no additives and in the case of the reactive aliphatic-aromatic tems are attributed to the hyperbranched core/shell structure.
curing agent, the pot-life was considerably shortened with structure The prevailing mechanical shear forces in the pigment grinding pro-
type 1 and at least slightly shortened with structure type 2. cess deform the flexible polymer shell of the dispersing additive,
Structure type 3 did not shorten the pot life. This different behaviour which makes the pigment-affinitive core temporarily accessible, allow-
can be attributed to the exposed aminic functionalities in structure ing it to be adsorbed on the pigment surface. After the pigment has
type 1 that catalyse the formation of polyurethane and thus shorten been ground, the polymer shell returns to its original state, thus re-
the pot life. shielding the aminic core that was temporarily accessible to the sur-
rounding liquid matrix during the grinding procedure (Figure 9). This
Stoving system shows ‘ differences in hardness then prevents any undesirable interactions.
Effective pigment stabilisation in solvent-borne and solvent-free re-
The differing influence of the various structure types on system prop- active coating systems imposes great demands on the dispersing
erties was also confirmed by the mechanical tests on the acid-cat- additives used. The aminic pigment-affinitive groups required for
alysed stoving system (Figure 8). Structure types 2 and 3 showed a sustained adsorption on pigment surfaces can cause undesirable in-
damping of the pendulum swing comparable to that of the reference teractions with these reactive systems.
system with no additives. Innovative dispersing additives based on hyperbranched core/shell
Because of the significant differences in results during testing of the structures can thus provide very effective stabilisation of the different
mechanical properties, it is assumed that structure type 1 led to in- pigment types without causing any undesirable interactions with the
complete curing of the system - an assumption based on the interac- reactive coating systems. This structure shows superior performance
tion of the acid catalyst with the freely accessible aminic functionali- overall to established linear copolymers with freely accessible aminic
ties in this molecular structure. anchoring groups as well as to polymers with sterically hindered amin-
ic anchoring groups.
How the hyperbranched
core/shell structures function REFERENCES
The selective interaction of the aminic pigment-affinitive core of struc- [1] Brock Th., Groteklaes M., Mischke P., Lehrbuch der Lacktechnologie, 2nd
ture type 3, characterised by efficient adsorption on various pigment edition, 1998, Vincentz Verlag, Hannover, p 16.
[2] As Ref. 1, p 71.
[3] Bielemann J., Lackadditive, 1998, Wiley-VCH Verlag GmbH, Weinheim, p
Figure 8: Influence of the structure types on pendulum hardness 87.
of the acid-catalysed stoving system
Figure 9: Schematic representation of the working mechanism

of the hyperbranched core/shell structures
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Source: Woszczak - Fotolia.com
Maximising
dispersion stability
High throughput testing optimises additive selection. By Veli Kilpeläinen, Alejandro Gutierrez, Sander van Loon, VLCI.
and Sam Peel.
Optimising the choice and addition rate of a pigment dis- Figure 1: Over view of the HT system
persant can be difficult and time-consuming. A method has
been developed to achieve this by using also high throughput
screening. This is used to establish the Hansen solubility pa-
rameters and optimum addition rates of dispersants. Those
with solubility parameters closest to that of the pigment can
be expected to perform best.
S electing a suitable dispersant for a filler or a pigment (solid parti-

cle) is not an easy task, when one has to take into account:
ąą The variety and amount of dispersants available.
ąą The surface modification and/or the nature of the particle, both of
which can vary greatly.
An effective dispersant performs the role of a protective buffer – with one
portion specifically attracted to the particle (e.g. a hydrophobic tail adher-
ing to the surface of the particle) and another portion specifically attracted
to the solvent medium (e.g. a hydrophilic head for water compatibility).
To match the dispersant with the particle in order to develop a stable
dispersion in the solvent, much needs to be known about the nature
of the dispersant, the particle and the solvent.

Di sp er s an t s 13
significantly different parameters.

The net difference between the parameters of two materials can be
quantified using the HSP distance, which is given by the following
Results at a glance equation, based on the three parameters mentioned above:
űű The selection of the optimum dispersant for a pigment or Dist = √((4(δD1 – δD2)2)+(δP1 – δP2)2 +(δH1 – δH2)2) Equation 1
extender and the optimum addition rate can be a difficult and
time-consuming task. Thus, the smaller the HSP distance between two materials, the more likely
it is that the two will be favourably associated. Ultimately it is possible to
űű A composite method has been developed which provides determine a solubility sphere or solubility radius: if this is determined for a
an efficient route to achieving this; HSP, ODC and highthrough- resin, then a solvent (or mixture) whose parameters fall within this radius
put formulation. will dissolve it, while those with further distant will not.
Initially this concept was applied to determine the most suitable solvent
űű The optimized process consists of first establishing the Han- or blend of solvents to dissolve polymers; but subsequently it has been
sen Solubility Parameters (HSP) of a particle, select dispersants developed to allow the calculation of ‘solubility parameters’ for insoluble
based on HSP and then obtain the optimum dispersant con- materials such as pigments and substrates. Applying this concept to in-
centration. teractions between dispersants and particles, once the HSPs of these
match, a stable dispersion can be formed.
űű Those dispersants whose solubility parameters are closest In this work, the HSP method was verified by the Optimal Dispersant
to that of the pigment can be expected to give the best perfor- Content (ODC) method [2], a classical method to determine the right
mance. dispersant in a trial-and-error manner. These methods will be de-
scribed and compared in this article to provide the selection of the
űű This procedure was applied to find the best dispersants for best water-based dispersant to disperse the hydrophobic talc prod-
a hydrophobic talc in waterborne systems. uct “Finntalc M15” in a water-based coating.
High throughput formulation simplifies selection
“Finntalc M15” and a broad selection of dispersants with different chem-

istries were studied in relation to HSP and ODC. In order to speed up the
process and make it more precise, samples were produced via the “For-
max” High Throughput (HT) equipment from Chemspeed technologies.
Solubility parameters provide the key to analysis A sedimentation time method in different solvents with different HSPs
was used to establish the HSPs of the talc product. Fast sedimentation
The information needed can be obtained by using the Hansen Solubil- means no compatibility with the solvents and slower sedimentation
ity Parameter (HSP) of the products, with sample preparation via high means better to good solvents. Good solvents are rated as 1, bad
throughput screening. Hansen solubility parameters (HSPs) are used solvents as 6 and the rest are in between. Based on this rating, a dis-
to define the attractive forces Hydrogen bonding, Polar forces and tinction can be made in the HSP space.
Dispersion forces[1] within solvents or solvent blends, or to map the The HSP can then be calculated via the dedicated “HSPiP” software
interactions of those with other materials. (version 4.0.05, www.hansensolubility.com), by introducing this rating.
By the principle of like-seeks-like, solvents and solutes with similar solubil- All ratings are relative for each of the products.
ity parameters are more likely to form stable solutions than those with For the surfactants, the normal HSP method was applied, meaning 
Figure 2: ODC analysis for the talc Figure 3: HSP data for the talc

 solvents were rated for good and bad solubility, again with rankings sis whilst processing, which is a unique feature.
between 1 and 6. Samples of the products with the different solvents On the HT platform, different processing methods can be operated,
are made via the HT system, as it requires quite a large amount of including mixing by horizontal shaking of glass tubes in a rack and
samples for each product. dispersing with a Cowles dissolver disc in a temperature-controlled
reactor.
Optimising the dispersant concentration In this HT system, the raw materials are thus brought to the glass
tubes and reactors, in order to not disturb the processing, as re-
An effective dispersant for waterbased applications performs the role of a quired to make proper formulations. For this project, the HT system
protective buffer – with its hydrophobic ‘tail’ adhering to the surface of the prepared the dispersions of talc in water via the HT reactors and the
particle and its hydrophilic ‘head’ associating favourably with the solvent HSP and ODC samples in glass tubes present in the HT stirring rack.
medium. Figure 1 provides an overview of the HT system used.
In addition to ionic repulsions between the particles, the dispersant-
rich region that forms whenever two particles happen to come close How optimum dispersant concentration is determined
together is subject to osmotic pressure from the surrounding solvent,
which tends to force the particles apart again. In a first step, the ODC analysis on the talc paste was performed with
As a dispersant is introduced into a pigment dispersion, there is a dra- respect to a selection of waterbased dispersants. The method for
matic reduction in the viscosity of the paste or slurry, as the particles each dispersant was to prepare tubes containing 30 % of talc in dis-
become more mobile in the solvent. The extent of the viscosity reduc- tilled water, which was then thoroughly mixed to a paste. The viscosity
tion is dependent on the amount of dispersant added. of the paste was then recorded.
However, the amount must often be minimised in order to reduce
costs or to prevent other harmful effects which might arise from us-
ing high proportions. If the amount of dispersant used is too small,
the full benefits will not be obtained. Clearly, for each system studied Table 1: Summary of ODC results obtained
there is an optimum dispersant concentration (ODC).
Many factors affect the ODC, including the chemistries of the dis-
Viscosity reduction
persant, solvent and pigment, and especially the surface area of the Dispersant Performance ODC (wt%)
(%)
pigment to be tested. The ODC is the concentration of dispersant at
which a plateau is reached in the pigment/solvent viscosity curve and “BYK 154” -- 5.0 % 26 %
this can be tested in order to adjust the final formulation. This experi- “Disperbyk 190” + 7.0 % 70 %
ment can be performed easily with HT screening on a wide range of
“Schwego Fluor 6536” -- 9.0 % 30 %
pigments and dispersants.
“Efka 4580” ++ 5.0 % 85 %
Principles of high throughput screening “Anti-Terra 250” ++ 4.5 % 87 %
“BYK 348” ++ 1.5 % 83 %
High Throughput (HT) is a valuable tool to automatically prepare for-
“Silco Sperse HLD-5” + 4.5 % 75 %
mulations in parallel with high precision. In order to be flexible in
various formulation preparations as in this project, an HT system was “Lopon 895” - 9.9 % 42 %
used that can add liquids, viscous and solid materials on a weight ba-
Figure 4: The concept of HSP distance including radii Figure 5: HSP plot for talc and dispersants

Di sp er s an t s 15
After the viscosity had been measured, a small amount of a dispersant far away. In this case, “Silco Sperse HLD-5” is very far away from the
was weighed into the tube, which was then thoroughly mixed. Again the HSP of talc, but is much closer to that of water than the other disper-
viscosity was measured and this process was repeated over and over sants. This might be one reason why this product is a good dispersant
until the viscosity values had plateaued, and then a little further. for water-based systems and therefore shows a good result from the
The viscosity of the paste with every dispersant and its concentration can ODC study.
be seen in Figure 2. The results of this ODC study are shown in Table 1. The
profiles of the dispersants showed some interesting characteristics: the HSP and ODC results combined
best of the dispersants displayed clear and large reductions in viscosity
that remained even at low dispersant concentrations. As shown, both the HSP and ODC study result in the same selection of
These ‘step-changes’ in viscosity varied in their slopes and in the mass- good and bad dispersants for the talc. As a couple of dispersant HSPs are
efficiency of each dispersant, but they all showed approximately the same now known, next time it is a matter of measuring the HSP of a particle
relative viscosity changes of around 80 % reduction relative to the origi- and plotting the dispersants in HSP space to see if there is a match or
nal talc-water paste. The dispersants which showed this behaviour most not.
clearly were “BYK 348” “Anti-terra 250” and “EFKA 4580”. Besides these, The best dispersants can then be selected and tested via ODC in or-
“Silco Sperse HLD-5” can also be considered good, but slightly less so than der to obtain the right amount of the dispersant for the particle. HSP
the others mentioned above. can reveal the best matching dispersant, so this one should have in
principle the best interaction, thus the lowest amount required with
Sedimentation tests to measure HSP values the highest viscosity reduction, but the ODC method is needed to ob-
tain the data.
Because talc does not show solubility but dispersion characteristics in The strong point of using this HSP method in the first place is that
a solvent, resulting in sedimentation, the sedimentation time of talc in it requires less effort than performing a full dispersant study for a
the different solvents with known HSPs was measured. The rating of particle via ODC.
each solvent was entered in the software, resulting in the HSP data and
solubility sphere for the talc as shown in Figure 3. An effective selection procedure in summary
In order to match the HSP of the talc with a dispersant, the HSP of
the dispersants was determined. The conventional HSP tests can also Table 3 summarises the data for Finntalc M15, obtained from ODC test
be extended to calculating the parameters of surfactants and disper- and HSP experiments, with the dispersants having the best perfor-
sants. In this case, the solubility in the different solvents is rated. mance shown first. The data collected for the ODC and the HSP study
Table 2 shows the experimental HSP parameters for the dispersants both show the same best-suited dispersants.
tested previously in the ODC studies, including the distance from the In terms of the minimisation of their addition levels and the efficiency
talc calculated in accordance with Equation 1. Although the HSP dis- of viscosity reduction obtained from ODC, low HSP distances from
tance between two materials is useful in itself, more understanding Finntalc M15 are also exhibited.
can be gained when the radii of the solubility spheres are also em- This leads to a useful method to select the right type and amount of
ployed in the analysis. dispersant to use with a solid particle:
Figure 4 describes how the HSP distance between the centres of two ąą Use the HSP method to obtain the HSP of the particle and then
spheres is related to the radii of those two solubility spheres and select dispersants with matching HSPs.
the minimum distance that separates their surfaces, taking into ac- ąą Use the ODC study with these best dispersants to obtain the optimal
count the values obtained in Equation 1. In Table 2 these separation amount of dispersant for the particle. 
distances are also given (Distsep), where of course the lower the value
the better.
This data can be depicted nicely by plotting it on a 3D grid, along with REFERENCES
the positions and radii of the sphere for the talc, as in Figure 5.
Based on the HSPs and distance data, it can be seen that the dis- [1] Abbott S., Hansen C., Yamamoto H., Hansen Solubility Parameters in Practice –
persants found to have the best performance from the ODC study software, eBook and datasets, www.hansen-solubility.com
are indeed inside the HSP sphere of the talc and the poor ones are [2] Bieleman J., in Additives for Coatings, 2000, p 65, Wiley-VCH.
Table 3: Summary of results with best dispersants shown at the

top of the listing
Table 2: HSP data for a selection of the dispersants tested
Dispersant Talc Particle-disper- ODC Viscosity
distance sant separation (wt%) reduction (%)
Dispersant dD dP dHw Radius Talc Distsep
distance “Anti-terra 250” 4.25 -7.37 4.5 % 87 %
“Byk 348” 18.1 11.48 11.14 15.6 3.65 -17.25 “Efka 4580” 6.77 -6.84 5.0 % 85 %
“BYK 154” 22.8 19.83 32.81 18.6 25.79 3.19 “BYK 348” 3.65 -17.25 1.5 % 83 %
“Disperbyk 190” 12.16 17.04 12.99 14.9 13.70 -6.60 “Silco Sperse HLD-5” 29.37 -3.10 4.5 % 75 %
“Efka 4580” 19.6 13.26 10.73 18 6.56 -6.84 “Disperbyk 190” 13.77 -6.60 7.0 % 70 %
“Silco Sperse HLD-5” 17.07 20.35 37.12 11 5.10 -3.10 “BYK 154” 17.11 3.19 5.0 % 26 %
“Anti-terra 250” 20.36 13.4 25.86 19.35 16.83 -7.37 “Lopon 895” 15.92 4.49 9.9 % 42 %
“Lopon 895” 23.08 13.23 35.62 17.75 25.59 4.49 “Schwego Fluor 6536” - 9.0 % 30 %

16 C o r r o s i on p r o te c t ion
Source: Anyka - Fotolia.com

Maintaining
protection
How dispersants affect corrosion resistance of water-
borne paints. By Martin Muth, Andreas Freytag, Max
Conrad, Byk-Chemie.
By utilising different test methods the impact of several dif- The impact of wetting and dispersing additives
ferent chemical types of wetting and dispersing agents on the
sensitivity of a waterborne primer towards water and mois- Wetting and dispersing additives are an important class of additives.
ture as well as anticorrosive properties has been evaluated. They provide three main features that are vital to produce coatings with
Clear performance differences depending on the chemistry good storage stability, application properties and optical appearance:
utilised have been found. However, the results obtained with ąą Wetting of the pigment and filler particles;
the five different evaluation methods did not correlate too ąą Dispersion of pigments and fillers;
well. This made it evident that the test procedure has to be ąą Prevention of the re-agglomeration of the primary particles.
selected according to the final requirements that have to be These aspects are almost impossible to achieve without the aid of ad-
improved. ditives due to the high surface tension of water.
Since the additive remains in the coating after drying, it may influence
I n the protective and marine coatings market, great efforts are be-
ing made to reduce the amount of volatile organic compounds
(VOCs) emitted during application. Many paint customers have been
the overall hydrophilicity of the coating film and therefore affect cer-
tain coating characteristics such as early water resistance and corro-
sion protection. To study this effect on the final coating, relevant test
switching to high-solids and solvent-free paints that combine low VOC methods must be compared.
content with the advantages of conventional paint systems.
Another option to reduce VOCs is the use of waterborne paints. Be- Mode of action and general structure of dispersants
cause of the demanding requirements and often uncontrolled applica-
tion conditions, the use of waterborne systems in the protective paint The process of the dispersion of solid particles as pigments and fillers
market is still very limited. Indeed, in this market sector, it is estimated falls into three stages: wetting of the particles, dispersion and stabili-
that globally the share of waterborne paints is around 6 %, while sol- sation. To understand the first process it is necessary to understand
ventborne, high solids and solvent-free systems retain 94 % [1]. the circumstances under which a liquid properly wets a solid. This
One key reason for this limited use is that waterborne systems restrict process is described by the Young equation:
the temperature and humidity conditions under which the paint can γs – γsl
= cos θ[1]
be applied. Low temperature and high humidity prevent proper and γl
sufficient curing of the coating. Additionally, the high surface tension Where
of water can cause problems with certain substrates or impurities and
lead to improper wetting, cratering and other paint defects. γs = surface tension of solid
Next to the application challenges, the formulation of waterborne γsl = interface tension solid/liquid
anticorrosive paints is also quite challenging. To ensure proper film γl = surface tension of liquid
formation after application, paint components must be carefully se- θ = contact angle liquid/solid
lected. To overcome some limitations, the use of additives is essential.
For complete wetting of a solid by a liquid, the contact angle becomes

C o r r o s i o n p r o t e c t io n 17
out by introducing energy to the system, for example by high-speed

dispersion with an agitator disk. The amount of energy needed to
separate the particles from each other and so increase the surface
Results at a glance area that needs to be wetted by the surrounding liquid is described
by the following equation:
űű Waterborne paints hold only a very small share of the mar-
ket for protective and marine coatings, as they have stringent dW = g · dA [3]
requirements for good surface preparation and drying condi-
tions. W: introduced work
g: interfacial tension
űű Wetting and dispersing agents play a critical role in the for- A: interfacial surface
mulation of waterborne coatings in particular. However, they Thus, the amount of work needed to generate a certain amount of
are necessarily partly hydrophilic, and this can impair the pro- surface area by breaking down the agglomerates into primary parti-
tective properties of the cured film. cles is directly linked to the specific surface tension. Wetting and dis-
persing additives reduce the work required by lowering the interfacial
űű Tests are reported on the impact of several different chemi- tension between liquid and solid.
cal types of dispersing agent on the anticorrosive properties of Stabilisation is then vital to prevent re-agglomeration of the dispersed
a styrene-acrylic based primer. particles. Two major stabilising mechanisms are utilised: electrostatic
and steric stabilisation, which may be combined. In summary, it can
űű The best results were given by two polyacrylates and a be said that wetting and dispersing additives always consist of two
polyurethane-based additive. However, a notable result is that domains, one of which interacts with the pigment surface (‘pigment
there was a poor correlation between the five different tests for affinitive group’) and one which interacts with the binder (‘binder af-
protective performance that were used. Thus, it is important to finitive group’).
ensure that the tests selected are appropriate for the planned The main currently available wetting and dispersing additives with
end-use. these characteristics are based on the following chemistries:
ąą fatty acids
ąą polyurethanes
ąą phosphoric acid esters
ąą polyacrylates
Different additives based on these chemistries were included in the
evaluations below.
0 °, which is the case when:
γl = γs – γsl [2] How dispersants affect waterborne coatings
To achieve proper wetting, the surface tension of the liquid must be
less than the surface tension of the solid [2]. Wetting and dispersing For the dispersant to be compatible with the system and able to inter-
additives directly influence the wetting process by adsorbing on the act adequately with the liquid matrix, the binder compatible groups
surface of the solids and thus changing the surface tension. need to have hydrophilic properties. These properties can be ob-
tained by using polar chemical domains, such as polyethers or polyes-
How the additives function during dispersion ters, or certain hydrophilic co-monomers.
Various wetting and dispersing additives use ionic salt structures to
In the dispersing process the agglomerates of pigments and fillers are obtain sufficient solubility of the additive or its binder-affinitive do-
broken down into so-called ‘primary particles’. This process is carried mains in the paint matrix. Alternatively, salt structures may be in- 
Figure 1: Sample of DSC result to determine water uptake and

melting peak of water Figure 2: Experimental setup for water diffusion test
Water

18 C o r r o s i on p r o te c t ion
 troduced, for example by neutralising acidic groups with bases. The To determine early water resistance, the test paint was applied to
chemical nature and volatility of the base also both influence the re- cold-rolled steel panels. Four and 24 hours after application, a cot-
sistance of the final coating to corrosion stimulants and water. ton wool ball drenched with distilled water was placed on the coating
The effect of the additives on parameters such as early water resist- then covered with a small plastic beaker to prevent the water from
ance, water uptake and corrosion resistance must be evaluated in the evaporating. After 24 hours, a cross-cut test was carried out according
search for an optimum wetting and dispersing additive. to DIN EN ISO 2409.
Evaluation of wetting and dispersing additives Formulation, application and choice of additives
To evaluate the influences of wetting and dispersing additives, a Several common pigments and fillers were incorporated to obtain a
standard primer formulation based on a styrene-acrylic dispersion pigment volume concentration (PVC) of 28 %. The dry film thickness
was used. Five test procedures were chosen to compare the effects of the coating was fixed at 80 µm on cold-rolled steel panels and on
of the products. PE foil to produce the free films. Drying conditions were set at seven
To determine water uptake, the paint was applied at a specific film days, at 23 °C ± 2 °C and a relative humidity of 50 % ± 5 %.
thickness to a polyethylene (PE) foil, dried for a fixed time interval, As regards the choice of additives, the aim was to represent a large
carefully removed from the foil and weighed. Next it was immersed in variety of different chemistries and variations. At least one represent-
distilled water. At fixed time intervals, the paint film was removed from ative from the groups of phosphoric acid esters, fatty acids, acrylates,
the water, and water droplets were removed with a cloth. The weight polyurethanes, and controlled-polymerisation acrylates was picked
gain was then established and the water uptake was determined as a initially. The chosen additives were used at an amount of 1.5 % active
percentage of the original dry film weight. substance calculated on pigments and fillers.
To check this method for reliability, some samples were evaluated by
differential scanning calorimetry (DSC). After immersion in distilled Results in summary
water for 24 hours, a sample was cooled down to -60 °C and heated
up to +80 °C. The melting peak of water and its melting enthalpy were In the early water resistance test, the best results in Table 1 are shown
used to calculate the amount of water inside the coating and this was by two acrylate-based additives, AC-4 and AC-5, and the PU-based
compared to the values generated by the gravimetric method (see additive, PU-1. Their good performance can be explained by their hy-
Figure 1). drophobic nature, although AC-5 contains a considerable additional
To measure water diffusion, a free coating film was produced by the number of hydroxyl groups. The very non-polar domains/co-mono-
PE foil application method, a small plastic cup was attached to its mers in the additive molecules make it far more difficult for water to
surface then filled with distilled water (see Figure 2). At certain time penetrate the coating, reach the interface between coating and panel
intervals, the IR absorption was evaluated at wavenumber 3400 cm-1 and lead to adhesion loss.
by means of an ATR (Attenuated Total Reflectance) measurement and In the water uptake test (see Figure 3) the parallel measurement of
compared to the absorption of a paint film without water contact. the water content by DSC in four samples shows that the values from
The salt spray test was carried out according to DIN EN ISO 9227. The both methods are the same within their variations. The tendency to
test paint was applied to cold-rolled steel panels which were exposed absorb water can be correlated quite well with the hydrophilicity of
in the salt spray chamber after drying. The panels were then checked the additives used.
for the amount of blistering according to DIN EN ISO 4628-2 and for The reference sample without additive shows the lowest water ab-
delamination/rust creep according to DIN EN ISO 4628-8. sorption, while the most polar additives AC-1, AC-3 and AC-5 (with a
Free films of the test paint were also fixed in a permeability cup. The test high content of hydroxyl groups) show the highest water uptake. The
was carried out according to DIN EN ISO 7783. At certain time intervals, other additives range between the values of the control and AC-3,
the weight lost by diffusion of water vapour through the coating was except for additive AC-4.
determined. After 24 hours of water exposure in the diffusion test, it can be seen
Figure 3: Water uptake after 6 hours of water immersion (gravi- Figure 4: Diffusion coefficients after 24 hours of water exposure,
metric and DSC test)

that AC-1, AC-2 and AC-3 show the highest diffusion and that almost vapour: the additive itself, poor film formation or pinholes generated
all additives show a higher diffusion rate than the control, except for by foam bubbles.
AC-4 and PU-1 (Figure 4). While the lower value of AC-4 can be ex- Finally, in the salt spray test (see Table 1) the acrylates AC-1 and AC-2
plained by its hydrophobic nature, the good performance of PU-1 is again gave the worst results, and were removed from the test after
surprising because of the high number of hydroxyl groups it contains. 140 hours due to severe blistering and delamination at the scribe.
Further investigations are needed to explain this effect, but it can be The products FS-1, AC-4 and PS-1 exhibited medium performance
said in general that a more hydrophobic additive leads to better dif- and were removed after 384 or 500 hours. The best performance was
fusion behaviour. shown by PU-1, AC-3 and AC-5, which endured the test for 700 hours.
Once again, the acrylate-based additives AC-1 and AC-2 show poor
results in the permeability test (Table 1). AC-3 shows a medium level Test results show some poor correlations
of performance, while all other additives exhibit values comparable
to the control. It is hard to explain the poor result of additive AC-3. Summarising all the results in one overview with a view to drawing
However, many factors could have increased the diffusion of water conclusions is rather difficult, as the results of the different methods
do not necessarily correlate with each other. This can be seen in Fig-
ure 5.
An initial observation is that only three samples show the same ten-
dency in all of the tests: the control, AC-1 and AC-2. The control shows
Figure 5: Over view of additives and their performance in differ- very good results in all aspects, and it could be asked why a wetting
ent tests and dispersing additive should be used at all.
The reason is quite obvious, as outlined in the introduction: the addi-
Early tive is needed to ensure good storage stability, application properties
IR Permea- Salt spray
Code Neutra-lisation Water uptake water
diffusion bility test and optical appearance. In fact, the control paint without any additive
res.
was barely producible due to its extreme high viscosity and bad wet-
Control
ting. It was impossible to apply it by spray, and its storage stability was
FS-1 Amine 1 very poor.
PS-1 Amine 2 This means that, although efficiency might be lost in the known pa-
rameters, a wetting and dispersing additive is necessary to be able to
PU-1 Amine 1
produce a stable and usable paint. The chemistry utilised for these
AC-1 Amine 3 types of additives has to be carefully selected to obtain additives with
AC-2 Base 1 a minimal impact on paint film properties.
AC-3 Base 2 Additionally it can be said that the different test methods do not nec-
essarily correlate with each other. This is a major finding, as it makes
AC-4 Amine 3
it very evident that, for example, a bad result in water uptake and
AC-5 Base 2 diffusion does not necessarily indicate a bad result in the corrosion
test (see additive AC-3), while, on the other hand, a good result in all
other parameters can still mean a medium performance in the salt
spray test (see additive AC-4). It is therefore important to carefully
Table 1: Summary of some results in three tests select the evaluation methods with regard to the subsequent use of
the coating and the parameter of greatest importance.
Early water
resistance: Permeability test
Test methods must be matched to end uses
cross-cut test after (24 hours)
water exposure Salt spray
Name Chemistry This work has shown that several testing procedures must be used to
test (hours)
After 4 After 24 evaluate the effect of additives and to compare them with each other
V [g/
hr. drying hr. drying R2 as there is no clear correlation, for example, between water uptake
(m2/d)
[GT] [GT] and corrosion resistance.
Several structural elements that affect the overall performance of the
Control 1 1 0.9994 26.3 600
additives could be identified. These structural parameters are range
FS-1 Fatty Acid 5 1 0.9991 26.4 384 from the basic “backbone” elements via specific co-polymers to the
PS-1 Phos. Acid Ester 2 2 -- -- 500 bases used for neutralisation.
PU-1 Polyurethane 0 0 0.9984 24.0 700 Although further work on these issues is required, it can be said that
by deliberate variation of structural elements, additives can be de-
veloped which have only a limited impact on the critical parameters
specified or which in future will even be able to improve the perfor-
AC-1 Polyacrylate 5 5 0.9949 46.2 140
mance of waterborne coatings. 
AC-2 Polyacrylate 5 5 0.9995 38.0 140 REFERENCES
AC-3 Polyacrylate 2 0.9979 29.1 700 [1] Marktstudie, European Protective Coatings Markets, M39E-39.
[2] Heilen W., Additive für wässrige Lacksysteme, Vincentz, 2009.
AC-4 Polyacrylate 0 0.9983 24.3 384
AC-5 Polyacrylate 0 0.9987 26.5 700

20 C o r r o s io n p r o t e c t io n
Claude Beaubien - Fotolia.com

Tailored
to endure
New dispersing additives help to protect aqueous
coatings against corrosion. By Philippe Favresse,
Frank Kleinsteinberg, Katrin Roland and Patrick Glöckner,
Evonik Industries.
Graft copolymer pigment dispersants were produced by free Wetting and dispersing additives enable a productive
radical and controlled radical polymerisation and their per- dispersion process
formance was evaluated in two pigment concentrates for
waterborne coatings. Both production technologies produced During the dispersion process, pigment agglomerates are ground
similar performance, but by modifying the composition of the to maximise the colouring capacity of what are often expensive pig-
additive the corrosion resistance of the coatings could be en- ments and to meet optical requirements such as colour value, colour
hanced. strength, chroma and transparency. Wetting and dispersing additives
wet the surface of the pigment and prevent reagglomeration of the
W etting and dispersing additives are indispensable for the pro-

duction of high quality pigment concentrates with high colour
strength and adequate storage stability. However, especially with
pigment particles once dispersed.
In high-quality aqueous coatings, polymeric wetting and dispersing ad-
ditives are used to anchor themselves to the surface of the pigment.
aqueous coatings, their hydrophilic structure can cause the resistance Anchoring is accomplished by means of functional group attraction.
of the resulting films to deteriorate. Because of their macromolecular structure and electrostatic repul-
The aim of this study was thus to develop polymeric wetting and dis- sion, they ensure adequate stabilisation of the coating matrix [1, 2 ].
persing additives for aqueous pigment concentrates which display no Compared to low molecular weight products, coating films with poly-
significant adverse impact on the corrosion protection of aqueous meric wetting and dispersing additives generally exhibit higher me-
coatings. The polymers were produced using various polymerisation chanical and chemical resistance properties. Nevertheless, even with
processes and were comparatively evaluated. polymeric additives there is still an adverse effect on the water and
Figure 1: Polymers with the same composition but with different Figure 2: Schematic representation of a statistical graft
constituents: (a) statistical copolymer (b) AB block copolymer copolymer

copolymers (b) there is a distinct accumulation of monomer units in

one part of the polymer. Block copolymers made from ‘anchoring’ and
‘stabilising’ monomers can therefore form highly effective wetting and
dispersing additives.
Graft copolymers are a special case whose anchoring groups are ei-
Results at a glance ther arranged in the side chains of the comb-like structures or directly
on the polymer backbones (Figure 2). These structures naturally lead
űű Graft copolymer pigment dispersants were produced by to a particularly high number of contacts on pigment surfaces and are
free radical and controlled radical polymerisation. consequently regarded as highly effective wetting and dispersing ad-
ditives. Figure 3 shows that graft copolymers can have a higher num-
űű Their capabilities as wetting and dispersing additives for ber of anchoring groups and stabilising elements per unit of volume
aqueous pigment concentrates and industrial coatings were than pure AB block copolymers.
investigated in terms of rheological, colouristic and corrosion
resistance properties. Dispersants may be made by several different routes
űű It was shown that both polymerisation technologies pro- There are a variety of known processes to produce polymers with a
duce a similar performance profile. However, the composition well-defined structure. These include polyaddition as well as ionic and
of the polymeric additive does affect its performance. radical polymerisation methods [4]. With regard to the radical meth-
ods, free radical polymerisation (FRP) of macromonomers to produce
űű The best of these wetting and dispersing additives satis- graft copolymers is just as well established as ‘living’ controlled radical
fies the requirements for rheological and colouristic properties polymerisation (CRP). This – like all living polymerisation methods –
while providing a high degree of corrosion resistance. allows the number of blocks, length of the blocks, and block length
distribution to be adjusted easily in the synthesis of block copolymers
[5, 6].
Each of the methods available has advantages and disadvantages that
can be of a technological or commercial nature. For example, living
controlled radical polymerisation (CRP) allows many different polymer 
Table 1: Formulations of the pigment concentrates

corrosion resistance of aqueous coatings. This effect can be explained
in part by the high polarity of the anchoring groups and is especially Raw materials PR 101 PB 15:4
noticeable when part of the polymer is in the coating matrix and not
Deionised water 17.4 33.9
fixed to the surface of the pigment.
Dispersing additive 21.0 25.0
How dispersant structure can affect performance TEGO Foamex 810 1.0 1.0
The efficiency of the polymeric dispersing additives is highly depend- Pigment 60.0 40.0
ent on molecular weight, the choice of monomers and the arrange- Aerosil 200 0.5 -
ment of the monomer units within the polymer [1-3]. Dispersing ad-
ditives attach themselves to the pigment surface especially well when Biocide 0.1 0.1
the anchoring groups are within close proximity to one another. Fig- Total [g] 100.0 100.0
ure 1 shows polymers with the same composition but with different
Additive solids on 14 % 25 %
constituents: with a purely statistical arrangement (a) the monomers
pigment
are distributed randomly throughout the polymer while in the block
Table 2: Colouristic properties of the 2K PU coatings based on pigment con-

Figure 3: Schematic representation of a pigment surface with (a) centrates PR 101 and PB 15:4 with different dispersing additives in full tone
a statistical graft copolymer and (b) AB block copolymer disper-
sant bonded to the surface Dispersant/
MS CRP FRP1 FRP2
pigment
With PR 101
Colour strength (F) 476 485 485 500

Haze 50 30 35 20
Gloss 20 ° 79 81 83 83
With PB 15:4
Colour strength (F) 710 740 740 745
Haze 90 85 85 85
Gloss 20 ° 89 90 89 90

22 C o r r o s io n p r o t e c t io n
 architectures to be created, but processing these polymers is often Figure 4 shows the dynamic viscosities of the different pigment con-
time-consuming. One process that exhibits this drawback is the sepa- centrates before and after storage. The research dispersing additives
ration of copper-based catalysts or alkyl halides, which must be car- (CRP, FRP1, FRP2) all produced a very good and stable viscosity profile.
ried out to prevent discolouration and avoid impairing the corrosion There is no significant difference between the measurement results
resistance of coating films. on these different research products. In a trend, the viscosity-reduc-
In comparison, free radical copolymerisation (FRP) of (meth)acrylates ing effect of the optimised wetting and dispersing additive (FRP2) is
often leads to a statistical distribution as the selectivity in attachment more pronounced.
depends largely on the copolymerisation parameters of the respec- The viscosity of the blue pigment concentrate based on the market
tive monomers towards each other [7]. The advantages of this meth- standard (MS) was slightly lower after storage. This can be explained
od are minimal requirements with regard to the purity of the starting by a wetting of the pigment subsequent to dispersion and therefore
materials and ease of handling on a large technical scale. suggests slower wetting. In the case of the PR 101 concentrate with
MS, the viscosity increase after storage can be regarded as undesirable.
Properties of pigments and additives studied
Colour strength is enhanced
For an extensive assessment of different production processes, wet-
ting and dispersing additives for aqueous coating applications were The research products tested largely produced similar colour proper-
investigated. Comb-like graft copolymers produced by FRP were com- ties as demonstrated in Table 2. FRP2 tends to produce higher colour
pared with those that were produced by CRP. The comparison addi- strength with better compatibility (less haze). The comparison with
tive was a conventional copolymeric dispersing additive that can be the market standard (MS) shows that with the organic blue pigment
regarded as a market standard for aqueous industrial applications. the research products (CRP, FRP1, FRP2) provide slightly higher colour
The aim of the study was to provide a wetting and dispersing additive strengths. With the inorganic red pigment, they show improved com-
with the best possible efficiency in terms of colorimetric properties patibility versus the market standard and demonstrate significantly
and corrosion resistance behaviour. higher colour strength (by up to 5 %).
Four different copolymer dispersants were compared in this study: It would appear that with aqueous graft copolymer dispersing additives,
ąą MS Market standard: conventional copolymeric dispersing ad- the distribution of the monomers throughout the polymer is less critical
ditive produced by free radical polymerisation (statistical distribu- (comparison between CRP and FRP1). On the other hand, the composi-
tion of the comonomers); tion is crucial, as the comparison between FRP1 and FRP2 indicates.
ąą CRP Graft copolymer dispersing additive produced by con-
trolled radical polymerisation (composition identical to FRP1 but
with an alternating structure); Figure 4: Dynamic viscosity (D = 100 s -1 mPas) of the pigment
ąą FRP1 Graft copolymer dispersing additive produced by free radi- concentrates with various dispersing additives based on pig-
cal polymerisation (statistical distribution of the comonomers); ments PR 101 (left) and PB 15:4 (right) before and after storage
ąą FRP2 Graft copolymer dispersing additive produced by free radi- at 50 °C for 7 days
cal polymerisation (optimised composition).
Two pigments were studied for this evaluation: a PR 101 red iron ox-
ide, and a PB 15:4 phthalocyanine blue. The formulations of the pig-
ment concentrates are shown in Table 1. Pigments were milled in a
Skandex shaker with 200 g glass grinding media (ø 2.5 - 2.8 mm) for a
dispersing time of 1 hour (PR 101) or 2 hours (PB 15:4).
Test coatings and test methods
In this study, colorimetric and salt spray results are reported on a

room temperature curing, aqueous, 2K industrial coating to which
the corresponding pigment concentrate was added (PR 101: 8 %, PB
15:4: 4 %). The results of the investigation were confirmed in other
formulations, such as an aqueous polyester-melamine stoving enamel
system. Because the results were similar, they will not be discussed
here. The test system for the investigation of water absorption was a
1K acrylate-based filler that was mixed with the PR 101 concentrate
in a ratio of 7:3.
The rheological properties were investigated in accordance with DIN
EN ISO 3219 using a “RotoVisco1” rheometer from Thermo Electron
(cone/plate type CP 35/2 ° and D = 0 - 1000 s-1). For the spectropho-
tometric investigation of the colour properties, the 2K PU test coating
was applied to “Leneta” cards at 150 µm wet film thickness and meas-
urements were made with an X-Rite “Type SP62” spectrophotometer.
The salt spray test was carried out according to DIN EN ISO 9227
(1200 h) on steel plates (2K PU test coatings). The gravimetric investi-
gation of water absorption was done in relation to the starting value
using a 1K filler on aluminium after the sheets had been stored in a
water bath for 24 h at room temperature.
Rheological properties of the pigment concentrates

Resistance to salt spray and water both improved Impact of structure and composition summarised
Figure 5 shows multiple aqueous 2K PU industrial coatings after the In this study, wetting and dispersing additives for aqueous pigment
salt spray test. With both the organic phthalocyanine blue and the concentrates produced by controlled and free radical polymerisation
inorganic red iron oxide, the coatings with the standard dispersing methods were compared. It was shown that the production method
additive (MS) exhibit the highest level of damage. Blister formation does not have much effect on the colouration or rheological proper-
and corrosion creep can be seen, suggesting inadequate protection. ties of aqueous pigment concentrates. Also, no significant differences
The coatings containing two dispersing additives of the same compo- with regard to corrosion or water resistance were found due to the
sition produced via controlled (CRP) and free radical polymerisation varying of production methods.
(FRP1) have the same degree of resistance. In particular, blister for- Therefore, whether the monomers are alternating (CRP) or statistically
mation with these two copolymer forms is slightly better than with the (FRP1) distributed throughout the graft copolymer does not appear
market standard. The coatings with the optimised dispersing additive to affect the properties evaluated. Compared to the market stand-
(FRP2) produced outstanding results. The coating remained largely ard, the wetting and dispersing additives evaluated have a higher per-
unaffected throughout the entire salt spray test. formance spectrum. This performance spectrum could be increased
The investigation of the water absorption confirms the results of the even further by optimising the composition as in the test product
salt spray test (Figure 6). The market standard dispersing additive re- FRP2 [9]. 
sults in the most water absorption. The coatings containing the two
dispersing additives of the same composition but produced by dif- REFERENCES
ferent methods (CRP, FRP1) provide similar results. The coating with
the optimised dispersing additive, variant FRP2, has the lowest water [1] Evonik Industries AG, The Big TEGO, edition 4, Essen, Germany, 2012.
absorption. [2] Heilen et al., Additives for waterborne coatings, Vincentz Network, Hano-
Practically speaking, lower water absorption results in higher mechan- ver, Germany, 2009.
ical resistance during water stress as swelling, which often produces [3] Glöckner et al., The star performer, Europ. Coat. Jnl., No. 05, pp 26-31,
softer and more susceptible films, is minimised. Lastly, changes in 2010.
appearance, such as blushing, are not observed with the optimised [4] Odian, Principles of Polymerization, 3rd Edition, Wiley Interscience, New
variant, FRP2. York, 1991.
[5] Metz N., Synthese von komplexen Polymerarchitekturen durch die
kontrollierte Polymerisation von Reaktivester-Monomeren, Dissertation,
Mainz, 2009.
Figure 5: Aqueous 2K PU industrial coating based on pigments PB 15:4 [6] Wittmann G., Aufbau definierter Polymerarchitekturen durch Radikalis-
(top) and PR 101 (bottom) after the salt spray test (DIN EN ISO 9227, che Polymerisation unter Atomtransfer (ATRP), Dissertation, Darmstadt,
1200 h) on steel plates (from the left, using the different dispersing addi- 2003.
tives: MS, CRP, FRP1, FRP2) [7] Glöckner, Ritter, Macromol. Rapid Comm., Vol. 20, pp 602-605, 1999.
[8] Glöckner, Der ökologische Umbau einer Produktpalette, in Wässrige
Kunststoffdispersionen und ihre Anwendung, 71. FH Texte, Aachen, pp
9-20, Jan. 2005.
[9] www.tego.de, Technical data sheet TEGO “Dispers 757 W”.
Figure 6: Water absorption (%) of a 1K acrylate filler with the PR

101 pigment concentrate based on different dispersing addi-
tives; substrate: aluminium, after being stored in water for 24 h
at room temperature

24 Wat e r bo r n e c o at i n g s
Source: Torsten Lohse - Pixelio
Improved pigment
concentrates
A new dispersant for waterborne coatings provides enhanced staibilisation. By Steffen Onclin, Harald
Frommelius, Paula Gómez Perea, Elena Martinez and Shailesh Shah, BASF.
The proper dispersion stabilisation of pigments is not only im-

portant for the final properties of a coating, it also helps pig-
ments to be used as efficiently as possible. Peak performance
G ood dispersing agents should provide excellent dispersing power
and the stabilisation of different pigment classes. This results in low
mill-base viscosities and high colour strength in the final paints. When pig-
on a broad range of pigments can be achieved using a dual- ment concentrates are stored and dispensed, low viscosity and long-term
dispersant approach. Two complementary dispersants were stability become particularly important. To keep in line with the trend to-
each designed to have an optimum performance with a se- wards more sustainable coatings, dispersing agents must contribute to the
lected group of pigments and at the same time to guarantee fulfilment of the most stringent emission requirements for VOC levels, so
inter-compatibility. that the paints produced can can carry eco-labels.
Figure 1: Different types of pigment stabilisation in aqueous systems

Wat e r bo r n e c o at i n g s 25
Precise design
Results at a glance Dispersing agents need to fulfil two main requirements. Firstly, they
should have a strong affinity for the pigment surface and secondly,
űű A new dispersant, using controlled free-radical polymerisa- they should provide robust stabilisation against flocculation. These
tion technology, has been developed for waterborne applica- demands can be fulfilled most effectively if the architecture of the
tion. The new product is an electrosteric dispersant with en- polymer is controlled at the design stage.
hanced steric character, which provides broad compatibility CFRP enables the precise design of polymer structures. Although
and improved pigment stabilisation. non-controlled, free-radical polymerisation can lead to good dispers-
ing agents, polymers with a highly defined architecture can be more
űű The new dispersing agent is particularly effective with inor- efficient, resulting in improved colorant stability and broader system
ganic pigments, including difficult to disperse pigments, such as compatibilities [2], [3], [4]. With CFRP technology, well-defined block
transparent iron oxides. copolymers may be prepared that are designed optimally to fit pig-
ment and resin chemistry.
űű The new product shows benchmark performance with in- As illustrated in Figure 2, dispersing agents designed with CFRP consist
organic pigments, but additionally good application results can of two defined blocks that are prepared by sequential polymerisation
be obtained with many organic pigments, giving it an all-round of monomers or monomer mixtures. Typically, a longer stabiliser block
character. is formed initially. This needs to be compatible with the relevant paint
system. The anchoring block contains functional groups which interact
űű The new dispersing agent complements the performance strongly with the pigment surface to allow for efficient and stable adsorp-
of a current steric stabilising CFRP dispersant which is recom- tion. For demanding applications such as organic pigments, the anchoring
mended for many demanding organic pigments and achieves a block normally contains aminic groups, which can be further modified if
high level of jetness for carbon blacks (5). required.
It is preferable to use this new technology to design high-performance
dispersing agents, because well-defined structures lead to anchor-
ing groups with a higher efficiency. This in turn increases adhesion
to the pigment surface, improves flocculation resistance and brings
enhanced colour development. Additionally, it allows for precise con-
trol of the polymeric backbone to achieve good stabilising properties
through the optimum compatibility achieved.
The correct design of dispersing agents can go a long way to achieving
overall top performance in a broad range of coating systems. Enhanced electrosteric stabilisation
The classical way to stabilise inorganic pigments in aqueous systems
is through electrostatic stabilisation (see Figure 1). This highly effective A new dispersing agent was developed using CFRP technology, which
mechanism is mainly used in low performance applications, for exam- shows positive results on inorganic pigments. It relies on an enhanced
ple, matt interior and façade paints, because dispersing agents car- electrosteric stabilisation mechanism. Both the charge density of the
rying a high charge density can potentially have a negative influence stabiliser block and the number of steric components were studied
on resistance properties. On the other hand, in the case of organic systematically. It was found that higher levels of steric components
pigments, better application results are obtained when stabilisation in the stabiliser block are beneficial to the performance of the final
takes place using steric hindrance and non-ionic interactions. [1] coating.
Electrosteric stabilisation, on the other hand, combines both mecha- The newly developed dispersant, “Dispex Ultra PX 4575”, (referred to
nisms, steric and electrostatic. Recently, a new type of polymer has later as D1) complements the performance of, a current steric stabi-
been developed that relies on electrosteric stabilisation with en- lising CFRP dispersant, “Dispex Ultra PX 4585” (referred to later as
hanced steric character. These “enhanced electrosteric” dispersing D2). The two dispersants were tested on a range of pigments using
agents are prepared by controlled, free-radical polymerisation tech- four commercially available products as benchmarks These are re-
nology (CFRP) and are designed to give broader compatibility across a ferred to as: B1, B2, B3 and B4. B1, B3 and B4 and are styrene maleic
wide range of coating systems. anhydride-based copolymers and B2 is an acrylic block copolymer. 
Figure 2: Structure of dispersing agents designed with CFRP technology

26 Wat e r bo r n e c o at i n g s
 The following data illustrates test results with three different pigment new dispersant and benchmark product B4 (Figure 5).
types as examples: Also, tests on transparent iron oxide red pigments demonstrated that
Firstly, transparent iron-oxide colorants. Figure 3 shows the mill-base D1 perfomed the best, followed by B1 and B4. The other benchmark
viscosity of yellow transparent-iron-oxide pigment concentrates. D1 products B2, B3 together with CFRP dispersant D2 showed some
shows low viscosity at the lowest dosage level, whereas the benchmark weaknesses in terms of viscosity and stability of the colorants.
products B2 and B4 only perform well at higher dosage levels. With The second pigment type is bismuth vanadate, which is the pigment
benchmark product B3 and D2, it was not possible to prepare a paste of choice to replace lead-containing inorganic pigments in high-end
that could be handled. The pigment concentrates were subsequently industrial applications. This material provides good colour saturation
let-down in a 2-pack, PUR clear coat and the transparency and gloss and durability, combined with high opacity. Optimally dispersing this
levels were measured. pigment is important, because it makes it possible to achieve com-
Figure 4 shows lowest scattering delta E values, and therefore the best plete hiding at lower film thicknesses.
transparency, for D1. This indicates an excellent stabilisation of the finely The rheological behaviour of pigment concentrates containing 60 %
ground pigment as well as a good compatibility with the let-down resin bismuth vanadate was examined. Figure 6 shows that low-viscosity
system. concentrates with good storage stability could only be achieved with
The results mentioned above are further illustrated with an applica- the two CFRP dispersants. All the benchmark products tested were
tion photo of a drawdown of two tinted clear coats prepared with the not able to produce pigment concentrates of low viscosity at the test-
Figure 3: Viscosity with transparent iron oxide yellow (30 %), Figure 5: Comparison of transparencies in transparent iron-oxide
dispersing agent dosage: 15 %/20 %/25 % active on pigment yellow using dispersing agents D1 and product B4
Figure 4: Transparency and gloss of a 2-pack PUR clear coat tinted with Figure 6: Viscosity development – fresh and after storage – of
transparent iron oxide yellow., dE* scattering: The lower the value, the colorants based on bismuth vanadate
higher the transparency

Wat e r bo r n e c o at i n g s 27
Figure 7: Colour strength and rub-out in bismuth vanadate ed pigment concentrations.

dispersions The poor rheological performance of the pigment concentrates con-
taining the current industry benchmarks is also reflected in the col-
our development in an industrial stoving system (Figure 7). D1 shows
good colour development, while the other tested dispersants either
could not be tested, because of very viscous pigment concentrates, or
showed poor colour strength.
Thirdly, carbon-black pigments were also tested to ascertain broad ap-
plicability of the new product. Figure 8 shows the viscosities of pigment
concentrates containing 35 % of carbon black. Again, the CFRP products
provide low-viscosity concentrates that are minimally affected by warm
storage.
Broad compatibility
The compatibility and colour strength of the pigment concentrates

were tested in a number of architectural and industrial systems.
Figure 9 shows the results in an industrial self-crosslinking system.
Already at a low dosage level, D1 provides good colour strength in
combination with excellent compatibility. Only D2 and one benchmark
product provide better colour development, although at higher dis-
persant dosages.
Figure 8: Viscosity development, fresh and after storage of A range of further pigments and systems were tested to assess the
colorants based on carbon black application performance of D1. Such pigments include additional
transparent iron oxides, a number of opaque inorganic pigments and
several organic pigments. It was generally observed that the peak
performance of the new product is with inorganic pigments, provid-
ing low viscosities at low dispersant concentrations, combined with a
broad compatibility in industrial and architectural paint systems. But
also with organic pigments, D1 shows good performance, giving the
product an all-round character. Best results with selected organic pig-
ments, however, are obtained with D2. 
References
[1] Auschra C., Pirrung F., Harbers P. E. L., FARBE UND LACK 2006, 10,
24-30.
[2] van den Haak H. J. W., J. Coat. Technol. 1997, 69 (873), 139-144.
[3] Pirrung F. O. H., Quednau P. H., Auschra C., Chimia 2002, 56 (5), 170-
176.
[4] Auschra C., Eckstein E., Muhlebach ((hier fehlt das Initial des Vornamens,
FR)) et al., Prog. Org. Coat. 2002, 45 (2-3), 83-93.
[5] Onclin S., Martínez E., Huguenard S., Asia Pacific Coatings Journal
Figure 9: Colour strength and rub-out with carbon black in a self- 2012, Vol. 25, No. 04, 20-22.
crosslinking acrylic paint

28 H ig h S o li d s
Source: Mark Huls - Fotolia.com
High solids
enhancements
Additive optimises both colour stability and viscosity in 2K systems. By Kirstin Schulz, Evonik Industries.
A new wetting and dispersing additive achieves a stable low Figure 1: Comparison of wetting and dispersing additives: “Tego
viscosity and consistently stable colour in two-pack high sol- Dispers 678” generates the lowest viscosities at various shear rates
ids paints. Raw material inventories can be reduced because it
also gives good results in medium solids formulations.
T he use of high solids formulations is a proven way of reducing

VOC emissions and meeting the European Directive 2004/42/EU.
The changeover from medium solids to high solids paint formulations
is relatively easy for paint manufacturers and for users, as the produc-
tion and application equipment are the same. In contrast, the use of
water-borne or radiation curing alternatives generally involves major
changes in raw materials and often also in equipment and application
techniques. The resulting investment can be avoided by the use of
high solids coatings. Because of its good cost/performance ratio, high
solids technology has now become common.
Despite the many similarities between medium solids and high sol-
ids technologies, there is a marked difference between them. At ap-
plication viscosity, high solids paints obviously possess a significantly
higher non-volatile content. This frequently poses difficulties in ap-
plication, with achieving high gloss, with drying and with the storage
stability of the paints.

H i g h S o li d s 29
during various methods of application and drying times.

Raw materials must be chosen carefully to avoid undesirable phe-
nomena such as pigment sedimentation, colour shifts or increased
Results at a glance viscosity after storage. The diverse pigment and filler surfaces must
be homogeneously wetted and stabilised, particularly in the case of
űű High solids paints offer a way to meet regulatory require- direct (multi-pigment) grinding, which is used when batches exceed a
ments without any need for major changes to raw materials, certain customer-specified size.
production or application equipment. Water-borne or radiation The ideal wetting and dispersing additive reduces the viscosity in the
curing alternatives often require substantial changes in all areas. paint and prevents pigment sedimentation during storage. Wetting
and dispersing additives which are well established in medium sol-
űű However, wetting and dispersing additives used success- ids technology are still frequently used in high solids formulations.
fully in medium solids formulations may not provide sufficient However, they no longer satisfy the increasingly stringent demands
viscosity reduction, colour stability or storage stability. of modern high solids technology. Often, the combination of viscosity
reduction with sufficient colour stability/pigment stabilisation is inad-
űű A new additive developed specifically for two-pack high sol- equate in high solids paints.
ids coatings was tested in a colour-critical mixed pigment and
mixed binder system and shown to provide superior viscosity Performance advantages of the new additive
reduction, colour stability in the rub-out test and storage stabil-
ity. Performance in basic physical tests was slightly better than A new wetting and dispersing additive has now been developed
the control sample. specifically to achieve stable, low viscosity and constant colour, par-
ticularly in high-quality two-pack high solids coatings. Because it also
űű The new product’s broad compatibility allows it to be used achieves excellent results in medium solids coatings, the new addi-
in medium solids formulations, thus helping to limit raw mate- tive meets the coatings industry’s need for a widely-useable prod-
rial inventories. uct that can help to limit the number of raw materials required in
manufacturing.
The new wetting and dispersing additive has been developed spe-
cifically for the direct grinding of mixed pigment two-pack high solids
coatings. The strong reduction in viscosity permits high pigment and
filler loading. In applied coatings, it generates a good topcoat finish
and stable colour while providing good gloss retention. Adhesion is
not impaired after exposure to condensation. The outstanding stor-
Key requirements for wetting and dispersing additives age stability of coatings manufactured with the new additive contrib-
utes to resource efficiency.
All the raw materials used influence the rheology of a coating, but wet- The high molecular weight polymer (50 % solids dissolved in methoxy-
ting and dispersing additives are of the greatest importance [1]. The propyl acetate/dibasic ester) exhibits very broad compatibility both
correct choice of wetting and dispersing additive decisively affects the in high solids polyesters and acrylates as well as in medium solids 
rheology of high solids paints (Figure 1). Adjusting the working viscosity grades of the same types of binder. The star-shaped polymer has a
of high-gloss high solids paints containing organic pigments is particu- high density of pigment-affinic groups and stabilises inorganic pig-
larly difficult. The desired colour should not change during storage or ments, organic pigments and carbon blacks with equal efficiency.
Figure 2: Rub-out test for colour flotation, 12 minutes after spray

application, left: highly-branched polymer with non-balanced
anchor groups in the molecule, centre: “Tego Dispers 678”, right:
PU chemistry, market standard Figure 3: Condensation-water test to DIN EN ISO 6270-2

30 H ig h S o li d s
Table 1: Test formulation (t wo-pack high solids PU) Table 2: Properties of “Tego Dispers 678” in t wo-pack high
solids paint
Raw material Parts by weight %
Property tested in “Tego

PART A: Millbase Market standard
two-pack PU Paint Dispers 678”
Acrylate resin (70 % in butyl acetate) 36.0
ΔE coated/rubbed
“Tego Dispers 678” (50 % in 0.7 0.4
2.0 surface before ageing
methoxypropyl acetate/dibasic ester)
Carbon black 0.2
ΔE coated/rubbed
surface after ageing 1.3 0.5
Phthalocyanine blue 0.4
(two weeks, 50 °C)
Titanium dioxide 12.0
Visual description of 55 % greyish super- 5 % slight whitish

aged specimens (two natant formed, no supernatant formed, no
Barium sulfate 4.0
weeks, 50 °C) sediment sediment
Acrylate (70 % in butyl acetate) as above 13.4
Cross-hatch ISO 2409

24 h after condensa- GT 1 GT 0
Methoxypropyl acetate 4.0
tion-water test
Let-down
Degree of blistering to
m1g1 m0g0
Polyester (80 % in butyl acetate) 16.0 DIN 53209
Butyl acetate 3.4
Cross-hatch to ISO
GT 0 GT 0
Blend of aromatic hydrocarbons 3.4 2409 on steel
Xylene 4.3
Optical appearance
(levelling, gloss, body)
OK OK
“Tego Airex 990” 0.3 after ageing (two
weeks, 50 °C)
“Tego Flow 300” 0.6

Viscosity of the paint
(Part A) prior to ageing
311 367
Total 100.0 (mPas at shear rate
100 sec-1)
PART B: Addition of hardener

Viscosity of the paint
(Part A) after ageing
for two weeks at 50 370 384
HDI trimer (70 % in butyl acetate) 28.0 °C (mPas at shear rate
100sec-1)
VOC in g/l (calculated) of useable coating 378

H i g h S o li d s 31
 Rub-out test confirms colour stability Gloss, levelling, settling and effectiveness in traditional medium solids
coatings were further criteria considered in the choice of structure for
With mixed pigmentation, the wetting and dispersing additive has to the new wetting and dispersing additive. The properties of the wetting
deal with the particular challenge of reducing the millbase viscosity, and dispersing additive in two-pack high solids paints are shown in
wetting widely different pigment surfaces and subsequently provid- Table 2 and compared with those of the market standard for medium
ing lasting stabilisation. Only by satisfying all three criteria can colour solids technology. The results of the settlement test after ageing can
shifts, flooding, floating and settling be avoided. also be seen in Figure 4.
It is known that organic pigments are stabilised by aromatic anchor
groups, while carbon blacks are stabilised by amine structures in the Selecting the star structure
wetting and dispersing additive [2]. With mixed pigmentation, a wet-
ting and dispersing additive with a customised molecular structure Technologies as PU and acrylat polymers with pigment-affine groups
with differing pigment-affinic groups is required because the different have been tested. To identify a successfull additive structure, a parent
surfaces must be stabilised to the same degree. To identify this struc- lacquer containing a wetting and dispersing additive was formulated.
ture, a high solids two-pack poly-urethane test formulation as shown The first disqualifier was the degee of decrease in viscosity. A low vis-
in Table 1 was used. cosity of the parent lacquers is required in order to allow the applica-
The mixed pigmentation was chosen because wetting and dispers- tion of the coatings via Airmix oder Airless with a high non-volatile
ing additives can be easily differentiated using this sensitive tint. The content. Therefore, the parent lacquer was measured using cone/
wetting and dispersing additive must wet equally the various types of plate geometry. It is important that the viscosity is as low as possible
surfaces in this formulation and adhere to them; otherwise settling, and remains stable during storage.
separation, or colour differences would show up in the rub-out test. The coating has been applied before and after storage. After an evap-
Figure 2 shows that the results of this test are clearly satisfactory. oration time of 12 minutes at room temperatur, a rub out was per-
formed. In the following, the rubbed and non-rubbed surfaces were
Good gloss and physical properties measured colorimetrically. An ΔE value as low as possible was used as
a means to measure the stabilisation of pigments and fillers and con-
In Part A of the formulation, a polyester was used in combination stituted another exclusion criterion to find the most suitable structure
with an acrylic resin to assess the necessary broad compatibility of of the additive.
the wetting and dispersing additive. In two-pack topcoats for plastics All in all, the new additive showed the best results and is distinguished
substrates, it is usually necessary to improve the elastic properties by very easy and uncritical handling and storage in the paint manufac-
by including a polyester resin. The adhesion and performance of the turing process. Even at -18 °C, it is still clear and liquid.
most promising structures were subsequently tested in a humidity
chamber (Figure 3). The paints were applied to degreased “R46” cold Broad range of applications and benefits summarised
rolled steel test panels from Q-panels. Prior to the condensation-wa-
ter test to DIN EN ISO 6270-2, the painted test panels were aged for The use of this new additive, “Tego Dispers 678” as a wetting and dis-
three days in an oven at 60 °C. persing additive for modern mixed pigment direct grinds simplifies
Subsequently, they were subjected to a cross-hatch adhesion test manufacture and application. It is a general purpose product and can
to DIN EN ISO 2409. The edges and cross-cut surface were careful- be used both for high and medium solid formulations.
ly masked off before the test panels were exposed in the humidity Modern high solids paints can be formulated to comply with the EU
chamber. After two weeks, the coatings were examined for swelling, Directive. The new additive satisfies the requirements of industrial
blushing and blistering. After 24 hours regeneration time, a further paint manufacturers because it:
cross-hatch test was carried out.
ąą achieves low ΔE values in situations such as the rub-out test, thus
providing stable colours;
Figure 4: Paints after ageing for t wo weeks at 50 °C, left: “Tego ąą exhibits good results in the water condensation test, thus proving
Dispers 678” left: star-structure, centre: highly-branched poly- it is ideally suited for use in mechanically and chemically resistant
mer with non-balanced anchor groups in the molecul, right: PU paints;
chemistry, market standard ąą lowers the viscosity of the millbase, thus permitting significantly
higher non-volatile contents;
ąą produces good results in terms of gloss and levelling after applica-
tion, thus achieving a superior appearance;
ąą possesses good storage stability, which increases process security;
ąą has a very low inherent viscosity (even at -18 °C) and is therefore
easy to handle during production;
ąą is also well suited for use in medium solids coatings and therefore
reduces the number of raw materials needed in the manufacture
of coatings.
REFERENCES
Heilen W. et al., Additives for Waterborne Coatings, Vincentz Network, Hannover,

[1]
Germany, 2009.
[2] The Big Tego, Evonik Industries AG, Essen, Germany, 2012.

32 S u r fa c tant s
Source: Evonik
Sticking to
the subject
New superwetting additives solve adhesion problems in
waterborne coatings. By Roger Reinartz, Jeanine M. Sny-
der and Ye Dai, Air Products.
New, low-foaming siloxane superwetting surfactants have itself. For spreading, or good substrate wetting to occur, the coating
been developed to provide improved equilibrium and dynamic must have a stronger association with the substrate than with itself.
surface tension reduction as well as improved flow and level- This is shown mathematically in Figure 1. When the coating-substrate
ling for hard-to-wet surfaces without recoatability problems. system has favourable surface chemistry, a desirable and well-func-
Practical examples of their use are presented. tioning coating can be formed. If not, many defects and failure modes
can occur, such as craters, crawling, picture framing, orange peel, Bé-
S urface chemistry is closely involved with wetting, flow and levelling

of a coating, as well as other associated properties. When a liquid
coating is applied to a substrate, the coating should wet the substrate
nard Cells, cissing, pinholing, foaming, pigment flooding and floating
[1-2], all of which can lead to other catastrophic deficiencies.
Waterbased technology offers a means to meet various environ-
easily and evenly to ensure good appearance and adhesion. mental and legislative demands, although formulation can pose
The coating will exhibit both an adhesive force (degree of association many problems. Water has a high cohesive strength and high sur-
between the coating and the substrate) and a cohesive force within face tension compared with most solvents; therefore additives are
Figure 2: Schematic structure of gemini surfactants: t wo

Figure 1: Adhesive and cohesive forces in a coating standard surfactant molecules linked by a spacer unit
Liquid coating
Air Adhesive force

Cohesive force
Solid substrate
Work of adhesion WA = γSA+ γLA-γSL

Work of cohesion W C = 2γLA
Work of coefficient S L/S = WA- W C

= γSA+ γLA-γSL - 2γLA

= γSA+ γLA-γSL

S u r fa c tan t s 33
trations. In contrast, a particular type of speciality surfactant struc-

ture, termed Gemini, has two hydrophobic tails connected to two
hydrophilic head groups on the same molecule. As shown in Figure 2,
each half of the “twin” surfactant is joined together by a spacer group,
forming the Gemini structure.
Results at a glance Because of their unique molecular architectures, these Gemini sur-
factants are much more surface active than their standard ‘monomer-
űű The increasing use of new resin technologies and non-fer- ic’ components [3]. Gemini surfactants are often used in waterborne
rous substrates to meet today’s product standards presents coating, ink and adhesive formulations for both dynamic surface ten-
significant challenges for formulators. Substrate wetting, re- sion reduction and foam control.
coatability and surface appearance are common problem areas There are many different interfaces in a coating formulation where
when using waterborne coatings. surfactants can concentrate (see Figure 3). Surfactants are still widely
used to stabilise the resin emulsions used in waterborne systems and
űű Many flow and levelling agents as well as wetting agents per- other surface active materials are used to disperse and stabilise pig-
form well but introduce foam problems. Effective defoamers in ments. However, for effective substrate wetting the surfactants must
such formulations may cause craters and can create a vicious cir- be active at the moving boundary between the liquid and substrate.
cle that is hard to break.
Basic parameters for substrate wetting
űű New, low-foaming optimised siloxane superwetting sur-
factants have been developed to provide equilibrium and dynam- Many surfactants can facilitate substrate and particle wetting by re-
ic surface tension reduction as well as improved flow and levelling ducing the surface tension of the formulation to a level that is equal
for hard-to-wet surfaces. Good results are shown in wood and to, or lower than, the substrate being coated. As the surface tension
plastics coatings and even a self-levelling flooring mix. of water is 72 mN/m and typical coating substrates are in the region
of 35-45 mN/m, surfactants must be used to decrease the surface
tension of any waterbased paint to allow it to flow smoothly onto the
substrate.
Additionally, in order for wetting to occur, the contact angle q must
be less than ninety degrees; contact angles greater than 90 ° result in
beading of the coating on the substrate. Figure 4 illustrates how lower-
ing the surface tension of the coating to below the surface energy of
the substrate results in a final film with excellent wetting.
needed to reduce the surface tension of water to allow good sub- Surface energies of some substrates may be less than 35 mN/m and
strate wetting. present a significant problem to the applicator. When this occurs, two
pathways are available. First, the substrate may be treated to raise the
Gemini structure for surfactants offers advantages surface energy, making it easier for the coating to wet out the surface.
When this is not a viable option, the formulator is then forced to look
Surface active agents, or surfactants, are materials that can adsorb at a stronger set of surfactants, including superwetters, to achieve the
onto surfaces or at interfaces and lower the surface or interfacial free low surface tensions needed to wet out the substrate.
energies of aqueous formulated systems. Conventional surfactants
have a polar or ionic, hydrophilic head group connected to a hydro- Chemical classification of surfactants
phobic, hydrocarbon tail group. Because of their amphiphilic nature,
surfactants will migrate to and accumulate at interfaces and reduce Surfactants can be classified in several ways. They may be non-ionic,
surface and interfacial tensions even when used at very low concen- anionic or cationic in nature and the choice of which type to use is 
Figure 4: Wetting agents facilitate substrate and particle wetting;

γSA, γSL and γLA are solid-air, solid-liquid and liquid-air interfa-
Figure 3: Various surfactant interactions in a formulation cial tensions
Adsorption at surface
Micelle
Crystallisation formation
Bilayer vesicle
formation
resin
pigment
Adsorption at
L/L interface Adsorption at
S/L interface

 often determined by the application and other components in the for- ferently when subjected to dynamic conditions and exhibit different
mulation. The largest and most commonly used class of surfactants, foam profiles.
the anionics, includes chemistries such as alkyl benzene sulfonates,
fatty acid soaps and dialkyl sulfosuccinates [4]. Improving performance with superwetting
While these offer excellent wetting at a relatively low cost in use, their surfactants
main drawback is their tendency to foam in coatings, thus requiring
the formulator to include strong defoaming agents which can lead to What happens when the surface tension of the substrate falls well
film defects and aesthetic issues. below the typical 35 mN/m range where traditional surfactants are
Non-ionic surfactants, many based on polyethoxylated materials, can no longer effective? Such low-energy surfaces might include plastic,
be excellent wetting agents and emulsifiers [4]. This group includes wood or even poorly prepared or oil-contaminated metal surfaces.
the gemini surfactants mentioned earlier and their derivatives as well This becomes even more challenging with lower VOC coatings, which
as siloxane-based surfactants and fluorosurfactants. are now formulated to well below 100 g/l and even down to 0 g/l, with
The final and smallest group, the cationics, is used less often in coat- less solvent to help flow, levelling, and appearance of the coatings. In
ings applications as they will react with any anionic species in the sys- such cases, the formulator may employ the use of superwetting sur-
tem; however, they are sometimes used as solid particle dispersants factants to reach the desired level of wetting.
or emulsifiers [4]. Superwetters are surfactants with structures that allow them to effi-
While all three types can offer excellent wetting, they perform dif- ciently adsorb and pack at interfaces, resulting in low dynamic surface
Figure 5: Wetting of a traditional siloxane surfactant vs. organic Figure 7: Equilibrium surface tensions vs dynamic surface ten-
superwetter: 0.1 wt% aqueous solution, oily metal surface, sions for select surfactants. Surface tension measured at 0.1 %
10 sec wetting time, 23 °C water solution
Traditional siloxane surfactant Organic superwetter
Figure 6: Dynamic Surface Tension (DST) comparison of aque-

ous solutions containing 0.1 wt.% surfactant (measured using
a Krüss “BP-II” bubble tensiometer) with new optimised siloxane
based superwetting surfactants
Figure 8: 2K polyurethane waterborne clearcoat applied to

polypropylene panels
No surfactant Siloxane - 1 Siloxane - 2
Siloxane - 3 Optimised siloxane Optimised siloxane

superwetter 1 superwetter 2

S u r fa c tan t s 35
tensions, fast wetting times and low contact angles on low surface en- other defects.
ergy substrates, as can be seen in Figure 5. They can be siloxane-based While siloxane and fluoro-based surfactants can achieve very low
or organic in nature. It has been recognised that it is actually the com- equilibrium surface tensions, their dynamic surface tension perfor-
pact structure of the surfactant hydrophobe that plays a major role in mance is poor because they are unable to quickly migrate to the new-
a molecule performing as a superwetter [5-9]. ly created interfaces under dynamic conditions and maintain that low
surface tension state [10].
The importance of dynamic surface tension Organic superwetting surfactants are able to achieve reasonably low
equilibrium and extremely low dynamic surface tensions; therefore,
Many coating-related processes, such as paint manufacture (e.g., pigment they are often excellent alternatives to traditional siloxane and fluoro-
dispersion), mixing and application, are high speed agitation processes, surfactants. Also, when used in a waterborne formulation, traditional
which disrupt the surfactant concentration and alignment at the surface, siloxane and fluoro-based surfactants will migrate to the air-coating
thus creating higher dynamic surface tension during and after agitation. interface, as they tend to be organophobic. This may lead to recoat-
Surfactants that quickly diffuse back to the interface, align and reduce ability issues should a second layer of coating be applied.
surface tension offer low dynamic surface tension, i.e., they provide In contrast, organic superwetting surfactants maintain their low dy-
low surface tension during and shortly after these dynamic agitating namic performance even during high speed coating processes. They
processes. They are effective and efficient at providing good wetting are also generally more compatible with most coating systems, have
and levelling, and avoiding problems such as craters, fisheyes and no or minimal foam stabilisation and present no issues regarding re-
coatability. Figure 6 highlights the equilibrium and dynamic surface
tension performance of some organic superwetters compared to
siloxane-based and fluorosurfactants.
Figure 9: 2K polyurethane waterborne clearcoat applied to Latest siloxane technology enhances performance
silicone release liner
Many waterborne resin systems suffer from application limitations
that can only be effectively eliminated by using high quality surfactants
No surfactant Silicone and defoamers. In particular, poor substrate wetting, edge retraction,
Optimised siloxane
superwetter 2 pinholing and other defects result in high product failure rates that
are costly to the manufacturer.
Choosing the right surfactant that provides effective wetting and level-
ling while minimising foam improves the overall performance of the
No wetting Poor wetting, Good wetting
craters coating formulation. Recently, new optimised siloxane superwetters
have been developed; these products exhibit the outstanding spread-
ing, flow and levelling usually associated with siloxanes as well as the
low-foam, dynamic wetting benefits attributed to organic superwet-
ting surfactants.
Figure 10: Polyurethane acrylic hybrid coating applied to red oak Figure 6 compares the dynamic surface tension performance of the
organic superwetters, a siloxane-based surfactant, a fluorosurfactant
and the new optimised siloxane superwetters. Because they possess
both siloxane and organic functionalities, these superwetting sur-
factants provide superior flow and levelling and low-foam wetting. Ad-
ditionally, they offer improved formulation compatibility and do not
suffer the recoatability issues that may be seen with traditional silox-
ane surfactants.
No surfactant Organic SW1 Silicone When trying to coat a very hydrophobic surface such as plastic or
wood, particularly when spray applying a coating, it is critical that the
wetting package be able to perform while under dynamic shear and
then again when the coating flows and levels across the substrate.
Figure 7 illustrates how these new optimised siloxane superwetters
Figure 11: Acrylic wood coating containing 0.2 wt% surfactant hit the target with respect to both equilibrium and dynamic surface
spray applied on wood tension reduction.
Plastic coatings are a critical application area
Efficient dynamic and equilibrium surface tension reduction are key

Optimised siloxane
superwetter 2 factors in affecting final wetting performance when coating substrates
Siloxane - 1 such as plastics with very low surface energies. As a demonstration,
a two-component polyurethane coating crosslinked with isocyanate
containing 0.2 wt% surfactant was prepared and spray applied to
polypropylene panels and a silicone release liner at 75 μm wet film
Optimised siloxane Organic SW1 thickness.
superwetter 1
Figures 8 and 9 show that with no surfactant the system completely
de-wets. Using traditional siloxane-based surfactants also results in
poor wetting and defects in the film as well. By incorporating the new
optimised siloxane superwetters, excellent dynamic and equilibrium 

 surface tension reduction is achieved resulting in excellent wetting plied on a plastic foil and after 15 minutes air was introduced using a
with no surface defects. notched trowel (upper half of the samples in Figure 12).
As can be clearly seen, siloxane-1 has poor levelling, suffers from pig-
Performance of wood coatings can also be enhanced ment flotation and has a significant amount of pinholes. Siloxane-2
increased viscosity, resulting in poor levelling performance. Of all the
Wood substrates are inherently difficult to wet out due to the poros- additives evaluated, only the new optimised siloxane superwetters
ity of the substrate, surface contaminants such as glue or sap and gave a robust performance, independent of the dosage level and de-
irregularities in the surface roughness. As the coating flows over the foamer combinations evaluated.
surface of the wood, penetration into the substrate occurs; this can
lead to surface imperfections from both inadequate wetting and foam Promising additives for most difficult applications
generation.
When the coating penetrates the wood and wets out the grain, air is The application of coatings, inks and adhesives on difficult-to-wet sub-
displaced which rises to the surface and can become trapped in the strates such as porous wood, plastics, films and oily metal presents
dried film. Selecting a wetting agent that offers excellent flow and lev- significant challenges for coatings formulators. Selecting the sur-
elling as well as foam control is critical for a high quality finish. Figure 10 factant is critical to maximising wetting and minimising defects such
illustrates a waterborne wood coating based on a polyurethane-acryl- as pinholes, edge retraction, and orange peel.
ic hybrid polymer system that has been brush-applied on red oak. New optimised siloxane superwetters have been developed to offer
When no surfactant is added, severe orange peel is seen in the coat- the formulator the ability to achieve low dynamic surface tensions
ing. In comparison, when incorporating Organic SW1 or a siloxane- with minimum foam generation while promoting excellent flow and
based surfactant, the surface appearance is greatly improved. How- levelling for a wide variety of coating systems. 
ever, only Organic SW1 can migrate quickly to the newly formed
interfaces during application and not only lower the surface tension
but also eliminate any foam generated by the wetting of the substrate. REFERENCES
The siloxane surfactant offers excellent wetting but stabilises foam,
which is still apparent in the dried coating. [1] Pierce P. E., Schoff C., Coating Film Defects, Federation of Series on Coat-
A self-crosslinking acrylic emulsion based wood coating was also pre- ings Technology, FSCT, Philadelphia, 1991.
pared and spray applied onto wood at a wet film thickness of 100 µm. [2] Bierwagen G. P., Prog. Org. Coat., 1991, Vol. 19, p 59.
As shown in Figure 11, compared to the siloxane-based surfactant and [3] Reinartz R. et al, New gemini surfactants as paint additives, 7th Nürn-
Organic SW1 surfactant, the new optimised siloxane superwetters 1 berg Congress, Vol. 1, Paper III, pp 217-229.
and 2 show improved crack filling and foam control when coatings are [4] Salager J.-L., Surfactants: Types and Uses, FIRP Booklet #E300-A, Uni-
spray-applied onto the wood surface. versidad De Los Andes, 2002.
[5] Hill R.M. et al, Langmuir, 1994, Vol. 10, p 1724.
Good results obtained in self-levelling epoxy [6] Goddard E. D., Ananthapadmanabhan K. P., Chandar P., Langmuir, 1995,
flooring Vol.11, p 1415.
[7] Hill R. M. et al, Langmuir, 1995, Vol. 11, p 1416.
The multifunctional benefits and broad formulation latitude of these [8] Stoebe T. et al, Langmuir, 1996, Vol. 12, p 337.
new siloxane superwetters can be nicely demonstrated in a highly [9] Rosen M. J., Song L. D., Langmuir, 1996, Vol. 12, p 4945.
filled solvent free epoxy/cycloaliphatic amine self-levelling flooring [10] Snyder J. M., Marcella P. C., A new, environmentally friendly wetting
system. The original starting formulation had poor stability and ap- agent for architectural coatings, PCI, April 2011.
pearance and suffered from pigment floating and pinholes, as can be
seen in Figure 12.
Various surfactants and superwetters were incorporated into the
blank formulation (5 minutes at 1000 rpm) at both 0.2 % and 0.8 %
dosage levels. The self-levelling flooring systems (10 x 10 cm) were ap-
Figure 12: Self-levelling solvent free epoxy flooring containing 0.2 % surfactant
Optimised siloxane
No surfactant Siloxane - 1 Siloxane - 2 superwetter 2

W o r ld o f C o l o ur 37
Source: Smile - Fotolia.com

Colourful
Powder
Basis of the colour powder
Gulal, which is used on holi
celebrations and festivals,
is usually cornmeal, corn-
starch or rice meal.
Three Holi Facts

ąą Traditionally, holi is a Hindu
celebration of the begin-
ning of spring.
ąą Its is also called festival of
colour or festival of love.
ąą The date varies and is
mostly in March or February.
Source: www.bbc.co.uk/nature/
humanplanetexplorer/events_and_festivals/holi

38 N a n o t e c h n o l og y
Source: Otmar Smit - Fotolia.com
A stronger shield
from storms
Nano-additives for toughening water-borne elastomeric roof coatings. By Detlef Burgard and Marc Herold,
Bühler Partec GmbH.
To fight global warming and to reduce energy costs, IR-reflec- degree of crosslinking, which in turn is susceptible to water absorption.
tive roof coatings are applied in hot regions. The properties of Additionally, the requirements for this kind of roof coating are not
waterborne coatings are often inadequate for this application. only a high elongation at break but also high mechanical durability.
Less than 1 % addition of a crosslinking nano-additive is shown This parameter is to some extent represented by the tensile strength
to increase tensile strength and reduce water absorption of of the film. But in many cases a high tensile strength often leads to a
two waterborne elastomeric roof coatings. decreased elongation at break.
As already mentioned, cool roof technology helps to reduce energy
D ue partly to global warming concerns, there is an increasing

trend to replace black or dark grey roof coatings with white coat-
ings that have a high reflectivity and therefore contribute to cooler
consumption. Therefore more and more IR-reflective roof coatings
are applied in hot and sunny regions. In order to further reduce en-
vironmental impacts, there is an increasing trend to switch from sol-
room temperatures. The coatings have to withstand various weather vent-based coating materials to waterborne coatings.
scenarios. Key issues are water resistance and a very good mechani- However, waterborne coatings still cannot fully replace solventborne
cal strength and high elongation at break of the dried film. alternatives due to their sometimes poorer performance and there is
When looking at the requirements that derive from these two issues, a steady need for further improvement. Using two elastomeric acrylic
they appear contradictory at first sight. Maximum water resistance formulations as examples, the beneficial effect of a nano-additive on
would require a non-swellable highly crosslinked polymer in the dry performance parameters such as tensile strength and reduced water
film. However, a high elongation at break demands a film with a low absorption is demonstrated.

N a n o t e c h n o l og y 3 9
Formulations and test methods
To investigate the effects of the additive, two white pigmented roof

coating formulations (Tables 1 and 2) were prepared based on “Primal
EC 1791 E” (further named “Roof coating P”) and “Acronal NX 3250”
Results at a glance (named “Roof coating A” respectively. Different amounts of nano-
additive were added to these formulations. From these formulations
űű In order to fight global warming and reduce energy costs, samples were cast according to DIN EN ISO 527 (see Figure 1) to test
IR-reflective roof coatings are increasingly applied in hot re- the stress-strain profile.
gions. To further reduce environmental impacts, these coatings The samples were dried at room temperature for one week and test-
should be waterborne, but their properties are often inferior ed on a Zwick Roell “UPM 1446” mechanical testing machine with a
to solventborne types and improvement is therefore needed. traction speed of 25 mm/min. The whole test procedure was set up
according to ASTM D2370-98 (2010).
űű Using two sample elastomeric acrylic formulations, the ben- For the determination of the water uptake, free-standing coating films
eficial effect of a nano-additive on performance parameters were prepared by pouring samples of the formulations into PTFE
was demonstrated. The addition of less than 1 % additive dis- cups. The samples were dried at room temperature for seven days
persion can reduce water absorption by more than 50 % and and the coating films were peeled off and weighed. The amount of wet
lower the diffusion coefficient of water to about one-third. paint was calculated to obtain dry films with a weight of approximately
1 g. The thickness of the resulting film is in the order of 0.2 to 1 mm.
űű Stress-strain studies show that the tensile strength is in- The films were immersed in water and removed from the water after
creased by about 50 % while elongation at break is unchanged, defined periods, dried and weighed. After the weight was determined,
leading to a coating with higher toughness and durability. the films were re-immersed into the water bath. The immersion ex-
periment was stopped when the water uptake of the films with and
űű Non-covalent crosslinking by the nanoparticles is believed without additive reached saturation (Ms). Two series of tests were car-
to explain these improvements. ried out with the blank formulation (see Table 1) and 99 % formulation
with 1 % additive.
The uptake of water by the polymer is assumed to proceed by a diffu-
sion process that can ideally be described by Fick’s law. For the initial
sorption period, a t 0,5 or √t law can be derived [1]:
Mt 4√ D
= √t
Ms L√ π (1)

In equation (1), Mt represents the amount of water absorbed at any
time t, Ms the greatest amount of water in the film when the satura-
tion stage is reached, L the film thickness (cm) and D is the diffusion
coefficient (cm2/s). Plotting Mt/Ms versus t 0,5 or √ t provides a linear
relationship that allows the diffusion coefficient D to be determined. 
Table 1: Elastomeric roof coating P Table 2: Elastomeric roof coating A
Ingredients Supplier kg Ingredients Supplier kg

Water 134 Water 69
“Orotan 850” Dow 4 1,2-Propanediol 3
Potassium tripolyphos- 1 Pigmentverteiler NL BASF 11

phate “Byk 035” Byk 9
“Nopco NXZ” Henkel 3 “Kronos 2190” Kronos 214

“DRB 8/25” Imerys 138
“Ti-pure 706” DuPont 372
“Imercarb” Imerys 9
“Ti-Pure R960” DuPont 62
“Microtalc IT” Omya 51
“Primal EC 1791 E” Dow 416 Ammonia 10 % 4
"Texanol" Eastman 6 “Byk 035” Byk 6
“NX 3250” BASF 436
Aq. Ammonia 10 % 2
Water 51
“Oxylink 3101” Bühler 0 20 “Oxylink 3101” Bühler 0-10

 Figure 1: Typical test specimen for the stress-strain test; grid Table 3: Effect of nano-additive on water diffusion coefficient D
distance is 1 cm
Diffusion coefficient Ratio D with/
Formulation
(10-6 mm²/s) without additive
No addi- With addi-

tive tive
Roof coating P (see 3.3 2.0 0.62
table 1)
Roof coating A (see 14.4 3.8 0.27
table 2)
Figure 2: Stress-strain test results for the white roof coating P Figure 3: Stress-strain test results for the white roof coating A
Figure 4: Water uptake plotted against film immersion time for Figure 5: Water uptake plotted against film immersion time for
the roof coating P with and without 1 % nano-additive (average the roof coating based on A with and without 1 % nano-additive
film thickness 0.44 mm (blank) and 0.48 mm with nano-additive) (average film thickness 0.76 mm (blank) and 0.51 mm with
nano-additive)

N a n o t e c h n o l og y 41
Tensile strength and water resistance are improved some indication for this crosslinking reaction with acrylic binders had
also been found [3-5].
The results of the stress-strain tests for the formulation in Table 1 No evidence has been found for a reduced elongation at break for
are depicted in Figure 2. The test results show an improvement of the films with nanoparticles, which makes the additive extremely ver-
the tensile strength when the additive is present in the formulation. satile for the crosslinking of roof coatings or elastomeric materials in
While the tensile strength of the blank sample is 1.5 N/mm², an im- general.
provement of > 30 % was observed, reaching saturation when 0.6 % It is assumed that the undisturbed elongation at break is due to the
additive was present. On the other hand the maximum elongation at non-covalent nature of the crosslinking. Indications for this kind of
break remains more or less constant at (300 ± 50) % over the com- non-covalent network bonds are also found when functionalised elas-
plete sample series. tomers are crosslinked with zinc oxide that is bound on the surface of
The results of the stress-strain tests for the formulation based on the silica [6]. As regards the slower diffusion of water in the film and the
other emulsion can be seen in Figure 3. The test results show an im- therefore reduced water uptake in the film, it is also suggested that
provement of the tensile strength when the additive is present in the the increased crosslinking induced by the nanoparticles is the cause
formulation. While the tensile strength of the blank sample is 2.4 N/ for this finding.
mm² an improvement of > 48 % was observed, reaching saturation Thus, nanoparticle-based additives such as “Oxylink” can increase the
when approximately 0.5 % additive is present. crosslinking density in 1K waterborne coating systems. As a conse-
On the other hand the maximum elongation at break again remains quence, various parameters including barrier properties, water resist-
constant at (100 ± 20) % up to 0.8 % addition of the “Oxylink” nano- ance or toughness are improved. In this work, it has been shown that
additive. Only if 1 % or more is present does the elongation at break at the same time the flexibility of elastomeric films is maintained. 
decrease down to 80 %.
The results of the water uptake of the roofing films of both formulations
over time are compared in Figures 4 and 5. The results show a faster wa- REFERENCES
ter uptake for the blank film sample when looking at the initial period of
the immersion in water. Diffusion coefficients were calculated by equa- [1] Perez C. et al, Prog. in Org. Coat., 1999, Vol. 36, pp 102-108.
tion (1) and the results are presented in Table 3. [2] Zosel A., Ley G., Macromol., 1993, Vol. 26, No. 9, pp 2222–2227.
[3] Pilotek S. et al, The Waterborne Symposium, New Orleans, Feb. 18-20,
Crosslinking explains nanoparticle benefits 2009.
[4] Burgard D., Herold M., Farbe und Lack, 2011, Vol. 117, No. 6, pp 14-18.
A reason for the increase in the tensile strength of the films that incor- [5] Herold M. et al, PCI Magazine, August 2010, pp 24-27.
porate the additive can be the crosslinking of the elastomeric polymer [6] Owczarek M., Zaborski M., KGK Kautschuk Gummi Kunststoffe, 2004, Vol.
in the formulation by the zinc oxide nanoparticles [2]. In earlier work 57, pp 218-223.

Source: LE BRUSQ - Fotolia.com

A little goes
a long way
The addition of nanoparticles can enhance the perfor-
mance of water-borne coatings. By Detlef Burgard and
Marc Herold, Bühler Partec GmbH.
Waterbased coatings have gained a significant market share Materials and methods
during the last few years, while the standards in quality of
these coatings have steadily improved. However, there is still A series of matt-clear coats for wood based on an aliphatic polyure-
a need to improve certain features to provide optimised solu- thane dispersion (Table 1) was prepared, in order to demonstrate the
tions for different applications. One possible way to gain en- effect of the additive. To compare the impact of the nanoparticulate
hancements is by the use of dispersed nanoparticles as perfor- crosslinking additive on both 1K and 2K formulations coatings with
mance additives. and without polyisocyanate were produced. In experiments, a HDI
S mall amounts of nanoparticles as additives can lead to a signifi-

cant performance increase in one-component waterborne polyu-
rethane coatings, especially in terms of chemical/solvent resistance, Table 1: Coatings and formulations
blocking resistance drying time and hardness. The increase in perfor-
mance can be achieved by a non-covalent crosslinking mechanism.
Ingredient Ingredient Amount /g
There are some first indications that such nanoparticle additives can
be a useful alternative to isocyanate crosslinkers in certain applica- ALX 1 ALX 2 ALX 3 ALX4
tions, enabling increased hardness or faster curing kinetics equivalent Alberdingk U Alberdingk Boley, 771.0 771.0 771.0 771.0
to shorter process times. Another advantage can be seen in the fact 9150 Germany
that the tested nanoadditives did not change the 1K characteristics Hydropalat 140 Cognis, Germany 4.0 4.0 4.0 4.0
of the formulation. On the other hand, these nanoparticle additives
can – under certain circumstances – be used together with isocyanate Tego Foamex Evonik, Germany 6.0 6.0 6.0 6.0
822
crosslinkers and further increase some performance parameters of
the resulting coatings. Acemat TS 100 Evonik, Germany 10.0 10.0 10.0 10.0
As shown earlier [1-4], nanoparticle-based additives like “Oxylink” can Diethylene 40.0 40.0 40.0 40.0
increase the crosslinking density in 1K waterborne coating systems. As glycol
a consequence, various parameters like barrier properties, resistance monobutylether
against solvents and water or blocking resistance can be improved. Water 149.0 149.0 149.0 149.0
Enhanced early properties can be achieved which may also lead to
Acrysol 2020 Dow, USA 10.0 10.0 10.0 10.0
shorter process cycles in industrial applications. In these works, em-
phasis focused on acrylic and styrene acrylic dispersions as resin bas- Oxylink 3102 Bühler AG, - 10.0 - 10.0
es. These nanoadditives can also be successfully used as cross linkers Switzerland
for PUD systems, both 1k but as well in certain 2k formulations. Bayhydur 3100 Bayer MaterialSci- - - 77.1 77.1
ence AG, Germany

panol (IPA), was also evaluated.

Results at a glance ąą The formulations were applied on leneta foil (PVC) with a roll coater
and approximately 60 µm wet film thickness
űű Small amounts of nanoparticles as additives can significant- ąą The samples were dried at room temperature (22-23 °C /40-60 %
ly enhance the performance of one-component waterborne rel. humidity) for 16-72 hours
polyurethane coatings, especially in terms of chemical/solvent ąą The samples were blocked for 24 hours at room temperature
resistance, blocking resistance drying time and hardness. ąą The samples were de-blocked and rated on a 0-5 scale (0=best)
For the determination of the gloss the formulations were applied on
űű First test series were done with 1K formulations ALX1 and glass plates with 100 µm wet film thickness by using a doctor blade.
ALX2 in order to evaluate the crosslinking effect of the nanoad- The samples where dried overnight and the gloss was determined by
ditive, using a MEK double rub test, where is was shown that the measuring the reflectivity at eight different points with a gloss meter
additive nearly doubled the MEK double rub resistance from (“Elcometer 402”) at 85° according to DIN EN ISO 2813.
22 double rubs (w/o additive) to 40 double rubs (w/o additive). The drying time for drying level four was measured with a “B.K. Drying
Recorder”. Therefore glass slides were coated with a 100 µm wet film
űű The results for the Koenig hardness measurements show and determined the duration until drying level d was reached (there
that the nanoadditive has the largest impact on the 1k formula- was no visible pin trace on the coatings surface).
tion. Already after one day drying, the hardness of the coating For the determining the adhesion the formulations were also ap-
ALX 2 with 1 % additive is about 20 % higher than the hardness plied on glass plates with 100 µm wet film thickness by using a doctor
of the formulation ALX 1 without additive. blade. The samples where dried at room temperature overnight and
the film-to-substrate adhesion was determined by using the cross cut
űű By the fast reaction of the nanoparticles, shown in Equation method with 1 mm distance between the cuts according to DIN EN
1, a large portion of carboxylic groups may be blocked and are ISO 2409. The adhesion was evaluated by ranking the results from 0
no longer accessible to undergo a reaction with isocyanates. (best) to 5 (worst).
The Ethanol resistance of the coating was tested with exposure times
űű There is the potential to further improve the performance of 1 hour according to DIN EN ISO 2812- 3 and DIN EN ISO 4628-2.
of 2K systems when the reaction kinetics of isocyanates and the The chemical resistance was evaluated by rating the results from 0
crosslinking nanoadditive are carefully matched. (best) to 5 (worse).
Results
The compatibility of the additive with all formulations was excellent.

(“Bayhydur 3100”) was used. The dosage level for the nanoadditive The gloss of the formulations remains nearly unaltered at (40 ± 2)
was constantly at 1 %. gloss units. The 1k formulations ALX 1 and ALX 2 have been stable at
The formulations with the polyisocyanate were prepared and applied 40 °C for more than three months and are still under observation. In
on the glass plates and lenata foil (PVC) substrates. For detailed analy- contrast to this, the 2K formulations ALX 3 and ALX4 have a pot life of
sis of the coating performance the following tests were carried out: approximately three hours.
The degree of cross linking was determined by crock meter double First test series were done with the 1K formulations ALX1 and ALX2 in
rub tests with 2-butanon (MEK)-double rub resistance test (crosslink- order to evaluate the crosslinking effect of the nanoadditive, using a
ing) according to ASTM D-5402. The resulting parameter is the num- MEK double rub test. The additive nearly doubled the MEK double rub
ber of double rubs needed to completely remove the coating from the resistance from 22 double rubs (w/o additive) to 40 double rubs (w/o
substrate. In a parallel test the double rub resistance against 2-pro- additive), as shown in Figure 1a. When applying Isopropanol (IPA) rubs 
Figure 1a: MEK double rub resistance with and without Figure 1b: IPA double rub resistance with and without
nanoadditive nanoadditive
A
A BB

 to the sample coating the effect was even more pronounced. The IPA The blocking of the coating was reduced by 1.5 marks from mark 4
double rub resistance, shown in Figure 1b, boosts by using the addi- to mark 2.5, as shown in Figure 3. Blocking of polymers and coatings
tive from 19 double rubs to 143 double rubs. is a process where parameters like the migration of substances, sur-
A reason for the increase in double rub resistance of the films that face roughness, chemical surface structure and surface energy are
incorporate the additive can be the crosslinking of the carboxylic involved [5-7]. Current research in this field has shown that blocking
groups of the polymer in the formulation by the nanoparticles. In ear- resistance of coatings can be achieved by prevention of migration of
lier works some indication for this cross linking reaction with acrylic low molecular weight polymeric material between the surfaces [8].
binders [1-4] was also found to be the case. This result shows that This migration can be prevented by increased crosslinking density, for
these findings can be transferred to PUD systems, as long as there are instance. In addition, anionic groups of these smaller molecules can
accessible reactive carboxylic groups. interact with the surface of the inorganic nanoparticles of the additive
Further evaluation of the time dependence of the cross linking effect and thus being immobilised or at least hindered in their migration.
in the ALX 1 and ALX 2 formulation by monitoring the drying times has The radar graph in Diagram 4 provides an overview on the different
also been carried out. The drying time is characterised by the time to performance improvements by the cross linking nanoadditive. In ad-
reach drying grade d (“end of pin trace”). “Oxylink” causes the drying of dition to the above mentioned improvements, no negative impact of
the formula to accelerate by 15 % from 21.2 min to 17.7 min. The dry the nanoparticle additive on other coating properties like adhesion
time acceleration is attributed to the early onset of the crosslinking or gloss could be found in this study. Figure 4 summarises the us-
reaction between the carboxylic groups and the nanoparticles, shown age properties of the two tested coating materials and compare the
in Figure 2. The fast onset of crosslinking results in a higher film tough- overall performance of the individual formulations with and without
ness throughout the drying process is such that a certain fastness is the nanoparticle additive. A very distinct improvement of the overall
reached already after a shorter period of time. performance can be achieved through the addition of nanoparticles
to the respective formulation.
The next step was to investigate in how far the performance of the na-
noadditive crosslinker can be compared to the performance of isocy-
Figure 2: Reduced drying time with nanoadditive in formulation anate crosslinkers which represent the current high quality state of the
ALX2 art. Results are described based on a comparison of the nanoparticu-
late crosslinker with an HDI – isocyanate – that has been used in the
formulations ALX3 and ALX4, shown in Table 1. In these first tests dry-
ing time and hardness development was being assessed, as this is in-
teresting for the application and further processing. For example, when
a subsequent sanding or polishing step is required, it is important for
the coating to harden early, therefore enabling the applicator to carry
out further processing steps as soon as possible after the coating is ap-
plied. In addition, a good final hardness improves abrasion-resistance.
The results for the Koenig hardness measurements in Figure 5 show
that the nanoadditive has the largest impact on the 1k formulation.
Already after one day drying, the hardness of the coating ALX 2 with 1
% additive is about 20 % higher than the hardness of the formulation
ALX 1 without additive. This 20 % difference in hardness is maintained
over the observed time of three weeks.
When looking at the 2K formulations ALX3 and ALX4, the effect of the
nanoadditive on the hardness development in the presence of the
HDI isocyanate is smaller but still remarkable. After one day drying,
Figure 3: Improved blocking resistance with nanoadditive cross Figure 4: Overall performance comparison for the formulations
linker in formulation ALX2 0 = best; no damage at all, 5 = worst; shows significant improvement by the use of the nanoadditive.
complete failure : ALX1; : ALX2 (100: Best performing in the respective test)

the hardness of the coating ALX4 is about 12 % higher than ALX3. further improve the performance of 2K systems when the reaction
Whereas the hardness of ALX3 is even slightly lower than the hard- kinetics of isocyanates and the crosslinking nanoadditive are carefully
ness of the 1K formulation ALX1, the formulation which contains both matched. Of course, this is still a theory and has to be further veri-
nanoadditive and isocyanate (ALX4) shows about the same degree of fied in the future. As well, further investigations will have to be done
hardness than ALX1. to further evaluate the influence of the nanoparticle crosslinker on
In both the 1K and the 2K system the presence of the nanoadditive other film properties of the 2K systems, such as chemical resistance
leads to a faster hardness development, higher early hardness as or weathering resistance. 
well as higher end hardness. For the 1K formulation, the cross linking
mechanism according to Equation 1 can be applied:
Accessible carboxylic groups of the polymer are chelating to the sur- References
faces of the nanoparticles. This reaction is usually very fast and starts
upon drying. This fast cross linking reaction is the main reason for the [1] Burgard D., Herold M., European Coatings Journal, Issue 7-8/2013
acceleration and increase of hardness development in coating ALX2. [2] Pilotek S., Burgard D., Herold M., Steingröver K., The Waterborne
For the 2K formulation ALX4, there are two different cross linking Symposium, New Orleans, Feb. 18-20, 2009.
mechanisms as there are two different cross linkers in the formula- [3] Burgard D., Herold M., Farbe und Lack, 117, 6 (2011) 14-18.
tion. Here the different kinetics of the two cross linkers may play an [4] Herold M., Burgard D., Steingröver K., Pilotek S., PCI Magazine, August
important role. The reaction of the carboxylic groups with the nano- 2010, 24-27.
particles is very fast and may be faster than the undesired reaction [5] Koromminga T., van Esche G., Plastics Additives Handbook, Zweifel, H,
with the isocyanate as shown in Equation 2. Ed., Hanser, 2001.
By the fast reaction of the nanoparticles, shown in Equation 1, a large [6] Horne S. E., Suarez J. J., SPE J. 1969, 25, 11, p. 34-38
portion of carboxylic groups may be blocked and are no longer ac- [6] van Esche G., Kromminga T., Schmidt A., Soc. Plast. Eng., Inc. Antec,
cessible to undergo a reaction with isocyanates, shown in Equation Conf Proc., 1998, 2837
2, so that more isocyanate can react with available OH- groups for [7] Vincent O., Osmont E., Soc. Plast. Eng., Inc. Antec, Conf Proc., paper 131,
urethane formation. In addition, less amides (and possibly CO2) as re- 2002
action product of isocyanate and carboxylate are present in the coat- [8] Wypych G., Handbook of Antiblocking, Release, and Slip Additives, 1st
ing film to influence the final film properties. There is the potential to Ed, ChemTec
Equation 1 Equation 2
Figure 5a: Development of Koenig hardness within the first t wo Figure 5b: Development of Koenig hardness within the first three
days weeks
A B

46 S m a r t c o at i n g s
Source: Victor Burnside - Fotolia.com
Permanent hydrophobic
and easy-to-clean effects
Universal surfactants for different coatings systems. By Carina Deschamps, Lada Bemert, Hugh Gibbs and Michael
Groteklaes, OMG Borchers and University of Applied Science Krefeld.
Functional surfaces with dirt repellent properties are increasingly Nature as a model
important as it takes less effort and surfactants to clean them.
Existing easy-to-clean effect additives are based on fluorosilanes Looking at the surfaces of particular plants like the lotus, and their abil-
and polysiloxanes. Their application is limited to special coating ity for self-cleaning thanks to their microstructured superhydrophobic
systems and their effectiveness often declines with time. In a surface, scientist established the term Lotus-Effect in the 1970s.
bachelor thesis the permanent easy-to-clean effect of non-ionic The self-cleaning of such surfaces is not particularly durable as the mi-
monomeric and polymeric fluorinated surfactants as additives
in various coating systems has been investigated. The additive
developed, with additional functionalities, is universal and may Figure 1: Over view
be crosslinked into different coating systems. The additives were
tested in a range of solventborne and waterborne coating sys-
tems. The easy-to-clean effect evaluation was performed with re-
sistance to abrasion stress for water- and dirt repellence and their
permanence. The results show that fluorinated polymers with
multiple functionalities especially generate hydrophobic surfaces
with a permanent easy-to-clean effect in different coatings.
A t first glance, most of the coating industry’s technical needs are well
satisfied. If you take a closer look at the scientific papers, however,
you discover that functional surfaces inspired by nature, which are then
used as the inspiration for future technology, are often mentioned as
a theme of interest. Functional coatings ensure that the product deliv-
ers a special performance [1], [2]. A study by the DFO shows that there
is great interest in functional coatings in industry, especially for self-
cleaning/easy-to-clean surfaces [3]. Easy-to-clean surfaces are defined
as hydrophobic surfaces that could be cleaned with less effort, to which
less dirt adheres and that have a contact angle with water of between
90 °and 130 °. Self-cleaning surfaces don’t need to be cleaned - water
and light do the job. The dirt repellence depends on the bad wettability
of the structured surface – the contact angle is higher than 130 °.

S m a r t c o at i n g s 47
lon in pans, or sprays with easy-to-clean effect in DIY. They have nu-
merous disadvantages, such as poor adhesion, poor recoatability, and
Results at a glance low permanence of the effect.
The aim of this work is to find a universal, permanent easy-to-clean
űű Using fluoropolymers one can create hydrophobic, water- additive for different coating-systems. In addition, it addresses the
repellent, permanent easy-to-clean surfaces in coatings. question of a method for evaluating the easy-to-clean effect, as there
is no industrial standard method available. An ASTM standard is un-
űű Best results are obtained using most hydrophobic modified der development. The following illustration summarises the experi-
fluoropolymers. mental part in the research (Figure 1).
űű After modification, there was permanence in the coating. Non-ionic addititves tested
űű The contact angle is high enough for an easy-to-clean effect. In this work, three groups of additives were tested as to their per-
formance of the easy-to-clean effect: hydrocarbon- and fluorosur-
űű The new coatings are easy to clean, environmentally re- factants and low molecular weight fluoropolymers. Surfactants are
sponsible and cost effective surface-active agents. Owing to their hydrophilic and hydrophobic el-
ements, and their amphiphilic structure, they orient themselves at the
interface, for example coating/air. The surfactants used in this work
are non-ionic, which means that their head-group carries no charge.
Both the hydrocarbon and the fluorosurfactants have ethoxylate-
groups as their hydrophilic part.
Low molecular weight fluoropolymers, tested here, show high hydro-
crostructure has little resistance to mechanical stress [4-10]. The chal- phobicity with surface activity. They allow the highest depression of
lenge is to enrich the permanent cleanability of the surface. Until now the surface tension.
there are different types of products with easy-to-clean effects. On Table 1 and 2 provide an overview over the tested additives. The fluo-
the one hand there is the Do-It-Yourself sector, with sprays. On the ropolymers are more surface active than the others. Table 1 shows
other, there are industrial technical surfaces such as Polydimethyl- the additives tested in the coating systems.
siloxanes and Polytetrafluoroethylene, like “Teflon®”. New binder al- The main objective of the paper is to explain the development pro-
ternatives are Polysilazanes for anti-graffiti applications and Sol-Gel- cess. At the end, the additive with the best results with respect to
Coatings with fluorosilanes [4, 10, 11]. competitor additives were compared. The competitor products are
Possible applications for coatings with easy-to-clean effect include car applicable only in certain systems, depending on the polymerisation
wheel rims, furniture and floor coatings, car signs, anti-graffiti coat- and solvent. The overview is provided in Table 2.
ings and general industrial applications, where the cost-effectiveness
could be increased with lower cleaning demand. The positive environ- How to achive permanence
mental effect is also important, as fewer cleaners and surfactants are
needed. Easy-to-clean coatings can protect railways carriages, build- In order to achieve the permanent easy-to-clean effect, the molecule
ings and possibly cars. should be anchored at the surface. Modification of additives simultane-
Existing market products with an easy-to-clean effect are additives ously with different functionalities allows crosslinking of the additives
based on fluorosilane or polysiloxanes, non-sticking coatings like Tef- into different coating systems, e.g. polyurethanes, acrylics, UV-cured 
Figure 2: Results of contact angle measurements with demineralised water in the 2-pack PUR-system, water-based. The additives
are ordered by increasing hydrophilic properties.

48 S m a r t c o at i n g s
 systems, melamines. The functionalities, inserted into the molecular drophilic properties in each group. They are categorised according to
structure are vinylic- and hydroxylic, both of which are on the hydro- three groups: fluoropolymers, fluoro- and hydrocarbon- surfactants.
philic part of the additive to ensure polymerization into each coating The blue bars are not modified (NM); the red ones are modified (M).
system with the hydrophobic part towards the air. To ensure compara- The Y-axis shows the contact angle in degrees. The value of the er-
bility of the effect, the concentration of the additives is kept constant. ror bars is calculated from the repeated measurements on different
places on the coating and after approximately 48 hours.
Measurement principles used Based on the results of Figure 2 and the results from the other coating
systems, the following conclusions follow:
Industry standards for evaluating easy-to-clean effects from coatings ąą Most additives increase the hydrophobicity of the surface. The contact
are not available at present. For this reason, proprietary test methods angle is higher than the contact angle of the coating without additive.
were developed and used. ąą The fluoropolymer additives are better at creating an easy-to-clean
Wettability is one of the important criteria for easy-to-clean effects. The effect in coatings than the hydrocarbon and fluorosurfactants.
value of the contact angle of the polymerised coating with water or oil ąą The highest contact angle generated is nearly 100° in the two-pack
provides an approximation of hydrophobicity and surface roughness. conventional polyurethane system.
The contact angle can be measured statically and dynamically. ąą In general, the modified additives show a slightly higher contact
Permanence of the effect was evaluated with the abrasion test with iso- angle than the unmodified.
propanol, which is often used in cleaners. If the additive is permanent ąą Compared to the competition, the fluoropolymers create higher
the contact angle should not change after numerous cycles of abrasion contact angles.
with isopropanol. If the additive is washed out, the contact angle will be ąą Fluoropolymers need to be used in lower concentrations as they
far lower after the abrasion. The testing procedure includes abrasion are highly effective.
with 5 mL isopropanol on cotton with different number of cycles and a ąą FP1 is selected as a good active ingredient for easy-to-clean addi-
weight 300 g above the cotton pad on the coating. To evaluate perma- tive, also due to the measurements in the other systems. It always
nency, the contact angle was measured before and after abrasion. The shows good contact angle results and the modified version will be
tests were performed on an abrasion tester. Pendulum hardness, gloss tested for coating permanency.
and haze and slip were also measured to see whether the surface is
rougher with and without additives, or after the abrasion. Measuring the permanence
To evaluate cleanability of the coating, a dirt suspension with a mix-
ture of dirt from the industrial environment was created, sprayed it Figure 3 shows the results of the abrasion stress with isopropanol in
over the coating and washed it with water in the dishwashing ma- different coating systems. The X-axis shows the four coating systems
chine. The dirt adhesion on the coating was tested by measuring the after 100 cycles in the abrasion tester. The Y-axis shows the contact
colour values before and after the dirt treatment. angle difference before and after stress with isopropanol. As the dif-
At first the additives were tested in four coating systems: waterborne ference of the contact angles increases, the permanency of the ad-
and solventborne two-pack polyurethane systems, conventional and ditive in the coating decreases. The unmodified fluoropolymer FP1
waterborne UV coatings. These systems are widely used in industri- shows a high contact angle difference after 100 cycles. After modifica-
al applications and UV-cured coatings are an environmental friendly tion, the contact angle difference of the polymer is lower than the val-
coating technology with great application especially for wood coatings. ues of the unmodified polymer. The values of the competitor and the
Investigations will now focus on other systems, including two pack modified fluoropolymer are comparable. They are both permanent in
clear coats, multi-layer coatings for automotive industry, unsaturated the coating systems. The modification makes our polymer permanent
polyester, epoxy system and coil coatings. in different coating systems.
Looking at the sample without additive, there was a negative contact
How additives influence the contact angle angle difference. This is the pure abrasion effect. The higher contact
angle after the abrasion test results from the surface roughness. The
One of the requirements of the easy-to-clean additive is its surface difference, resulting from the roughness, was taken into account in
activity. During polymerisation, the active substance should migrate
to the surface layer. Surfactants lend themselves for such applica-
tions due to their self-organising properties at the interfaces. The next Table 1: Additives in test
question is the value of the hydrophilic-lipophilic balance of the sur-
factant molecule needed for the migration tendency to the liquid-air
Hydrophilic properties
interface. Systematic investigation was started from the well-known
carbon-based fatty alcohol ethoxylates over the short-chained per- Hydrocarbonsurfactans C13E5 C13E7 C13E10
fluorinated surfactants to polymeric perfluorinated surfactants. Un-
modified and modified substances were compared, whereby the
modification with two functional groups should not have a large im-
Fluorosurfactants FS1 FS2 FS3
pact on the HLB value. Figure 2 shows the results for the contact angle
with demineralised water.
Since organisation of the chosen molecules was expected at the sur-
face with the hydrophobic part towards the air, the contact angle was Fluoropolymer FP1 FP2 FP3
measured with demineralised water on the coating with additive. Con-
tact angle provides a highly sensitive response that depends on the
surface hydrophobicity. Figure 2 shows the measured contact angels Table 2: Competitor additives
in the waterborne two-pack polyurethane system; results in the other
coating systems show the same tendencies. The X-axis shows the application area waterborne solventborne UV systems
tested additives, competitor product (X) and the coating without addi- Competitor X1 X2 X3
tives. The other additives are ordered from left to right by growing hy-

S m a r t c o at i n g s 4 9
the samples with additives. The measured values due to the abrasion additives or with those of the competitor.
effect were normalised according to: The measurement of gloss, haze, pendulum hardness and slip were
∆ a∙n[°] = ∆ an[°] – ∆ a0[°] not performed in evaluating the easy-to-clean effect, but were meas-
with ured to see whether our additives or modifications had any other ef-
∆ a∙n – plotted contact angle difference, fects. There were no negative effects when applying our additives for
∆ an – measured contact angle difference from sample with additive, pendulum hardness or gloss. The haze values were slightly better us-
∆ a0 – measured angle difference from sample without additive (zero). ing the fluoropolymer, which acts partly as a levelling agent.
In further investigations the optimal concentration of the fluoropoly-
The contact angle difference was measured and calculated using the mer in the coating were determined. This did not lead to the same ef-
following formula: fect for increased contact angles with higher concentration as with the
∆ an[°]=a’ [°]-a’’[°] competitor additive. It seems that the other effect is critical; increas-
whereby ing the concentration: over a defined concentration the contact angle
∆ a – contact angle difference, does not increase and is nearly constant. This is assumed to be due
a’ – contact angle before abrasion, to the migration of the additive in lower coating layers due to the oc-
a’’ – contact angle after abrasion. cupancy of the surface with fluoropolymer molecules. In other words,
one molecule of fluoropolymer takes about 3 nm2 (approximation) on
Figure 4 shows the results of the contact angle with the FP1 and the the surface. Only one layer of fluoropolymer is needed to achieve the
competitor in the four coating systems. The fluoropolymer is used at necessary effect. The concentration of active ingredient should be not
the same concentration as the competitor product. In this system, the higher, as since the surface area divides by 3 nm2, the residual mol-
modified fluoropolymer always has a higher contact angle than the ecules will migrate into the deeper coating layers and cause no ad-
competitor. However, if one uses 10 times the quantity of the compet- ditional increasing of contact angle.
itor product, the contact angle is now higher. In other words, the con-
tact angle depends on the quantity of the competitor additive used. Conclusion
Hardness and gloss are not influenced Using fluoropolymers it was possible to create hydrophobic, water-re-
pellent, permanent easy-to-clean surfaces in coatings. The best results
Generally it was not possible to create oleophobic properties with our were obtained with the most hydrophobic modified fluoropolymer. Af-
ter modification, there was permanence in the coating. In all four tested
Figure 3: Resistance to abrasion stress with isopropanol in coating systems, the contact angle is high enough for the easy-to-clean
detecting the permanence of the additives. effect. Similar effects were achieved in all four tested waterborne and
solventborne systems with one additive, but there is no universal com-
petitive solution. In conclusion: fluoropolymer additives could make your
coating functional – the cleaning effort decreases. It is also environmen-
tally friendly as you need less effort to clean the surface. Visually, your
product looks clean for longer. 
References:
[1] Stenzel V., Rehfeld N., Functional Coatings, 1. Auflage, Vincentz Network,
Hannover, (2011), 13
[2] Zhang Y. et.al., Recent progress of double-structural and functional
materials with special wettability, Journal of Material Chemistry, 2012, 22,
799-815
[3] Roths K., Gochermann J., Forschungsagenda Oberfläche, 1.Auflage,
DFO, Neuss, (2007), 86
Figure 4: Comparison of the additive with the best contact angle [4] Brock T., Millow S., Schmutzabweisende Oberflächen, Roempp Online,
in the tests before, the modified Fluoropolymer 1, with the 3.17, Georg Thieme Verlag, (2009), Dokumentkennung: RD-19-06128
competitor additives and with zero additive. [5] Barthlott W. , Neinhuis C. , Purity of the sacred lotus, or escape from
contamination in biological surfaces, Planta, 1997, 202, 1-8.
[6] Bhushan B., Jung Y. C., Koch K., Self-cleaning efficiency of artificial super-
hydrophobic surfaces, Langmuir, 2009, 25, 3240–3248
[7] Nosonovsky M., Bhushan B., Multiscale dissipative mechanisms and
hierarchical surfaces: friction, superhydrophobicity, and biomimetics,
Springer, Heidelberg, 2008
[8] Nosonovsky M., Bhushan B., Roughness-induced superhydrophobic-
ity: a way to design non-adhesive surfaces, J. Phys. Condens. Matter,
2008, 20, 225009
[9] Nosonovsky M., Bhushan B., Biologically-inspired surfaces: broadening
the scope of roughness, Adv. Funct. Mater., 2008, 18, 843–855
[10] Barthlott W., Neinhuis C., Biologie in unserer Zeit, 05, (1998), S.314
[11] Sepeur S., Laryea N., Goedicke S., Groß F., Nanotechnology, Vincentz
Network, Hannover, 1.Auflage, (2008), S. 40 ff
[12] Mahn M., Osterod F., Jung und Wirkungsvoll, Farbe und Lack 11, (2010)

50 Crosslinkers
Source: teptopng - Fotolia.com

The best of
two worlds
Silane-urethane hybrid crosslinkers create scratch-resist-
ant clearcoats. By Tobias Unkelhäußer, Markus Hallack,
Hans Görlitzer and Rainer Lomölder, Evonik Industries.
A range of silane-urethane hybrid crosslinkers has been de-

signed to generate multifunctional, scratch resistant coatings
usable on a variety of substrates. Addition of one such product
to a 2K polyurethane automotive clearcoat greatly increased
scratch resistance. An ambient-cure clearcoat applied over
wood as well as plastic also showed very high scratch resistance. Table 1: Properties of 2K PUR System modified with various
amounts of Crosslinker M 95
A new and versatile product family of crosslinkers and binders

for high performance coatings has been developed. The novel
approach combines the benefits of silane chemistry with the perfor- Level of
mance of polyurethanes, providing excellent scratch resistance while Crosslinker 0% 10 % 30 % 50 % 100 %
maintaining urethane properties in coatings. M 95
3-isocyanatopropyltrimethoxysilane (IPMS) is the core building block
Hardness
of the novel technology platform and provides a broad freedom of 171 174 164 162 143
(König) 1 d
design by creating tailor-made binders and crosslinkers. This resin
concept also enables non-isocyanate (NISO) crosslinking technology
Erich-
that matches or exceeds polyurethane performance.
sen cupping 8.0 8.5 7.0 6.0 7.0
Modern aliphatic 2K polyurethane clearcoats are considered as to-
(mm)
day’s benchmark for environmental etch, weathering and durability.
They are in general well known for their excellent balance of flexibility
and hardness. Furthermore, superb overall properties and good ad- Impact, direct
> 80 > 80 > 80 > 80 80
hesion to various substrates are advantages which have helped the (in-lb)
technology to set the benchmark in clearcoats for the automotive in-
dustry in recent decades.
Here, the automobile topcoat in particular, which is crucial to a car’s Acid etch
visual appearance, needs to have several properties each at the high- (20 %
47 °C / 48 °C / 44 °C / 40 °C / 46 °C /
est level to satisfy the premium requirements of the car manufactur- H2SO4), first
65 °C 67 °C 62 °C 61 °C 71 °C
impact/de-
ers and their customers.
stroyed
Clearcoats need to meet very high requirements

MEK
> > >
resistance ( > 150 > 150
The clearcoat layer of a car (approximately 40 μm thick) is its first de- 150 150 150
double rubs)
fence barrier against all kinds of mechanical, physical and chemical

Crosslinkers 51
still a need to significantly improve certain characteristics - particularly

the scratch resistance - while also if possible adding more features
Results at a glance such as an easy-to-clean effect [1].
This trend is not just limited to automotive clearcoats. It is also true for
űű The “Vestanat EP-M” range is a family of silane-urethane hy- ambient temperature curable clearcoats applied on other substrates
brid crosslinkers designed to generate multifunctional, scratch such as wood or plastic, which are more heat sensitive.
resistant coatings usable on a variety of substrates. Some will
cure even at ambient temperature. Crosslinking of silane-urethane systems outlined
űű These crosslinkers and binders can be used in automo- An appropriate way to gain reliable enhancements, in increasing the
tive OEM and refinish applications and on many different sub- scratch resistances of clearcoats and to satisfy market needs and
strates such as wood, plastic and metals or glass etc. trends concerning a further integration of functions, is ensured by the
use of silane-urethane hybrid crosslinkers.
űű Incorporation of these products into an existing 2K polyu- As shown in Figure 1, the IPMS that represents the key building block
rethane clearcoat formulation had little effect on most physi- of the system can be converted with any kind of isocyanate-reactive
cal properties but produced a considerable increase in scratch groups (R-group) preferably with the hydroxyl groups of diols, polyols
resistance. High levels of scratch resistance were also obtained or oligomeric diols to build a urethane linked but alkoxy-silane func-
on an ambient-cure clearcoat applied over wood. tional non-isocyanate (NISO) crosslinker/binder.
The choice of R-group will primarily determine the properties of the
űű Resistance to suntan lotion of automotive clearcoats could crosslinker and hence will also significantly influence the attributes of
also be improved. the coating. For example, the longer the backbone of the crosslinker
the more it acts as a flexibiliser in the coating. In contrast, a branched
űű Other modifications can also be incorporated, such as flu- and short R-group will result in higher hardness. It is also possible in
orine, which was shown to produce a more hydrophobic and principle to use diols with additional functionalities incorporated, such
oleophobic surface, leading to easy-to-clean properties. as fluorinated compounds, to create coatings which are even more
multifunctional.
But due to the fact that the urethane linkages are imparted by formu-
lating with IPMS-based crosslinkers, the beneficial properties which are
expected from aliphatic polyurethanes such as high chemical resistance,
good adhesion and excellent mechanical properties, are retained.
There are two possible reaction mechanisms by which the IPMS-based
influences and thus has to resist many attacks – whether by UV radia- crosslinkers shown can react via their alkoxy groups in coating sys-
tion, abrasion caused by car wash brushes and dust, leaving micro- tems. One reaction is a combination of hydrolysis and condensation
scratches, or aggressive chemicals such as acidic rain or suntan lotion to form siloxane linkages (Si-O-Si). The other crosslinking mechanism
causing swelling and discolouration (haze). is a transesterification reaction which occurs only if a hydroxyl group,
The clearcoat needs to remain shiny, glossy and transparent for as for example that of an acrylic or other polyol, is present. Each of these
long as possible – even after years it should still look like new. The mechanisms can be accelerated by using appropriate catalysts which
quality of clearcoats has steadily improved, but nevertheless there is are extensively described in diverse publications [2, 3]. 
Figure 1: IPMS-based silane-urethane hybrid crosslinker containing urethane groups, terminated by tri-functional alkoxy-silane
structures

52 Crosslinkers
 This paper describes a performance analysis of coatings which have er (hexamethylene diisocyanate) “Vestanat HT 2500 L” (PUR-hardener
been crosslinked using unique alkoxy-silane terminated crosslinkers , NCO:OH ratio 1:1) and several levels of the silane-urethane hybrid
which contain urethane structures within their backbone. The paper crosslinker “Vestanat EP-M 95” (crosslinker M 95, low viscosity liquid,
focuses on systems which facilitate the self-crosslinking mechanism of 100 % solids) where the R-group is a short chain, linear aliphatic diol.
the alkoxy functionalities (Figure 2). Also, to accelerate the crosslinking of the alkoxy groups a catalyst
The new silane-urethane hybrid crosslinkers were used both in stand- “Vestanat EP-CAT 11” (Cat 11, alkyl ammonium salt) was added [4].
ard OEM-clearcoat 2K PUR formulations and in 1K self-crosslinking, The clearcoat concept based on these products is shown in Figure 3.
moisture-cure systems. To provide a broader understanding of the influence of siloxane net-
works on the resulting coating properties, the dosage of crosslinker M
Test procedures summarised 95 was varied. In the figure, the 50:50 pbw blend refers to the ratio of
the solids of acrylic polyol plus PU crosslinker and the silane-urethane
To analyse the impact of siloxane networks in standard 2K PUR sys- hybrid crosslinker. In other words, the hybrid crosslinker was added
tems, clearcoats were formulated using an acrylic polyol, an HDI-trim- at the same amount (on solids) as the resin plus PUR hardener. The
Figure 2: Hydrolysis-condensation reaction forming siloxane net works
Figure 4: Residual gloss after modified scratch test of a 2K PUR

Figure 3: Example of a clearcoat formulation with 50:50 pbw (on system formulated with PUR-hardener and additional levels of
solids) of resin/PUR-hardener and crosslinker M 95 crosslinker M 95

Crosslinkers 53
clearcoats were cured at 140 °C (oven temperature) for 22 minutes. crosslinker was compared with a 2K PUR system with regard to resist-
ance against an SPF 30 suntan lotion in a temperature gradient oven
Scratch resistance shows significant improvement test for 30 minutes.
While the standard 2K PUR coating shows swelling and discolouration
The compatibility of the hybrid crosslinker with other formulation con- (Figure 6) even at 37 °C, the boosted formulation with 100 % hybrid
stituents was excellent in general. In all cases high gloss clearcoats crosslinker remains stable even at higher temperatures up to 55 °C.
were obtained (82 ± 2 gloss units at 20 °) The better resistance against suntan lotion can be explained by an
As shown in Table 1, all coatings based on the hybrid crosslinker show increase in crosslink density via the dense siloxane network [5, 6].
a well-balanced mechanical property profile which is satisfactory
for many high end applications. When the concentration of hybrid Silane-urethane hybrids for moisture curing systems
crosslinker is increased, the hardness and flexibility of the clearcoat
slightly decreases, while chemical resistance against sulfuric acid is Even in ambient curing systems, special silane-urethane hybrid prod-
maintained. ucts can act as a crosslinker as well as a binder at the same time to
It becomes apparent that the typical polyurethane characteristics create multifunctional scratch-resistant coatings. In the field of wood
such as outstanding hardness combined with flexibility (reference coatings in particular, the drying speed of the coating is an essential
system = 0 % dosage hybrid crosslinker) were only slightly diluted by factor. For this special purpose the “Vestanat EP-MF” product family
the addition of the siloxane network. But even in the 100 % system the was designed based on products of the “Vestanat M” family but de-
mechanical performance is still at an excellent level, as confirmed by signed to be curable at room temperature (see Figure 7).
the direct impact test. “Vestanat EP-MF 201” (crosslinker MF 201) is a solvent and isocyanate
The scratch resistance was tested by a modified crockmeter test (wet free, ready-to-use version of an alkoxy-silane terminated crosslinker
abrasion). The test performed consists of a bar with an abrasive textile or binder requiring no other crosslinkers (i.e. polyisocyanates). It can
brushing the coated surface in a detergent solution 160 times with a be used for 1K moisture curing systems. The resulting coatings show
2 kg weight attached to it to provide sufficient force. After this test, outstanding scratch, stain and chemical resistance.
the gloss is measured again and the residual gloss is calculated in 2K formulations are obtained by combining the silane-terminated
percent. This test is similar to scratch tests for automotive OEM re- product with polyols. The right mixing ratio between both compo-
quirements [5]. nents must then be determined. Due to the formation of an inter-
The resistance against scratching increases dramatically with the ad- penetrated network, properties including scratch, stain and chemical
dition of hybrid crosslinker. Figure 4 shows that even small propor- resistance can be adjusted on demand. There is also no need to add
tions of approximately 10 % show a significant effect. The residual polyisocyanate crosslinkers. The final coating is still a NISO system and
gloss after the modified crockmeter test was significantly higher com- – depending on the characteristics of the polyol – potentially low in
pared to the reference system (0 % dosage hybrid crosslinker). VOC.
The scratch resistance differences of the formulations can be meas- Figure 8 shows a technology comparison between a 2K PUR (left) and
ured but they are also easily visually detectable (Figure 5). a 2K formulation based on use of the silane-terminated crosslinker-
binder (right). Both systems were applied on wood and were scratched
Resistance to suntan lotion can also be improved using a modified crockmeter test. While many and very distinctive
scratches occur on the unmodified 2K PUR, the formulation based on
The “100 %” formulation was also investigated in relation to other silane crosslinking resists the abrasive attacks keeping its shiny, initial
aspects of chemical resistance. Resistance against suntan lotion is appearance.
known to be very relevant for automotive interior coatings but recent- In addition to the field of wood coatings, there is also an attractive
ly this has also become relevant for automotive exterior clearcoats. application in terms of plastic coatings. Here the same properties will
The clearcoat formulation based on the 100 % dosage of hybrid lead to scratch, stain and chemical resistant coatings. This outstand- 
Figure 6: 2K PUR with additional dosages of crosslinker M 95

Figure 5: Modified crockmeter test: 2K PUR (left) vs. 2K PUR (left - less structured surface at 55 °C) vs. 2K PUR (right - highly
formulated with 100 % addition of hybrid crosslinker (right) structured surface due to less suntan resistance at 55 °C)

54 Crosslinkers
 ing product profile is essential for sporting goods or in the automotive enhance the easy-to-clean behaviour of a coating significantly. It was
industry. also noted that all clearcoats tested had in general a high abrasion
resistance. The only deficit observed was a continuing decrease of
Fluorine incorporation enhances cleanability hydrophobicity after several scratch test cycles. 
The backbone of the novel crosslinker technology is variable, which

leads automatically to a high freedom of design for creating tailor- REFERENCES
made crosslinkers or binder with multifunctional qualities in the fu-
ture. [1] Roths K., Gochermann J., Forschungsagenda Oberfläche,
An experimental (not currently commercially available) fluorine-con- 1. Auflage, DFO, Neuss, 2007, 86.
taining silane-urethane hybrid hardener was investigated. Fluorine is [2] Lomölder R., Görlitzer H., Hallack M. et al., Coating Agent
well known for its positive effects on surface properties, such as the With High Scratch Resistance, Patent Application EP 2 676
improvement of water and oil repellency of coatings, also known as 982, 2012.
the easy-to-clean effect [7]. One indirect but valid method for detect- [3] Witucki G.: J. Coating. Technol. 1993, Vol. 65, pp 57-60.
ing the hydrophobicity of surfaces is to measure the contact angle of [4] Lomölder R., Raukamp A., Nauman S. et al., Adducts of
a drop of liquid onto that surface. In this case water and squalene, a Isocyana toalkyl Trialkoxysilanes and Aliphatic, Alkyl-
triterpene which can be obtained from shark liver oil, were used as branched Diols or Polyols, Patent application EP 2 641 925,
liquids. US 20130244043, 2012.
Clearcoats were formulated both with the “Vestanat® EP-M 95” (refer- [5] Noh S., Lee J.W., Nam J.H. et al., Prog. in Org. Coat. 2012,
ence) and with several levels of the experimental fluorine containing Vol. 74, pp 192-203.
silane-urethane hybrid crosslinker. The coatings were cured at 140 °C [6] Plueddemann E. P.: Silane Coupling Agents, Plenum Press,
(oven temperature) for 22 minutes. New York, 1982, pp 141-181.
The results obtained, shown in Table 2, demonstrate that even small [7] Gururaj N. M., Arvind R. S., Ramanand N.J. et al., Prog.
proportions of a silane-urethane crosslinker containing fluorine can in Org. Coat. 2012, Vol. 75, pp 139-146.
Table 2: Easy-to-clean effect of silane-

Figure 7: Silane-urethane-hybrid crosslinkers based on IPMS designed for creating urethane hybrid crosslinkers containing
multifunctional, scratch resistant coatings in different systems and curing conditions fluorine
Crosslinker Fluorine
Contact angle
M95 content crosslinker
Water Squalene
100 % 94 33
95 % 5% 109 72
85 % 15 % 113 72
Figure 8: Modified crockmeter scratch test : 2K PUR (left) vs. 2K based crosslinker MF
201 formulation (right)

W o r ld o f C o l o ur 55
Source: InPixKommunikation - Fotolia.com

Shiny Season
The reflective, mirror-like
properties of christmas tree
ornaments are usually gai-
ned by a silvering solution
used as a coating on the
inside. On the outside, a co-
lourful lacquer over a white
basecoat is applied.
Shaping UP
Traditionally, glass orna-
ments were blown by hand
over a bunsen burner.
Nowadays, most factory-
produced ornaments are
shaped by compressed air
blown in the mold.

56 H a r de n e r
Source: You can more - Fotolia.com

Standing
on perfor-
mance
High performance waterborne hardener for zero VOC
self-levelling floors. By Shuyuan Liu and Tushar Trivedi,
Incorez Ltd.
thus are easy to apply and can level into a smooth film or layer after
A new water-soluble epoxy hardener for epoxy-based floor application. Water-based curing agents can eliminate or reduce vola-
coatings has been developed by using a controlled molecu- tile organic compounds (VOCs) in the formulations, and so reduce the
lar architecture. The hardener is VOC-free with very low free odour and environmental and health risks associated with the pres-
amine monomer levels. Advantages include excellent work- ence of such compounds.
ability and mechanical properties, low shrinkage, long pot life However, most amine-based hardeners have strong unpleasant
yet fast cure. Highly breathable coatings permit application amine odours and eliminating solvent alone cannot solve such a prob-
onto damp and green concrete. lem. It is therefore desirable that the hardener itself should have a low
or zero odour.
T wo-pack amine-epoxy resins are widely used in applications rang-

ing from coatings, adhesives and composites to civil engineering
applications such as formulations for concrete flooring, self-levelling
Despite recent advances in WB epoxy technology, there remains a
need for epoxy hardening systems and water-dispersible curing
agents for epoxy resin formulations which are easy to mix, low odour,
flooring and grouts. Despite recent advances in this technology, there have a suitable pot life (in the range of up to 1 hour), rapid cure (even
is a constant need for improvement in order to meet ever more strin- at low temperatures) and provide high hardness after curing in order
gent legislation and customer demands for better performance at
lower cost.
Self-levelling floors are an important application for epoxide coatings Figure 1: Architectures of t wo epoxy amine adducts
in that they provide relatively thin coatings of high hardness and wear
resistance. These systems are applied to floor areas that demand
exceptional performance and hygiene such as ‘clean rooms’, baker-
ies, dairies, food processing areas, pharmaceutical production areas,
motor showrooms, workshops etc. They are easy to apply by simply
spreading the compound to the required thickness with a trowel.
Benefits and limitations of waterborne epoxies
Waterborne and solvent-free epoxy technology is particularly attrac-

tive in floor coating applications for environmental reasons. Water-
based epoxies are normally two-component systems consisting of a
liquid epoxy resin and a water-based amine-functional curing agent.
The properties of the amine functional curing agent are vital to coat-
ing performance.
Many waterborne epoxy systems are relatively low in viscosity and

H a r de n e r 57
in low porosity and therefore poor water vapour transmission, which

would lead to delamination due to the osmosis effect from damp
ground.
Results at a glance The root cause of shrinkage on curing
űű Epoxy-based technology for coating applications such as Shrinkage is caused by high tension in a cured network which has
self-levelling flooring faces great challenges in combining VOC a high level of internal energy. The architectural design of the hard-
compliance, high performance, low odour and low cost. ener is critical to controlling the level of shrinkage. Poor distribution
of crosslinking or branching sites can lead to high localised tension
űű A new water-soluble epoxy hardener has been developed in the polymer network. This is increasingly a problem in high build
to meet technological, economical and legislative requirements systems such as self-levelling formulations where the binder content
in concrete floor protection. is normally low.
This kind of resin dilution means there is more ‘space’ between the
űű The hardener is VOC-free with very low levels of free amine epoxy and hardener. The evaporation of volatile components, in this
monomer, allowing low hazard zero emission formulations to case water, is relatively slow compared to thin-film coating applica-
be produced at costs equal to or below those of existing WB tions. Therefore, the space between the resin molecules remains little
epoxy hardener systems. changed during cure. As a result, the size and position of the binding
sites of the curing agent in relation to the size and structure of epoxy
űű Technical advantages include very good workability, long resins affects the level of tension generated from the coupling be-
pot life, fast cure and a very low level of shrinkage combined tween amine and epoxy groups.
with very good mechanical properties. Very good breathability Further to this, the compatibility of the whole system can be another
allows for use over damp and green concrete without blistering important factor in causing shrinkage. Phase separation and folding of
or delamination due to osmosis. the molecules would result in shrinkage due to progressive diffusion
and migration of binder molecules during the curing process.
Molecular engineering design of

an amine/epoxy adduct
Epoxy curing agents can be made by forming amine epoxy adducts.

Several factors are crucial to performance. In a very simplified scheme
to provide a fast return to service. shown in Figure 1, the amine epoxy adduct can show distinctly dif-
In addition, the final coatings should exhibit low shrinkage and low or ferent architectures in terms of the type of building blocks and the
no colour so that they can be used for transparent coatings without placement of reactive amine groups. The dark green arrow blocks
changing the base colour of the material to which they are applied. represent amine functional groups and the red ‘inverted’ arrow blocks
Finally, they should preferably provide good adhesion on concrete, epoxide groups. Yellow, blue and green bars represent building blocks
good impact resistance, good water vapour transmission and excel- between the functional groups.
lent compressive strength. In Adduct A the amine functional groups are located close together
One of the biggest challenges of water-based epoxy hardeners for around some points of the adduct backbone. When mixed in a two-
high build applications is shrinkage of the cured product. High shrink- pack formulation, epoxy molecules would be dispersed evenly. Only
age would have many adverse effects, such as gaps/cracks around the those epoxy groups close to amine functional sites can react, leaving
edges of the applied floor and even delamination from the surface or unreachable amine and epoxy groups ‘starved’. The first impact would
substrate. be slow cure as a result of starvation. The second impact would be
High tension within the network of a high shrinkage system normally shrinkage caused by the pulling effect when these functional groups
leads to poor compressive strength and modulus. This also results have to move to allow coupling between amine and epoxy groups. 
Figure 2: A hardener sample (left) and the cured disc and strip of Table 1: Typical properties of the new epoxy hardener
self-levelling compound
Property Value
Amine value (mg KOH/g) 220 - 240
Active hydrogen eq. weight (g/kg) 200
Addition level (phr) 95 - 105
Typical viscosity at 20 °C (mPa.s) 8000 – 12000
Density (g/cm3) 1.05 - 1.10
Colour (Gardner) <1
Solids (%) 55 ± 2
Flash point (°C) >100

58 H a r de n e r
 In the case of Adduct B where the amine groups are spread evenly low viscosity (Table 1) and sweet, pleasant odour. The low viscosity
across the adduct backbone, the curing process and the structure of makes general handling easier for applicators and also reduces wast-
the cured network can be quite different. When dispersed evenly in a age in the drum or tank. The hardener is made without any solvent or
2K self-leveller formulation, epoxy and amine groups can react easily plasticiser, so is itself zero VOC.
without having to migrate, as all amine functional groups are equally This has been confirmed through a micro-chamber emission test on a
accessible. This leads to relatively fast cure, a low tension network and self-levelling formulation (Table 2) at 2 mm thickness. The result (Table
reduced shrinkage. 3) shows minimal emission levels and is classified as zero emission un-
Clearly the architecture of Adduct B is favoured in terms of its potential der AgBB/DIBt (German restrictions for VOC emissions for construc-
for rapid cure, low shrinkage, high breathability and good mechanical tion products).
properties. Meanwhile, the physical properties of the building blocks The synthesis process for the new curing agent has been optimised to
on the hardener backbone play an important role in compatibility and consume all of the starting amine compounds. The level of free (low
therefore, have a significant influence on the performance as well as molecular weight) amine is not quantifiable by standard GC and HPLC
shrinkage in a water-based two pack epoxy formulation. analytical methods. Low hazard formulations are critical for applica-
Accordingly, a new waterborne epoxy amine adduct curing agent has tions for schools, hospitals, food processing, homes and offices where
been developed which has been specifically engineered to have a de- the health and safety of people around is of high concern.
sirable architecture with relatively low viscosity and low colour. In a typical self-levelling epoxy formulation (Table 2), the hardener ex-
hibits excellent workability and flow characteristics as well as excellent
Environmental and application advantages surface appearance with matt finish and minimal pinholes. In Figure 2
(right) the cured self-levelling disc sample was made by pouring the
The new hardener is a pale yellow solution (Figure 2) with a relatively compound directly onto a polypropylene sheet and allowing it to flow
without trowelling. The smooth, even surface and thickness of the disc
clearly demonstrate excellent flow behaviour.
Table 2: Two-pack epoxy self-levelling floor formulation
Fast cure and low shrinkage
Part A Product Supplier Amount
As previously explained, the favourable hardener architecture and ex-
Curing agent “Incorez 148-700” Incorez 10 cellent compatibility with epoxy facilitate fast cure on application (typi-
Defoamer “Byk 1615” Byk 0.8 cally at 2-3 mm thickness) even at relatively low temperatures (15 °C,
Diluent Water 4 50 % RH). Under standard conditions the hardness can reach Shore D
Pigment “Tiona 595” Cristal Global 3.8
Filler “EWO” Sachtleben 13 Table 3: Emission evaluation according to AgBB/DIBt (note the
different units in test and requirement columns)
Filler Quartz powder M6 Sibelco 27
Filler Quartz sand (0.1-0.3 35
Emission tests 3 days 28 days
mm)
Results AgBB Results AgBB
Thixotropic agent “Deuteron VT 819” (3 Deuteron 0.4
µg/m3 requirements µg/m3 requirements
% aq)
mg/m3 mg/m3
Diluent Water 6
TVOC (C6-C16) 188 0 ≤ 10 7.2 0 ≤ 1.0
Total 100
Σ SVOC (C16-C22) 0 None 0 0 ≤ 0.1
Part B R dimensionless 0.439 None 0.003 0≤1
Epoxy resin “DER 358 (180)” Dow 9 Total VOC 11.2 None 0 0 ≤ 0.1
Total 109
Total carcinogens 0 0.0 ≤ 0.01 0 0.000 ≤ 0.001
Figure 3: Debonding of impermeable coating caused by moisture in substrate (left), but no debonding for semi-permeable coating (right)

H a r de n e r 5 9
60 in 24 hours and 70 within 48 hours. product (using the formulation in Table 2) has been test-
This is particularly beneficial for applicators, as the floor can receive ed according to EN ISO 7783-1/-2. At a film thickness of
heavy loads soon after applying, minimising any delays during con- 2 mm the water vapour diffusion rate is measured at
struction or refurbishment work, thus increasing productivity for the 2.85 g/(m2.d) corresponding to an equivalent air layer thickness of 8.2
end user. In addition to this, the smart hardener architecture means m, which indicates good breathability of the coating.
minimal shrinkage can be achieved, typically below 1 %. It is well known [1-8] that moisture in concrete can cause blistering
It can be seen in Figure 2 that after full cure the self-leveller sample and delamination of coatings that are water vapour impermeable (Fig-
made on a polypropylene sheet shows minimal curling, indicating a ure 2) by osmotic pressure build-up from water beneath the coating
low tension network. This was also demonstrated using a cured self- trying to evaporate. Good water vapour permeability can therefore
leveller strip cast from a 435 mm long silicon mould – no bending or prevent debonding of coatings from damp concrete substrates (Figure
curling, again illustrating very little shrinkage after full cure. This will 3), prolonging service life.
assist long term adhesion and prevent delamination, so ensuring the Table 4 shows some physical properties of the formulation in Table 1
long service life of the flooring system. after full cure (23 °C and 50 % relative humidity for 28 days). These
properties are typical for this type of system and meet the require-
Physical and chemical properties summarised ments for wide range of applications for concrete protection.
As industrial coatings can be subjected to a variety of conditions and
Water vapour diffusion rate through a sample of cured chemicals during their service life, a sample of the cured material also
underwent a 24 hour spot test with a range of chemicals and stains.
Figure 4 shows a comparison between the new hardener and a com-
Table 4: Physical properties of fully cured self-levelling epoxy system mercial equivalent. The resistance was rated according to the level of
residual marks from heavily damaged, marked as 0, to no effect at all
as 5. It can be seen that the new hardener system offers the better
Test Results
performance.
Bond strength by pull-off-test (EN 1542) 220 - 240
Bond strength by pull-off-test (EN 1542 200 All-round performance benefits
Bond strength by pull-off-test (EN 1542) 95 - 105
This summary shows that the architectural design of a new amine
Typical viscosity at 20 °C (mPa.s) 8000 – 12000 epoxy hardener by way of molecular engineering is able to meet in-
Density (g/cm3) 1.05 - 1.10 creasingly stringent market demands on legislation compliance, opera-
tor and environmental impact, and high productivity whilst showing an
Colour (Gardner) <1
excellent cost-performance balance in self levelling epoxy systems. 
Solids (%) 55 ± 2
Flash point (°C) >100
REFERENCES
[1] Guenter M., Hilsdorf H. K., Stresses due to physical and chemical
Figure 4: Chemical and stain resistance test, in graphical form actions in polymer coatings on a concrete substrate, Proc. Adhesion
and visually, where Sample A represents the new curing agent between polymers and concrete, Chapman and Hall, London, 1986, pp
8-21.
[2] Raupach M., Wolff L., Durability of adhesion of epoxy coatings on con-
crete, causes of delamination and blistering, Concrete Repair, Rehabilita-
tion and Retrofitting II, 2009, pp 921-928.
[3] Warlow W. J., Pye P. W., Osmosis as a cause of blistering of in-situ resin
floorings on wet concrete, Mag. Concrete Research, 1978, Vol. 30, No.
104, pp 152-156.
[4] Wisser S., Behaviour of solvent-free epoxy resin systems on water
absorbent concrete surfaces, Kunstharz Nachrichten (Hoechst).
[5] Defects in epoxy resin flooring, BRE Technical File No. 14, July 1986, pp
32-34.
[6] Pye P. W., Blistering of in situ thermosetting resin floorings by osmosis,
International Colloquium, ‘Industrial Floors’, Esslingen, 1995.
[7] Stenner R., Magner J., Influence of moisture from substrate to blistering,
International Conference on Polymers in Construction, 1995.
[8] Pfaff F. A., Gelfant F. S., Osmotic blistering of epoxy coatings on concrete,
JPCL, Dec. 1997, pp 52-64.

60 L e v e ll i n g A ge n t
Source: Cytec
Primed for improvement

Hydrophilic agent enhances levelling and intercoat adhesion.
By Michael Bessel, Guillaume Jaunky and Mark Heekeren, Byk-Chemie.
Acrylate levelling agents have little effect on the surface ener- The importance of surface energy in coatings
gy of coatings, while silicone or fluoro-based additives reduce
it. However, a high surface energy is desirable in primers to Levelling additives are an inherent component of many coating for-
increase intercoat adhesion. A new branched polyacrylate lev- mulations, helping to minimise differences in surface tension during
elling additive designed to increase surface energy has shown the curing process and provide a smooth surface appearance.
positive results in waterborne automotive primer surfacers. A standard polyacrylate levelling additive has a polymer backbone with
a linear molecular structure (see Figure 1). It has a relatively low Tg and
M any consumer goods used in our daily life are coated to achieve
a variety of features and beneficial effects. For instance, pack-
aging coatings protect foodstuffs from exposure to oxygen and the
is slightly incompatible with the coating matrix. The polyacrylate concen-
trates on the surface of a wet film and keeps the surface tension of the
coating constant during the curing process.
metal of a can from aggressive acids in beverages or tinned fruit. Pa- In order to obtain low surface energy of the coating or to coat contam-
per coatings on the pages of a magazine help to protect the print- inated substrates that exhibit areas of low surface energy, additives
ed art and allow the pages to be easily separated. Wooden floors based on modified polydimethylsiloxanes or fluoro-based chemistry
are coated to withstand humidity or to achieve scratch and stain are used (see Figure 1). Low surface energy is often desirable in coat-
resistance. ings when water repellency, water resistance, a low coefficient of fric-
In the automotive sector, excellent coating performance in terms of tion and easy-to-clean properties are required.
durability, scratch resistance, levelling and layer-to-layer adhesion is Due to regulatory restrains and environmental considerations, a trend
sought after. An OEM coating consists of a cathodic electro-deposi- towards developing more waterborne coatings has been observable over
tion (CED) coating on a metal substrate for protection against corro- the last few decades in the automotive industry. In general, an automotive
sion, then a primer surfacer layer followed by a pigmented basecoat coating system consists of three to four layers, as mentioned above.
and clear coat. The preparation of each of the coating layers requires Within such a multilayer coating system, low surface energy can have an
the use of a variety of additives for good wetting of the substrate, sta- adverse impact on the recoatability of a coating in relation to the other
bilisation of pigments or surface features such as carwash resistance. layers. Therefore, the first coating layer on the substrate must have the
highest possible surface energy and, at the same time, a surface ten-

L e v e ll i n g A ge n t 61
Testing the effects of additives on surface energy
Results at a glance A waterborne primer surfacer 1K OEM stoving system based on “Seta-
qua B E 270” (a saturated polyester resin) and “Bayhytherm 3246 XP”
űű Levelling additives are widely used in coatings to improve (an aliphatic self-crosslinking urethane resin) was chosen as a refer-
flow during cure and create a smoother surface. Standard poly- ence formulation and test results are shown in Table 1. The version of
acrylates have little effect on surface energy, while siloxane or the additive tested is the one sold as “Byk-3560”.
fluoro-based products reduce it. The surface energy of the cured coating was determined from the
contact angles with five standard liquids: water, glycerine, ethylene
űű While low surface energy is desirable in finishing coats to glycol, n-octanol and n-dodecane. The polar and disperse part of the
improve water repellency and reduce surface friction, it can in- coating’s surface energy were also calculated according to the Owens-
terfere with recoatability. Wendt-Rabel-Kaelble method.
As shown in Table 1, standard polyacrylate additives do not influence
űű A branched polyacrylate additive has now been designed to the surface energy of the cured coating (see entries 2 and 3). However, 
increase the surface energy of cured primer coats and improve
application of subsequent coats.
űű While primarily designed for use in waterborne systems, it Figure 1: Structures and features of standard levelling additives
can also be effective in any other coating with which it is slightly compared with the new product
incompatible. Optimum dosage is affected by a number of vari-
ables including curing temperature.
űű It was confirmed that in a waterborne primer

surfacer formulation the new additive provided better levelling
than a standard polyacrylate while also improving wetting by
the subsequent basecoat.
sion that is low enough to allow good wetting of the substrate. It is for
this reason that a polyacrylate levelling agent that significantly increases
the surface energy of cured coatings and paints has been developed.
Structure of the hydrophilic surface additive
A polyacrylate levelling additive modified with certain polyether grafts

has been developed to increase the surface energy of cured coatings.
A special chain transfer polymerisation technology was applied to cre-
ate a branched polyacrylate backbone with very hydrophilic polyether
graft structures, as shown in Figure 1.
The polyacrylate backbone is slightly incompatible with common coat-
ing matrices and this, with its branched structure, drives the polymer
to migrate to the surface. The polyether structures are responsible for
the increase in surface energy of the cured coating. The hydrophilic
polyether side chains can exhibit a linear or hyperbranched structure
to reduce the tendency of the additive to crystallisation.
The polyether side chains are incorporated into the polymer back-
bone in the form of polyether macromonomers (or macromers for
short). These are specific polymeric structures that contain one reac-
tive group at one chain end. This reactive group can be an acrylate,
methacrylate or vinyl group, for instance, and can be subjected to
radical polymerisation reactions with other conventional monomers.
This branched polyether-modified polyacrylate levelling additive (also
referred to below as a hydrophilic additive) is an excellent levelling agent
which provides its distinctive properties in a broad range of coatings.
In order to achieve the hydrophilic surface effect, the additive has to
be slightly incompatible with the liquid coating matrix in which it is
used (see Figure 2). Therefore, the hydrophilic additive is most effec-
tive in waterborne paints and coatings and in coatings with a very non-
polar formulation.

Figure 2: Images of water drops on different cured films modified with an hydrophilic additive: the hydrophilic effect is obser ved
when the additive is slightly incompatible with the coating
Figure 3: Optimum dosage of the hydrophilic additive in a primer Figure 4: Relationship bet ween the contact angle of water and
surfacer test formulation is reached at 0.3 wt % on total curing temperatures of the test primer surfacer formulation

L e v e ll i n g A ge n t 6 3
 the total surface energy of the film was increased to 58.5 mN/m by ap- off time of 10 minutes at room temperature was applied. Afterwards,
plying 0.3 wt % of the hydrophilic additive (see entry 5). The disperse the films were cured for 10 minutes at 80 °C and then for 20 minutes
part of the coating’s surface energy was reduced by around 50 % to at a temperature between 120 °C and 180 °C.
10.9 mN/m compared to the control without additive. In contrast, the As shown in Figure 4, the hydrophilic effect obtained with the additive
polar part of the surface energy was greatly increased to 47.6 mN/m. reaches its maximum at 0.3 % dosage at 160 °C, which is also the
The hydrophilic effect provided by the new hydrophilic additive is optimum recommended curing temperature for the primer surfacer
always accompanied by an increase in the polar part of the surface formulation. This implies that a lower curing temperature requires a
energy and a decrease in the disperse part, both to varying extents. It higher amount of the hydrophilic additive. Conversely, it is assumed
should be noted that the absolute values of surface energy obtained that both the coating and the additive suffer from degradation at 180
vary with the type of coating, the polarity of its formulation, its curing °C and long exposure times of 20 minutes.
procedure and the amount of additive used. The hydrophilic effect was found to be virtually independent of dry
It is important to add that the hydrophilic additive does not influence film thickness. The contact angle with water changed only from 32°
the surface tension of the liquid film or the wetting performance of the to 35° as film thickness increased from 10 µm to 45 µm. With no ad-
liquid coating on the substrate. ditive, the contact angle was also essentially constant at 87-88°. The
optimum curing conditions for the waterborne formulation were cho-
Several factors affect optimum additive sen based on the results shown in Figure 4: 10 min. flash-off time at
concentration room temperature after application with a wire bar, 10 min. at 80 °C
and 20 min. at 160 °C.
As mentioned above, the concentration of the hydrophilic additive in- The hydrophilic effect has also been observed to be dependent on
fluences the absolute values of the cured coating’s surface energy. the substrate. As shown in Table 2, the contact angle of water on the
Figure 3 shows a series of increasing dosages of the additive in a wa- cured coating indicates a stronger hydrophilic effect on the CED panel
terborne primer surfacer coating. The optimum effective concentra- compared to a glass panel. It is assumed that the hydrophilic addi-
tion was obtained using 0.3 wt % hydrophilic additive on total formula- tive interacts with the glass surface rather than floating to the air/film
tion, which thus corresponds to saturation. interface.
In many solvent-based paints, a higher dosage of around 1.5 wt %
of the hydrophilic additive is needed to provide the best results with Good wetting confirmed in
respect to the increase in surface energy. a waterborne coating system
The activity of the hydrophilic additive has been found to be influ-
enced by the curing temperature, as in the case of the reference The performance of the hydrophilic additive was then investigated in
primer surfacer formulation. The curing procedure was designed as a waterborne polyester-melamine primer surfacer formulation. Op-
follows: after application of the film on CED pre-treated panels a flash- timised levelling, as demonstrated by a significant reduction of Wa 
Table 1: Surface energy of a 1K OEM primer-surfacer calculated Table 2: How the substrate modifies the performance of the
according to the Owens-Wendt-Rabel-Kaelble method from con- hydrophilic additive
tact angles of five standard liquids determined with a Krüss “G2”
instrument
No Waterborne formulation based on Calculated surface energy of
“Setaqua B E 270/ cured coating in mN/m
No ESTA application, addi- Contact Calculated surface energy of Bayhytherm 3246 XP”
tive concentrations ap- angle in ° cured coating in mN/m Substrate Dosage of Contact Surface Dis- Polar
plied as recommended hydrophilic angle of energy perse part
Waterborne coating Water Surface Disperse Polar additive water in ° part
based on “Setaqua B energy part part
270” and “Bayhytherm
3246 XP” 1 Glass No additive 87 27.0 22.0 5.0
panel
1 Control without additive 89 27.4 21.8 5.6
2 Glass 0.2 wt % on 78 27.0 18.9 8.1

2 0.6 % polyether-modi- 89 25.0 21.4 3.6 panel total
fied polyacrylate
3 0.6 % polyacrylate with 88 26.5 22.5 4.0

polar modifications 7 CED No additive 88 26.8 21.2 5.6
panel
4 1.2 % silicone-free 84 26.9 21.5 5.4
surfactant
5 0.3 % hydrophilic 16 58.5 10.9 47.6 8 CED 0.2 wt % on 36 46.6 11.1 35.5
additive panel total

 and Wb surface smoothness values in comparison to standard poly- New additive has a broad range of applications
acrylates, was achieved in horizontal and vertical electrostatic spray
applications (ESTA) with the use of 0.2 wt % of the hydrophilic additive The increasing usage of waterborne formulations requires new solu-
(see Figure 5). tions for levelling and surface additives, especially in multilayer coat-
In addition to the very good levelling performance, the hydrophilic ad- ing applications. The newly developed hydrophilic additive exhibits
ditive increased the surface energy of the primer surfacer layer. In outstanding levelling performance and very good compatibility.
comparison to a standard polyacrylate for waterborne formulations, In addition, this additive increases the surface energy of a cured coat-
the use of 0.2 wt % of the additive increased surface energy of the ing and therefore improves the wettability and recoatability of the
cured coating by 18 mN/m (see Figure 6). film. Its use is not limited to waterborne formulations; it has also been
It was then confirmed that high surface energy makes for better wet- successfully applied in a number of solvent-based paints, UV-curable
ting of the primer surfacer layer by a waterborne basecoat. A (red) systems and powder coatings. However, a slight incompatibility of the
pigmented basecoat was applied to a panel coated with the additive- additive in the paint is required to observe the hydrophilic effect.
modified primer surfacer (Figure 7). The thickness of the basecoat was The uses of the hydrophilic additive are likely to be expanded into
increased from 0 µm at the top end to 25 µm at the bottom end of the much wider fields of application than those currently investigated. 
panel. The panel coated with the additive-modified primer surfacer
exhibits much better wetting and spreading with the red waterborne
OEM basecoat at low film thicknesses than the control panel without
additives.
Figure 5: Levelling performance of the hydrophilic additive used in a waterborne poly-ester-melamine primer surface on horizontally
and vertically coated panels (determined with a Byk “Wave-scan dual”)
Figure 6: Compared to a standard polyacrylate for waterborne Figure 7: The red OEM basecoat shows much better wetting on
systems, the hydrophilic additive increases the surface energy the primer surfacer modified with the hydrophilic additive than
of the cured coating (polye ster-melamine primer-surfacer) on the control panel

Source: platongkoh55 - Fotolia.com W o r ld o f C o l o ur 65
Coloured Trees
50,000 litres of protecti-
ve coatings were used on
Singapore‘s Gardens by the
Bay. This attraction consists
of the world‘s largest clima-
te-controlled glass houses
as well as 18 of the pictured
supertrees.
MImicking Nature
Not only the consevatories
of Gardens by the Bay but
also the trees are home to
many tropical plants. They
provide air intake and mimic
the ecological functions of
real trees.

66 Slip additives
Source: Mario Beauregard - Fotolia.com

Smoothing
the surface
Performance of structurally different slip agents
compared. By Juan Carlos Corcuera, Kim Quackenbush
and Ogul Arseven, Dow Corning Europe SA
Additives that improve surface slip properties have many ben- weight and chemistry of the silicone on the final performance prop-
efits in different applications. Tests are reported on various erties of the cured films. The degree to which the molecular weight
silicone and wax slip additives. A high molecular weight PDMS affects the slip (in terms of the Coefficient of Friction, CoF), hand-feel
material, supplied as an emulsion in special surfactants, is and scratch resistance of the cured film was evaluated, together with
shown to be very effective at low dosages. In some cases, com- any potential adverse impacts the different chemistries may have on
bining it with waxes may be beneficial. surface levelling, wetting and recoatability.
The active silicone families within this study differ in their chemistry.
S ilicone polyether technology has been available to the formula-

tor to enhance wetting, levelling and slip performance for some
years. The typically low molecular weight and high hydrophilicity - due
Type 1 materials are polydimethyl siloxanes (PDMS) that have high
to very high molecular weight. These are delivered as low viscosity
emulsions, meaning they are easy to incorporate despite the relatively
to polyoxyalkylene side chains - give excellent compatibility in coat- high viscosity of the active component. Type 2 are based on silicone
ings, paints or inks, but performance can vary significantly from one polyethers (SPE) and are classed as having low to medium molecular
formulation to another. weight. Typical commercial products on the market today are classed
These materials lack the very high degree of slip performance that as having low molecular weight. Typical structures of these materials
higher molecular weight silicones can bring, and the resulting hand- are illustrated in Figure 1.
feel is not luxurious or valued by the end consumer. The SPE materials differ from the PDMS based materials in two ways:
This paper will show how moving to higher molecular weight (MWt) sili- ąą The degree of hydrophobicity. Ethylene and/or propylene oxide
cone technology will allow the formulator to improve slip, hand-feel and
abrasion resistance to a degree that the end customer will appreciate.
Figure 2: Friction reduction in acrylic based flexographic ink with
Structure of different types of silicone additives different MWt silicone additives
In this study a variety of silicone based additives were tested in paints,

inks and coatings formulations, evaluating the impact of the molecular
Figure 1: Typical molecular structures of polydimethylsiloxane

(PDMS) (top) and silicone polyether co-polymer (SPE) (bottom)

Slip additives 67
acts as a compatibiliser in the coating or ink.

Results at a glance A number of wax additives, used to obtain similar property improve-
ments to silicones, were also evaluated. The full list of materials tested
űű Additives are widely used in the coatings and inks industries can be found in Table 1.
to improve surface slip properties. The reduced coefficient of
friction (CoF) allows for faster processing and protects coating The critical importance of slip properties
surfaces from mechanical damage during processing, transport
and use. Tactile properties may also be improved. Numerous coatings applications require a reduction in the coefficient
of friction (CoF). In the furniture coatings market, for example, an im-
űű Tests are reported on a number of silicone and wax ad- provement in slip properties can improve resistance to damage during
ditives designed to improve slip properties. High molecular international shipment, construction and in use. In the printing indus-
weight polydimethylsiloxane (PDMS) materials are not normally try, slip allows for faster production speeds, insurance against paper
used, as they are hard to incorporate and may cause surface jams and of course, sensory benefits for the end user. The molecular
defects. However, a material of this type has been developed weight of the silicone additive can vastly impact its slip performance, and
using special surfactants to avoid compatibility problems. this is seen consistently across multiple coating and ink formulations.
Figure 2 shows the static and dynamic CoF of a waterborne acrylic
űű In a range of tests, the high MWt PDMS additive was shown based flexographic ink with some of the different silicone additives
to provide better slip (lower friction) properties at lower addi- listed in Table 1. This shows a direct relationship between increased
tion rates than the more widely used silicone polyethers and silicone MWt and higher slip performance.The two CoF values for the
waxes. control without any additives are 0.865 and 0.803. While these are re-
duced by all the silicone additives, the highest reduction by far is seen
űű In some cases, further benefits could be obtained by com- with the silicone emulsion additive, with values of 0.167 and 0.117
bining waxes with this additive. respectively with 0.5 % dosage.
Figure 3 shows the static and dynamic CoF of a waterborne acrylic
based wood coating with two different dosages of silicone polyethers
and silicone emulsion, 0.2 % and 0.4 %. Again the biggest reduction in
CoF is with the silicone emulsion additive, so a lower dosage could be
groups on the silicone backbone impart some hydrophilic charac- used to achieve the same desired slip.
ter that typically improves their compatibility. Figure 4 shows the impact on the dynamic CoF of an overprint varnish
ąą The degree of polymerisation is typically far lower in SPE chemistry formulation and the effects of dose rate. This is quite significant up to
than in PDMS based chemistry and as a result the viscosity of the 0.5 %, then increasing to 1 % the reduction is not as significant as before.
active silicone material is orders of magnitude lower than that of Experience suggests that 1 % should be the highest dosage if the additive
the PDMS based materials. is well dispersed in the formulation, having on average great benefits be-
The use of pure PDMS-based materials is practically zero in paints, tween 0.1 % and 0.5 % in this type of formulation, inks and wood coatings.
coatings and inks due to their incompatibility with organic resins and
their tendency to cause surface craters. For the PDMS materials eval- Silicones can be more cost-effective than waxes
uated in this study, the delivery system is also critical to their perfor-
mance. The compatibility of these high MWt PDMS-based emulsions is In many instances waxes are used to lower the coefficient of friction.
dependent on the use of a non-traditional surfactant technology that Whilst these can appear efficient on a price per kg basis, this compari- 
Figure 3: Acrylic based wood coating with different MWt silicone additives

68 Slip additives
 son often looks quite different when these materials are compared to hand-feel’, having the control as reference with a value of zero. The 2
silicone-based materials on a cost-in-use basis. In Figure 5 the CoF of % HDPE wax emulsion sample was also rated as zero. It can be seen
a waterborne acrylic wood coating is evaluated when using synthetic in Figure 6 that all samples with 0.1 % of the silicone emulsion perform
waxes versus competitor’s grades of silicone polyethers and the high significantly better for a silky hand-feel than the samples with 2 % wax
MWt silicone emulsion additive in waterborne acrylic based wood emulsion alone.
coating formulation. The impacts on gloss of a combination of additives on this high gloss
Using the axis on the left hand side of the graph, the green line shows clear coat, measuring the gloss at an angle of 20°, are shown in Figure
the dynamic coefficient of friction. Abrasion resistance was measured 7. The silicone emulsion at the low recommended use level of 0.1 %
by change in gloss. Using the axis on the right hand side of the graph, has little impact on gloss. The dots in blue indicate the samples con-
the blue and red bars on the graph show the initial gloss and the taining the silicone emulsion.
gloss after 1400 cycles in a reciprocating abraser using felt pads with In some cases, the silicone emulsion + wax combinations (PE wax
a weight of 15 N. The calculated percentage reduction in gloss is re- emulsion (1), paraffin wax emulsion, and HDPE wax emulsion (1)) have
corded at the top of the two bars. higher gloss values than the sample containing silicone emulsion
In this case the emulsion has by far the biggest impact on CoF reduc-
tion compared to silicone polyethers and waxes, at vastly reduced ad-
dition levels by weight of the total coatings formulation: 3.5 % against Figure 4: The dynamic coefficient of friction shows the impact of
0.1 % if slip values are compared. So the highest MWt silicone emul- silicone emulsion on slip in a waterborne acrylic based overprint
sion has biggest impact in CoF reduction with a superior slip com- varnish
pared to waxes, and to achieve this, the addition level required for the
silicone emulsion is very low.
Synergy benefits of combining silicone with waxes
The effects of combining the silicone emulsion with different types of wax
emulsions will next be examined. The impact on surface modification,
hand-feel (something desirable in many applications), gloss, slip and abra-
sion in a waterborne high gloss acrylic wood clear coat are examined.
The silicone emulsion was combined with the wax emulsions used in
the work described above, where silicone emulsion is tested alone,
but with a lower wax dosage of 2 %, instead of 3.5 %. A second poly-
ethylene wax of interest for wood coatings was also evaluated.
The testing was carried out using a high gloss waterborne acrylic
wood clear coat. The panels prepared with waxes, silicone emulsion
and the combinations were all similar in appearance and were rated
by touching the surface and assessing what may be called the ‘silky
Figure 5: Impact of silicone additives and waxes on slip and abrasion resistance in waterbased acrylic wood coating

Sl ip a ddi t i ves 69
alone. Conversely, the PE wax emulsion (2) had a significant impact on Using the axis on the left hand side of Figure 8, the green line shows the
gloss, reducing it from the 109.5 of the control sample to 82. coefficient of friction. Abrasion resistance was measured by change in
In all cases, silicone emulsion plus wax showed a significant improvement gloss. Using the axis on the right hand side of the graph, the blue and
in slip over samples with waxes alone (see Figure 8). Likewise, in all cases, red bars on the graph show the initial gloss and the gloss after 1400
the addition of 0.1 % of the silicone emulsion + wax showed a significant cycles. The calculated percent reduction in gloss is recorded above
improvement in abrasion over the wax-only sam- the two bars.
ples. The data was obtained with a reciprocating abraser
using felt pads with a weight of 15 N. Why the silicone emulsion gives good performance
The presented additive is an ultra-high molecular weight silicone dis-

Table 1: Nature of paint additives tested persion having an average of 64 % solids and hydroxyl (silanol) func-
tionality (see Table 2 for general properties). The typical viscosity is
Product Chemistry Relative silicone 4000 centipoise. This additive can be added directly, typically in post
active MWt addition, but preferably pre-diluted with water to help dispersion of
Silicone polyether 1 Silicone polyether low the actives to achieve the highest benefits with lowest dosage, de-
pending on the level of surface modification required.
Silicone polyether 2 Silicone polyether low
So why does the higher MWt silicone emulsion give superior slip,
Silicone polyether 3 Silicone polyether low hand-feel and abrasion resistance performance compared to the oth-
er materials? The actives in the silicone emulsion of this study have a
Competitor additive 1 Silicone polyether low
low surface tension and therefore migrate to the air/liquid interface.
Competitor additive 2 Silicone polyether low The siloxane backbone then orients to the air/polymer interface, thus 
Silicone emulsion PDMS Very high
PE wax 1 Polyethylene wax 26 % solids polyethyl-

emulsion ene wax emulsion Table 2: General properties of the high MWt PDMS additive
HDPE wax High density polyethy- 35 % non-ionic emul-
lene wax emulsion sion based on an Property "Dow Corning 52 Additive"
oxidised HD polyethyl-
Description Ultra-high molecular weight silicone
ene wax
dispersion in water
Paraffin wax Paraffin wax emulsion 35 % non-ionic emul-
sion based on a modi- Reactive group OH-functional, silanol
fied paraffin wax Appearance Smooth, milky white liquid
PE wax 2 Polyethylene wax 42 % non-ionic Non-volatile content 62-67 %
emulsion polyethylene emulsion Viscosity at 25 °C (77 °F) 3,000-5,000 cP
Figure 6: Rating of the impact of wax and silicone emulsion combinations on hand-feel property

70 Slip additives
 forming a very thin lubricating layer on the coating surface to reduce printed pieces do not stick together or scratch. Printers can then im-
the coefficient of friction. prove productivity.
This high molecular weight silicone emulsion brings the paint formu- For trim and joinery, the main goal is durability and a better abrasion re-
lator the chance to differentiate their coatings, paints and inks in the sistance is always welcome. In wood coatings, slip and hand-feel makes
market. It provides excellent slip properties and helps differentiate the initial difference for the end user, with better durability thanks to
products by creating a sensation that the end user will see, feel, ap- higher abrasion resistance. Finally, a different surface appearance and
preciate and value. feeling is of some interest for both external and internal paints.
Inks, industrial wood coatings, trim and joinery, together with the No matter which benefits are considered most significant, the silicone
interior and exterior paint markets are already benefiting from this emulsion is highly effective when used alone, but further benefits may
high MWt emulsion technology. With inks, increased slip means that be achieved by combining it with waxes. 
Figure 7: Impact of wax and silicone emulsion combinations on gloss
Figure 8: Impact of wax and silicone emulsion combinations on slip and abrasion

w o r ld o f c o l o ur 71
Source: Vesna Cvorovic - Fotolia.com

Fresh from
the printers
Around 11.3 million litres of
printing ink are used for the
world‘s inkjet printers over
the course of a year.
Olympic
Proportions
This amount of ink could fill
4,5 olympic swimming pools
or 15 million wine bottles. It
also equals half an hour of
rainfall over the UK.
Source: www.neowin.net

72 H a r de n e r s
Source: Yvonne Prancl - Fotolia.com
Getting on with acrylics

A new hardener compatible with acrylic resins. By Mauro Usai, S.A.P.I.C.I Spa.
Polyurethane resins are a useful tool in the coatings industry. the market sector for aromatic-aliphatic hardeners is an established
They can be combined with polyols. However, the hardeners one, but a weakness is the compatibility. It is not possible to combine
needed for curing often show incompatibility with acrylic poly- all acrylics with this class of hardener. The goal was to produce a fully
ols. A new hardener has been developed to overcome this. compatible, aromatic-aliphatic hardener for acrylic system.
This work is a comparative study of a new aromatic-aliphatic hardener
P olyurethane is one of the most versatile technologies as regards

application in the coatings sector. This does not just make a prod-
uct for general use, but rather gives it the possibility of covering the
with other products on the market of the same family from various
companies as a reference. The first step, a look at the reactivity, helps
to position the product. A second step, the application in a standard
performance requirements of sectors as varied as wood, metal, plastic, cycle in comparison to an aliphatic hardener, shows a new way to
leather, etc. At the same time, it meets the specific need for chemical- think acrylic polyurethane coating. The aim was not to compete with
physical resistance. The possibility of combining polyurethane with aliphatic on topcoat, but rather to demonstrate that formulators can
other technologies makes it one of the materials mostly used in sol- choose something different from aliphatic hardener to combine with
vent-based systems. Polyurethane has better performance and can acrylic resins.
be combined with a polyol and a hardener for curing. Polyols consist
of acrylic, alkyd and polyester resins and curing takes place with an Reactivity
aromatic, aliphatic or aromatic-aliphatic hardener. Obviously, an aro-
matic-aliphatic hardener possesses intermediate properties between The starting point was the evaluation of the reactivity. This was carried
the first two. Its main characteristics are faster curing than aliphatic out by monitoring the evolution of viscosity during the standard pot
materials and less yellowing than aromatic. Therefore, it can cover all life. In order to avoid any external influence, each hardener was mixed
those applications in which colour drift is not so important such as with the same oxydrilated resin to reach the same degree of crosslink-
general undercoats (primer, sealer etc.) or a substrate such as wood, ing and then diluted to the same solid content. The resulting curves
the properties of which change more than the coating itself. In general, of the different mixes depicted in Figure 1 show that the initial behav-

H a r de n e r s 73
one was the new aliphatic-aromatic product. Once this first parameter
was established, the evaluation of the final formulation was carried
out in order to underline the influence of reactivity in an actual ap-
plication situation. But prior to this, it was important to verify compat-
ibility when standard products were used in the formulation. The work
was focused on standard filmogen and aromatic solvents, because
Results at a glance these are the products that can have a more important affect on the
final transparency. It was not possible to cover the complete range of
űű Polyurethane technology for 2K applications is often com- additives on the market, but all the formulations developed using the
bined with polyols. The hardeners are often incompatible with new aliphatic-aromatic hardener contained the most commonly used
acrylic resins. wetting, defoaming, levelling and dispersing agents from a range of
producers. The evaluation was made on the hardener itself in combi-
űű The new product has better compatibility and full solubility nation with increasing quantities of filmogen solution. The level of ad-
in aromatic solvent. ditions reached a percentages beyond those encountered in real-life
formulations in order to investigate the limit of the compatibility of the
űű It shows no haze when mixed with acrylic resin and it shows different aromatic-aliphatic hardeners. The solutions were CAB (CAB
low yellowing. 381/0.5 20 % - 40 % MEK - 40 % MPA), Nitro (NC E14 20 % - Xy 5% - BA
75 %), Vinylite (30 % VROH- 80 % BA). As can be seen from the Figures
űű The material has similar properties to current, commercial- 2 and 3, the new aliphatic-aromatic hardener is the material with the
ized products with the advantage of compatibility with acrylic best compatibility and is fully soluble in aromatic solvent.
resins. Once the above behaviour had been established, the materials were
evaluated in combination with acrylic resin. Clearly, it was impossible
űű The new hardener can replace other products in several ap- to make a comparison with all the products on the market, but the
plications with the advantage of faster curing. major materials used in the wood and metal markets were compared
to all the hardeners and a larger test was carried out on the new al-
űű The material reduces the coating raw material price with di- iphatic-aromatic hardener. In the case of the new aliphatic-aromatic
rect impact on the final cycle. hardener, both products with different properties (OH number, vis-
cosity) and those with same properties, but from different producers
were tested. None of the mixtures showed any haze. To do this, the
correct quantity of hardener was added to each acrylic resin to reach
100 % of crosslinking. Figure 4 shows one of the tests of comparison:
only two samples were transparent, the one with aliphatic and the
one with the new aliphatic-aromatic hardener. It was impossible to
measure the degree of haze, because the value for those with haze
was outside a measurable range. As regards the combination of the
new aliphatic-aromatic hardener with the different acrylic resins, the
values were between 1.1 and 1.4.
iour of all the hardeners was similar due to solvent evaporation. After
this, the curves developed different slopes. The steeper the slope, Yellowing resistance
the higher the reactivity. This confirmed the expected performance
of Hardener 1, a fast curing product. Hardener 2 and a competitive The other key factor taken into consideration was the yellowing be-
product had the same, slower reactivity and at the end the slowest tween the different aromatic-aliphatic isocyanurates. It was not pos- 
Figure 1: Comparison of the evolution of viscosity of a variety of Figure 2: Comparison of the compatibility of various hardeners
hardeners

74 H a r de n e r s
 sible to compare them with the full aliphatic as is discussed later, but is firstly that pigment hides the change in colour and secondly the trans-
the materials had to guarantee good light resistance for a number of parent system absorbs the direct light and the reflection from the white
applications. The evaluation of yellowing was made on a metal plate sealer. The difference between each set of values, and that of the final
coated with white, non-yellowing sealer and subsequently coated with aspect, are quite similar (Table 2).
pigmented and transparent high-gloss topcoat 170 g/m2. The topcoat
was formulated as set out in Table 1 and mixed with different quantities Lowest viscosity
of hardener in order to achieve the same degree of crosslinking. The
formulations were not based on acrylic resin, because of the problem Drying and resistance tests were also performed on these formula-
of compatibility of traditional products with respect to the new aliphatic- tions. The drying test is important, because in the final high-gloss for-
aromatic hardener. This material needed to be combined with an acrylic mulation it is not possible to detect differences in the dust-free or
resin and a special, absolutely non-yellowing alkyd resin, in order to in the touch free formulation. The evidence of a longer curing time
reach compatibility. The different samples were exposed to the QUV ac- is more visible when a mat topcoat is formulated, and it is reflected
celerated weathering test for 100 hours and subsequently the yellowing more by the higher gloss of the new aliphatic-aromatic hardener than
was evaluated using a colorimeter. Table 2 shows the value for the two from the longer time needed to detect it discussed earlier. The new
different topcoats. There is a big difference between them. The reason aliphatic-aromatic hardener is the lowest in viscosity, so at the end
Figure 3: The solubility of various hardeners in xylene Figure 4: Degree of haze in mixtures with acrylic and aliphatic resins
Table 1: Formulations of topcoats with different quantities of hardener
Pigmented topcoat Gloss clear topcoat

Component A Component A
“Rexin 2268” 22.5 % “Rexin 2268” 62.0 %
“Domacryl 546” 30.0 % Butyl acetate 12.0 %

TiO 2 32.0 % Xylene 9.0 %
Butyl acetate 9.0 %

Ethyl acetate 7.0 %
MPA 4.0 % MPA 3.0 %
MIBK 1.5 %
MEK 6.0 %
“Byk 141” 0.5 % “Byk 141” 0.5 %
“Byk 306” 0.5 %
”Byk 306” 0.5 %
100
100
Component B
Component B
Mixed isocyanurate* 50.0 %
Mixed isocyanurate* 58.0 %
Ethyl acetate 25.0 % Ethyl acetate 21.0 %
Butyl acetate 25.0 % Butyl acetate 21.0 %
100 100
*Competitor/OKD/OKDS/OK-HP *Competitor/OKD/OKDS/OK-HP

H a r de n e r s 75
it is possible to increase the matting agent in the final formulation Same topcoat
without an increase in final viscosity, a change that can affect the ap-
pearance. With regard to the chemical physical resistance, all the tests In conclusion, it seems that the evaluation of yellowing, a feature
performed and the differences observed are within the margin of er- considered only at the end of the work, can modify the idea and the
ror for each evaluation. The only test that differs and gives the new planning of the pigmented cycle made with 2K acrylic and isocyanate
aliphatic-aromatic hardener higher hardness is the Sclerometer test. systems. The proposal is to use the new aliphatic-aromatic hardener
The new aliphatic-aromatic hardener performs in a similar way to in the sealer rather than the topcoat, as it is known that the yellowing
products well known on the market, with the additional advantage of of the sealer can have an effect on the final finish. Thus it is essential
the possibility to combine it with acrylic resin. This property makes it to evaluate this effect by applying in parallel two cycles with two coats
worth comparing the new material with aliphatic hardeners, to date of sealer, both with the same component A, but with a different hard-
the only hardener that are fully compatible with acrylic resins. This ener, i.e. the full aliphatic and the aromatic-aliphatic. To do this both
does not necessarily mean that the aliphatic-aromatic technology samples were coated with the same aliphatic topcoat and then ex-
should be recommended for the application in pigmented non-yel- posed at the QUV. As can be seen from Table 3, in one cycle there was
lowing topcoats. Figure 5 shows the results of QUV tests made on a yellowing of the basecoat, but this had no effect on the final finish.
a yellowing substrate such as wood and in a sealer for pigmented The values were calculated taking the full aliphatic as a reference to
systems. The behaviour on light and dark wood shows that in both ensure that there would be a greater difference between the differing
cases what yellows most is the substrate. Thus, there is no advantage, coats of sealer. However, as can be seen from the value ΔE=0.3, there
apart from the compatibility question, to use aliphatic. Talking about was no influence on the final appearance.
the pigmented system, the evaluation of colour change starts from a Compared to previous formulations, the new product has a further
screening of the possible application on different substrates, i.e. the advantage. Products using the new aliphatic-aromatic hardener are
testing of the adhesion and flexibility on a general pigmented for- touch-free at room temperature after three hours. With aliphatic, the
mula. The conclusion is that the new aliphatic-aromatic hardener can time needed is six hours. Both have a pot life in excess of eight hours.
be used in a similar way to the aliphatic material on different flexible It is clear that this reduces the curing time and/or temperature, with a
substrates, from plastic to metal, each time modifying the formulation direct impact on environment and energy saving.
of component A (oxydrilic component) and using known methods of Finally, the new aliphatic-aromatic hardener can help also to reduce
achieving good adhesion. Generally speaking, with respect to aromat- the impact of the coating raw material on the final price – a subject
ic, the idea is to have a rigid and brittle system. The new aliphatic-aro- that, in this time of crisis is a sensible one for everyone. 
matic hardener is designed in order to reach the maximum flexibility:
7.5 at the conical mandrel, the full scale.
Figure 5: Results of QUV tests made on aliphatic and aliphatic- Table 2: Degree of yellowing of t wo different topcoats
aromatic coating cycle for dark and clear wood
∆E [100 h]
PTCH * CTCH **
Competitor 2.2 11.5
“Polurene OK.D” 2.4 14
“Polurene OK.D.S.” 2.3 11
“Polurene OK-HP” 2.1 14
* Pigmented top coat high gloss, ** Clear top coat high gloss
Table 3: Degree of yellowing after QUV of t wo different cycles
dL da db ∆E
1st coat sealer -0.58 0.72 4.25 4.3

2nd coat sealer -0.48 -0.6 3.62 3.7
PTCH 0.07 0.05 0.25 0.3

76 C r o s s l i n ker s
Source: Evonik Industries
Bio building
blocks
A method for the economic biological production of new
industrial amines as crosslinkers. By Philip Engel, Evonik
Industries.
Industrial amines have a broad range of applications in the

chemical industry, such as polyamides, surfactants and
crosslinkers. For crosslinkers in coating applications, amines
T he global market of biobased chemicals reached $9.1 billion in
2011 [1]. Demand is continuously growing with above average
growth rates. More and more biochemicals have been launched into
in epoxy resins play a major role. To overcome the limitations the market, that are not only biobased but also produced by a bio-
of petro-based crosslinkers, a new technology platform that process (biocalaysis or fermentation).
allows the synthesis of amine building blocks based on renew- Well-known examples for large scale products include 1,3-propan-
able resources such as glucose and isosorbide has been devel- ediol, that was launched in 2006 by DuPont [2]. Furthermore, other
oped. products are just now reaching commercial scale, e.g. succinic acid
(Succinity, BioAmber, Myriant, Reverdia) [3], 1,4-butanediol (Genom-
atica) [4], and isobutanol (Gevo).
Figure 1: Reaction cascade to produce amines from alcohols

Cr o s sli n k e r s 77
The vast majority of the amines are today produced from petrochemi-
Results at a glance cal resources by chemical conversion. For example, carbonyl com-
pounds, aldehydes or ketones, can be effectively reductively aminated
űű To overcome the limitations of petro-based crosslinkers, [8]. However, the chemical conversion of alcohols to amines is not as
a new technology platform that allows the synthesis of amine established. The conversion of alcohols to amines was described by
building blocks based on renewable resources has been devel- a “borrowing-hydrogen” methology, eliminating hydrogen as cosub-
oped strate and using ammonia as nitrogen source [8]. Despite promising
first results, these approaches are not economically viable yet and
űű Amines are one of the central building blocks in the chemi- further development concerning the catalyst synthesis, recycling, and
cal industry, used in the production of polymers, agrochemi- immobilisation is needed.
cals, emulsifiers and in epoxy resins for crosslinker applications Enzymes are another established technology to produce amines from
carbonyl groups. Transaminases (TA) are a group of enzymes that can
űű For the biological production of amines from alcohols in produce enantiomerically pure amines with very high selectivities.
one step, different types of enzymes have to be coupled to a Due to the high stereoselectivity of transaminases they already play
reaction cascade an important role in the synthesis of pharmaceutical intermediates,
where enantiopure products are needed [10]. As an amine donor for
űű The reaction cascade was successfully applied for a range the transaminase reaction amino acids are most common.
of alcohol educts and showed excellent selectivity and conver- The platform developed here provides a new approach to biological
sions for a number of the tested alcohol educts production of different industrially relevant amines directly from alco-
hols. A major aim is to show the perspective for a cost reduction, since
űű After the redox self-sufficient reaction system was estab- amine building blocks for the chemical industry are substantially lower
lished for the in-vitro reaction, the enzyme cascade was trans- in prices compared to pharmaceutical amines.
ferred into a living whole cell system, (an E.coli host), a step
required for the economic production of amines as chemical Developing enzyme cascades for conversion of
building blocks. alcohols to amines
űű The formation of the respective a,w-diamins and amino- For the biological production of amines from alcohols in one step,
alcohols was analysed and it was shown the developed enzyme different types of enzymes have to be coupled to a reaction cascade.
cascade could be successfully transferred from an in-vitro sys- First, the alcohol group has to be converted to an aldehyde or ke-
tem to a whole cell system tone by an alcohol dehydrogenase (ADH). This enzyme requires the
cofactor NAD (Nicotine adenine dinucleotide) or NADP (Nicotinamide
adenine dinucleotide phosphate) for electron transfer. This reaction
is coupled with a second enzyme, a transaminase that converts the
carbonyl group to the amine by transferring nitrogen from an amino
acid, e.g. alanine, as amine donor. The amino acid amine donor is con-
The most common resource for biotechnological fermentation pro- verted to a keto acid, e.g. pyruvate.
cesses are carbohydrates. Today the majority of industrially used car- Overall the combination of alcohol dehydrogenase and transaminase
bohydrates originate from sugar cane and sugar beet. In particular requires two cosubstrates, NAD and amino acid. For the biological
with respect to recent biofuel initiatives, a lot of research efforts focus production of large volume chemicals it is by far too expensive to
on sugar production from non-food lignocellulosic biomass such as provide these co-factors stoichometrically to the reaction, particularly
wood, straw of other biological residues. However, in the near term it NAD is very expensive. Therefore, the reaction was extended with a
cannot be expected that sugars from non-food biomass will be avail- third enzyme, an alanine dehydrogenase, to create a redox self-suffi-
able in large volumes [5]. cient reaction system that regenerates the needed NAD cofactor. The 
For the production of biobased chemicals employing a bioprocess,
carbohydrates can be directly used as fermentation raw material, e.g.
for 1,4-butanediol or succinic acid. Furthermore, biochemicals can be Figure 3: Successful conversion of different a,w-diols to di-
produced from other sugar derived intermediates, e.g. isosorbide is a amines in a whole cell system. 10 mM is equal to 100%
bycyclic furofuran compound produced by catalytic hydrogenation of concversion. For reaction details, please refer to [13]
glucose to sorbitol and subsequent dehydratisation to isosorbide [6, 7].
Biological production of industrial amines
Amines are one of the central building blocks in the chemical indus-
try. They are used, for example, in the production of polymers, agro-
chemicals, emulsifiers and in epoxy resins for crosslinker applications.
Figure 2. Reaction from isosorbide to the aminoalcohol [7]

78 C r o s s l i n ker s
 alanine dehydrogenase regenerates the keto acid using ammonia and For different primary alcohols excellent conversions to the diamine of
at the same time converts NADH, formed by the alcohol dehydroge- 80-100 %, with nearly 100 % selectivity for the diamine, were achieved
nase, to NAD. Thereby, both cofactors can be effectively regenerated within only a few hours reaction time. Therefore, it was clearly shown
and only cheap ammonia as nitrogen source has to be added. The that the developed enzyme cascade could be successfully transferred
reaction cascade is illustrated in figure 1. from an in-vitro system to a whole cell system.
The reaction cascade was successfully applied for a range of alcohol
educts and showed excellent selectivity and conversions for a number Conclusions and outlook
of the tested alcohol educts, shown in table 1. The reaction was also
successfully performed for diols as educts and it was found that for bi- The new technology platform developed provides a novel way for the
functional molecules with two alcohol groups the reaction occurs se- production of industrial amines, e.g. for coating applications. It was
quentially, i.e. first one alcohol group is converted to an amine and the shown that the individual reactions can be performed enzymatically
subsequently the second alcohol group is converted to an amine [11]. and that the combination of different enzymes to a redox self-suffi-
As a sugar derived and particularly bulky molecule, the amination of cient cascade is possible. Furthermore, the reaction was successfully
isosorbide to the aminoalcohol, as shown in Figure 2, and further, to transferred in a whole cell system, which is an essential milestone to-
the respective diamine was investigated in depth [12]. After extensive wards the economic biological production of new amines. 
enzyme screening and engineering it, suitable enzyme system com-
prised of an alcohol dehydrogenase, a transaminase and an alanine
dehydrogenase was identified to aminate isosorbide. For isosorbide Acknowledgments
as educt the bifunctional amination can lead to three different ste-
reoisomers, diaminoisoidide, diaminoisosorbide and, diaminoiso- This work was funded by the BMBF project “Bioxamine” (Grant No.
mannide. The respective amionoalcohol was the main product of the 0316044B). We would like to thank all project partners, particularly the
reaction and reaching concentrations of 1-2 g/L. Additionally, the re- groups of Prof. W. Kroutil, Uni Graz; Prof. A. Skerra, TUM and Prof. V. Wendisch,
spective diamine was also identified in this study [12]. Uni Bielefeld for providing the data shown.
Production of amines using enzymes

in living whole cell systems References
After the redox self-sufficient reaction system was established suc- [1] Lucint el homepage. w w w.lucint el.com/repor t s/chemical_composit es/
cessfully for the in-vitro reaction, the next step was the transfer of the global_ polymer_indust r y _2012_2017_t rends_f oreacast_ june _2012.
enzyme cascade in a living whole cell system. This step is required for aspx (acce ssed Feb 4, 2014)
the economic production of amines as chemical building blocks, as [2] Nak amur a C. and W hit ed G., Met abolic engineer ing f or t he microbial
the need for expensive co-factor addition hampers the economics of product ion of 1,3- propanediol, Curr. Opin. Biot echnol., 2003, Vol. 14, pp.
the process even though the developed cascade is self-sufficient. By 454−459.
transferring the reaction in a microbial system no addition of external [3] Scholt en E., Renz T., T homas J., Cont inuous cult i v at ion approach f or
co-factor is needed, but supplied from the natural cell metabolism, f erment at i ve succinic acid product ion f rom cr ude glycerol by Basf ia suc-
using glucose as cheap and abundant co-substrate for energy supply. ciniciproducens DD1, Biot echnol. Let t., 2009, Vol. 31, pp. 1947−1951.
The enzymes successfully applied in the in-vitro system were trans- [4] Y im H., Haselbeck R., Niu W., et al., Met abolic engineer ing of Escher ichia coli
ferred in an E. coli host. After growing the cells, they were transferred f or direct product ion of 1,4- but anediol, Nat. Chem. Biol., 2011, Vol. 7, pp.
in a aqueous buffer system and contacted with different a,w-diols. 445−452.
The formation of the respective a,w-diamins and amino-alcohols was [5] Bioref iner ies Roadmap, f eder al Government of Germany, 2012.
analysed (see figure 3) [13]. [6] Climent M., Corma A ., Iborr a S., Conver t ing car bohydr at es t o bulk chemicals
and f ine chemicals over het erogeneous cat alyst s, Green Chem., 2011, Vol.
13, pp. 520–540.
Table 1: Amination of different primary alcohols (for details [7] Schaf f er S., Haas T., Biocat alyt ic and f erment at i ve product ion of
please refer to [11]) a,w - bif unct ional polymer precur sor s, Org. Progress Res., 2014,
Vol. 18, pp. 752-766.
No. Substrate Conversion % Aldehyde % Amine [8] Pagnoux- Ozherelye v a A ., Pannet ier N., Mbaye M., Gaillard S., Renaud R.,
% K nölker ’s iron comple x : an ef f icient in sit u gener at ed cat alyst f or reduct i ve
1 1-hexanol >99 <1 >99 aminat ion of alk yl aldehydes and amines, A ngew. Chem., 2012, Vol. 124,
pp. 5060–5064.
2 1-octanol 50 <1 50 [9] Imm S., Bähn S., Zhang M., et al., Improved r ut henium - cat alyzed aminat ion
of alcohols wit h ammonia: synt hesis of diamines and amino est er s, A ngew.
3 1-octanol 57 <1 57
Chem., 2011, Vol. 123, pp. 7741–7745.
4 1-decanol 2 <1 2 [10] H öhne M., Bornscheuer U., Biocat alyt ic rout es t o opt ically act i ve amines,
ChemCat Chem, 2009, Vol. 1, pp. 42-51.
5 1-decanol 25 <1 25
[11] Sat t ler H., Fuchs M., Tauber K ., et al., Redox self- suf f icient biocat alyst net-
6 1-dodecanol 10 <1 10 wor k f or t he aminat ion of pr imar y alcohols, A ngew. Chem., 2012, Vol. 124,
pp. 9290 –9293.
7 benzyl alcohol >99 13 87 [12] L erchner A ., Achat z S., Rausch C., Haas T., Skerr a A ., Coupled enzymat ic
alcohol - t o - amine conver sion of isosor bide using engineered t r ansami -
nases and dehydrogenase s, ChemCat Chem, 2013, Vol. 5, 3374-3383.
8 cinnamyl alcohol >99 30 70
[13] K lat t e S., Wendisch V., Role of L- alanine f or redox self- suf f icient aminat ion
of alcohols, Bioorg. Med. Chem., 2014, Vol. 22, pp. 5578–5585.
9 3-phenyl-1-propanol >99 <1 >99

Source: ShanePhoto - Fotolia.com w o r ld o f c o l o ur 79
Ancient Paints
Popular pigments used for
cave paintings were iron oxi-
de, maganese oxide and char-
coal, mixed with water, spit or
fat. Researchers assume that
other raw materials were ore,
feldspar, blood, limestone, re-
sin, milk and herbal juices.
From Brushes to
Spray Painting
The paint was applied with
branches, stamps or
fingers. In addition to this,
paints were also spray
painted using pipes made
from bone.

80 Emul sifier
Source: jpramirez - Fotolia.com
New chemistry for

reactive emulsifiers
Benefits found in production and performance of aqueous alkyds. By Charles F. Palmer, Jr., Ethox Chemicals.
The conversion of alkyds to waterborne form has a number

of problems. Very high viscosities may occur during the invert
emulsion process, while the surfactants used may impair the Table 1: Composition of emulsified alkyd
properties of the dried film. A new emulsifier that crosslinks
during drying can improve final properties, while allowing
Material % by weight Amount used
emulsification to be completed before the solvent is stripped
from the original alkyd
“Beckosol 6422-K3-
75” (25 % methyl
W hile they are no longer the most widely used binders in coat-
ings, alkyd resins are still of major importance since they re-
main the most commonly used resin or binder system in oil-based and
n-propyl ketone
solvent) short oil alkyd
(Reichhold)
49.4 % 741 g
solvent-based coatings.
Alkyd coatings are relatively inexpensive and perform well, often with
fewer film defects than other coatings. They are used in many indus- Reactive A 4.0 % 60 g
trial and architectural applications. The hydrophobic nature of the alkyd
polymer makes them good choices when water repellency is important.
However, formulating alkyds into low VOC (volatile organic compound) Ammonium hydroxide 0.74 % 11.1 g
waterborne coatings results in a number of problems, which can be
minimised by the use of a new reactive emulsifier as described below.
The general nature of alkyds Deionised water 45.86 % 687.9 g
Alkyd resins are polyesters generally prepared from a polyol, phthalic Solids content 41 %
anhydride and unsaturated vegetable fatty acids such as linseed, soy,

Emul sifier 81
to speed curing, improve water compatibility or solubility or reduce

viscosity.
Results at a glance Solvents are employed in traditional alkyd manufacture to reduce
the viscosity of the oligomeric polyester and often to help remove by-
űű Alkyd resins continue to be used in large volumes in sol- product water formed in the synthesis. These solvents include xylene
ventborne coatings. However, the conversion of alkyds to water- or ketones.
borne form has a number of problems.
Role of alkyds in the shift to waterborne coatings
űű Waterborne alkyds may be prepared either by grafting
onto an emulsion polymer or directly by the invert emulsion The legislation in many countries to reduce VOC content in coatings is
process. The latter is more flexible, but the surfactants used limiting the usage of alkyds in many applications, since most traditional
lead to very high viscosities during production and may impair alkyds have a significant level of solvent. The solvent is necessary to
the physical properties of the dried film. reduce the viscosity of the alkyd resin and to allow easy application.
A number of new technologies have been developed recently to ren-
űű A new type of emulsifier based on the styrenated phenol der solventborne alkyd coatings more environmentally acceptable by
hydrophobe and containing allyl groups crosslinks during dry- replacing some or all of the solvent with water. Alkyd resins are con-
ing, thus improving final properties. It also allows emulsification verted into useable waterborne products by one of two methods.
to take place before the solvent is stripped from the original One method is to graft an alkyd resin onto an emulsion polymer. This
alkyd, reducing viscosity problems. gives the coating some properties of both polymer types. The emul-
sion polymer and the surfactant additives that are used to manufac-
űű The reactive emulsifier produced a more hydrophobic ture the emulsion render the emulsion/alkyd polymer dispersible in
film which resisted water penetration better than a standard water, while the grafted alkyd imparts alkyd-type properties such as
waterborne alkyd. Gloss and adhesion to metal also showed toughness and resistance against various chemicals to the coating.
some improvement Additional processing steps are needed to make these hybrid products.
The alkyd polymer needs to be of a particular type and structure in order
to make a viable alkyd/emulsion coating. In some cases, the durability
of these products is superior to those of emulsion polymeric coatings.
However, the alkyd resin chemistry must be altered to maximise the
benefits from the grafting of alkyd resin onto the emulsion backbone.
The additional processing steps increase costs. This process also em-
or tung oil (see Figure 1). The inclusion of the fatty acid confers a ten- ploys additives such as coalescing solvents to improve properties such
dency to form a flexible coating. Alkyds are often categorised as long, as the gloss and flexibility of the coating.
medium or short oil, based on the amount of vegetable oil in the alkyd; Emulsification of the alkyd resin into water is the other method to re-
thus, long oil alkyds have more fatty acid content than short oils. move some or all of the VOCs in the emulsified product. A key advan-
Fatty acids known as drying oils have multiple double bonds which will tage of the emulsification process is that the alkyd resin used does
air cure to give a hard coating. This curing reaction crosslinks the oligo- not necessarily need to be altered to prepare the emulsion, so long
meric alkyd chains to increase molecular weight and improve durability as the proper surfactant and emulsification process is used to make
and other properties. the product.
Alkyds are sometimes modified with other radical reactive monomers The proper surfactant is one with the proper molecular weight, struc-
or polymers for a number of reasons. These are included (for example) ture, and HLB (hydrophilic/lipophilic balance). Nonionic surfactants 
Figure 2: Generic chemical structures of

styrenated phenol-based surfactants
Figure 1: Generic scheme of alkyd synthesis (‘Reactive A’)

82 Emul sifier
 generally outperform anionic surfactants in making stabilising emul- to a high enough temperature to reduce its viscosity to a manageable
sions - as demonstrated by improved water sensitivity, better colloidal level. The solvent used to make the alkyd is usually removed prior to
stability and lower foam profile when compared to an emulsion made emulsion preparation and the alkyd is kept at elevated temperature to
with an anionic surfactant. However, in some cases, a small amount of keep it from solidifying.
anionic surfactant is used in conjunction with the nonionic surfactant The surfactant package of choice is then added to the molten alkyd,
to provide some charge stabilisation. followed by gradual addition of hot water. As the water is added, the
mixture forms a water-in-oil emulsion However, as the water content
Limitations of the emulsification process increases and the emulsion nears the inversion point (‘flipping’ from a
water-in-oil emulsion to an oil-in-water emulsion) the viscosity often
However, there are a number of technical difficulties and limitations becomes unmanageably high.
with the emulsification process as described in the patent literature. The temperature is maintained as high as possible to reduce the vis-
Usually what is termed an invert emulsion process is preferred since it cosity, but one problem is that surfactants, especially nonionic sur-
does not require high shear mixing and produces less foam. factants, have lower water solubility at high temperatures. Once the
In this process, the undiluted alkyd with little or no solvent is heated inversion point is crossed, forming the final oil-in-water emulsion, the
viscosity decreases.
These alkyd emulsions contain a few percent of surfactants that re-
Table 2: Comparisons bet ween reactive and non-reactive main in the formulation and thus are present in the coating after appli-
surfactant based alkyd coatings cation. There they can cause a number of problems. When surfactant-
coated micelle spheres stack on a surface during the drying process
Reactive surfactant Non-reactive surfactant and start to coalesce, the concentration of surfactant molecules at the
formula formula intersection of micelles can become relatively high.
If the surfactant molecules remain unbound and free to migrate, when
“Beckosol 10-539” 38.2 38.2
long oil alkyd the dried coating is later exposed to water some of the surfactant mol-
ecules can dissolve. This reduces the surface tension of the water, im-
proves its wetting of the coating surface and promotes its penetration
Reactive A 1.8 --
through the coating.
Damage to the substrate to be protected becomes much more likely.
On metal substrates, this can lead to corrosion and loss of adhesion.
POE 20 DSP -- 1.8
In addition, extraction of the surfactant can lead to pitting and degrade
the integrity of the coating. Free surfactants can also plasticise the al-
kyd and prevent it from reaching maximum hardness upon curing.
Ammonium 0.6 0.6
hydroxide
Solving the problems created by surfactants
Water 58.8 58.8 Many of the problems that are caused by extractable surfactants can
be reduced if the surfactant can co-cure into the alkyd coating. This
locks it into place so that it cannot be extracted by water. A number
Catalyst blend 0.6 0.6
of patents claim reactive surfactants that can do this. They are usually
based on fatty acid alkoxylates in which the fatty acid has a number of
double bonds similar to the drying oil fatty acids.
Drawdown properties However, most of the known ones have some significant drawbacks.
after 2 weeks They are nonionic surfactants and so have lower solubility in hot water,
which limits their ability to make inverse emulsions with manageable
viscosity. Nonionics also cannot take advantage of charge stabilisation
Cross-cut adhesion 0B (100 % fail) 0B (100 % fail) mechanisms to reduce particle size and improve emulsion stability.
Most nonionic surfactants used for alkyd emulsions have long ethoxy-
late chains to give them the high HLB value which is required to make
Pencil hardness F 2B a stable emulsion. These nonionics have a strong tendency to retard
drying, probably due to complexation of metal ion drying agents. Long
chain nonionics also have a tendency to plasticise alkyd coatings, re-
ducing their hardness.
A new class of reactive surfactants has now been developed, based
on the styrenated phenol hydrophobe and containing allyl groups, as
60 ° gloss 117 113
shown in Figure 2. Instead of curing through fatty acid double bonds,
these cure through the pendant allyl groups. Styrenated phenol is a
polyaromatic hydrophobe, so these surfactants have good affinity for
Water contact angle 84.5 ° 79.0 °
the aromatic groups in the alkyd. They are also inherently lower foam-
ing than most linear surfactants.
Appearance of The alkoxylate chain is relatively short so that it has less affinity for
water drop on chelating metal ions. Curing times have not been affected with the dri-
surface of er packages tested. The anionic character gives it charge-stabilisation
dried film ability. This surfactant chemistry is also available as a nonionic and as
a phosphate ester.

Emul sifier 83
Emulsion preparation procedure outlined As Figure 3 shows, the particle size of the alkyd emulsion remained very
low, actually decreasing from the solvent-containing emulsion stage.
The materials used in alkyd emulsion preparation and their addition The solids content was significantly higher. These results were not opti-
levels are shown in Table 1. The procedure used is as follows. Charge mised; the solids concentration could probably have been significantly
the solventborne short oil alkyk, (‘Reactive A’), and ammonium hydrox- increased further.
ide to a reactor flask equipped with nitrogen sparge, thermocouple, This result shows that the use of these anionic surfactants can over-
overhead mixing and condenser. Once the mixture is homogeneous, come the viscosity problem inherent in the invert emulsion proce-
begin adding water at ambient temperature to the mixture in a slow dure by leaving the solvent in the mixture and then removing it after
stream so that the water is incorporated evenly into the mixture and emulsion formation. The anionic sulfate has sufficient water solubility
does not pool on the surface. to remain an effective emulsifier even at the elevated temperatures
As the water is added, the viscosity will rise until the inversion point is needed for practical solvent stripping. This procedure will allow coat-
met, then the viscosity will begin to drop. When all the water is charged, ing manufacturers to convert existing low-cost solventborne alkyds to
allow the emulsion to mix for several minutes and then check the parti- waterborne products containing no VOC.
cle size. This emulsion was prepared at 41 % solids.
After ensuring that the particle size is satisfactory, raise the tem- How different surfactants affect coating properties
perature of the emulsion by heating to 70 °C with a nitrogen sparge.
Gradually increase the temperature until vapours are detected in the Two more waterborne emulsions were prepared using the proce-
condenser and allow the emulsion to strip until all of the solvent is dure as given above, but with a long oil solventborne alkyd. Identical
removed. amounts of reactants were used. The only difference was the emulsi-
After cooling, the particle size, percentage solids and viscosity were fier. Both emulsifiers (“RS-1618” referred to as ‘Reactive A’ and POE
checked. This emulsion was 47.9 % solids and contained 0.4 % residual 20 DSP (poly(oxyethylene) with 20 POE units)) are distyrenated phenol 
solvent. The viscosity was not measured but was quite low. based, have nearly the same ethoxylate chain length, and are both sul-
Figure 3: Alkyd emulsion particle size with solvent (left) and after solvent stripping (right)

84 Emul sifier
 fates. The only significant difference between them is that Reactive A is tected the steel much better than did the non-reactive one. In another
reactive, while POE 20 DSP contains no reactive allyl groups. test of adhesion, drawdowns were made of an aqueous short oil alkyd
After the emulsions were prepared, a cobalt-based drying catalyst emulsion prepared with the difunctional Reactive A surfactant accord-
package was added to the emulsion and drawdowns were made on ing to the first example above and a commercially available waterborne
steel “Q-panels”. After two weeks, the adhesion, pencil hardness, gloss, short oil alkyd (assumed not to contain a reactive surfactant).
and water contact angle were checked. Results are shown in Table 2. Both were catalysed with the same drier package. After 24 hours, a
Review of the data in Table 2 shows that the alkyd coating with the crosshatch pattern was scribed onto the alkyd surfaces. The attempt
reactive surfactant has a higher water contact angle. This indicates to scribe the crosshatch pattern on the commercial alkyd failed, while
that the coating is more water repellent, evidence that the reactive it was successful on the alkyd with reactive surfactant (see Figure 5).
surfactant is cured into the alkyd and not available to dissolve into the This failed the tape pull, however.
water and reduce its surface tension. The reactive surfactant emulsion thus had significantly better adhe-
The coating with the reactive surfactant is also significantly harder than sion to the steel panel. It is not known what the mechanism for the
the other. Presumably, this is due to the plasticisation of the coating by improved adhesion is.
the unbound surfactant. The gloss of the coating is also higher with the
reactive surfactant. This suggests that the surface has fewer defects. Benefits of reactive surfactants summarised
This might be due to a more homogeneous particle size distribution.
The reactive surfactants described here allow the viscosity problems
Adhesion to metal and rust protection are improved found in the invert emulsion process to be reduced. They give a more
hydrophobic coating (as measured by water contact angle) than struc-
Water drops were placed on each of these drawdown panels and allowed turally similar non-reactive surfactants. Similarly, they produce a more
to stand covered so that they would not evaporate. The water drop on water-resistant coating (as measured by rust resistance) than structur-
the alkyd coating with the non-reactive surfactant had significantly wet the ally similar non-reactive surfactants.
coating and had spread out to cover a much larger area than the drop Both gloss and adhesion to metal can be improved by the use of reac-
on the reactive surfactant coating. After two days, rust on the panel was tive surfactants. Further work to develop and understand this technol-
clearly visible on the panel with non-reactive surfactant (see Figure 4). The ogy is therefore under way. 
coating with the reactive surfactant resisted the ingress of water and pro-
Figure 4: Outlines of water drop on alkyd coating drawdown on steel panels. Left: Coating with reactive surfactant. Right: Coating
with non-reactive surfactant
Figure 5: Crosshatch adhesion test on steel panels coated with aqueous alkyds

Source: phanuwatnandee - Fotolia.com

Like Clockwork
Big factories can coat up to
100,000 pencils a day. The
pencils are pushed in a pipe-
like case with paint. Surplus
coating is then wiped off
when they are extruded from
the container. The process is
repeated up to seven times.
Less is More
Only small amounts of coa-
ting are needed to coat a
pencil – less than one gram
is used apiece. The pencil
has a long history – its first
precusors were produced in
1565 in England.
Source: Deutsches Lackinstitut

86 R h e ol og y M o d i f ie r
Getting
more
with less
New bio-based rheological additives for low-
temperature process. By Germain Fauquet and
Yohann Trang, Arkema.
Source: Scanrail - Fotolia.com
Recently, a new generation of thixotropic amides (SLT) has

come onto to the sealant market. It reduces cost and cycle
R heology modifiers are normally used in adhesives and sealants
to improve their properties during the three different stages of
their life, i.e. during storage, in the application phase and finally during
times and also improves reliability and rheological perfor- the use of the cured sealant.
mance. More than 90 % of its ingredients are bio-sourced and During storage, a good rheological additive will provide anti-settling
bio-renewable. It is also 100 % solid and therefore VOC free. properties, i.e. the fillers and pigments will remain homogeneously dis-
Furthermore, this development will enable formulators to tributed in the liquid phase without any syneresis or phase separation.
produce sealants at lower temperatures (cold process), thus It will also enhance long-term stability by preventing advanced curing
reducing energy consumption and cycle time and leading to and viscosity variations after several weeks or even months of storage.
lower manufacturing costs. The ideal rheological additive shows excellent shear-thinning behav-
iour. This will enable to play a major role by providing a good extrusion
rate and workability during the application phase. This is important,
Figure 2: Processing time comparison bet ween the products SLX

Figure 1: Amide fibres 3D net work and SLT

R h e o l og y M o d i f ie r 87
Over the years, several technologies have been developed to achieve

these different properties. These are used nowadays by sealants and
Results at a glance adhesives manufacturers. For example, on one hand inorganic tech-
nologies such as fumed silicas, precipitated calcium carbonates and
űű The new rheological additive presented in this article organoclays, and on the other, organic materials such as hydrogen-
(SLT) is a bio-based material which allows adhesive and sealant ated castor oil and polyamides.
formulators to use a cold manufacturing process. Inorganic rheology modifiers, for example, fumed silicas, are widely
used today, because they are activated at low temperature, have a
űű This fact enables them to reduce their energy cost and in short processing time and give high viscosity build. However, they cre-
the same time to shorten their production time. ate dust, are difficult to handle (low density) and have a major impact
on mechanical properties.
űű SLT also exhibits higher rheological performance (higher Precipitated calcium carbonates are easy to process at low tempera-
viscosity, good shear thinning behaviour, good pseudoplastic tures, easy to handle, but act as fillers. Much higher concentrations
properties) and it is by 10 to 25 % more efficient than older ge- are needed leading to a significant impact on mechanical properties.
nerations. Organoclays are easy to handle and to process, but their efficiency
is system dependent. They do not behave so well in solvent-free sys-
űű This new development therefore extends the existing tems and the polarity of the final system is a key factor. Furthermore,
range of additives and offers various solutions to the formula- they can have an impact on the final colour of the sealant and may
tor depending on processing conditions – from cold to hot pro- require pre-gel preparation.
cess – and systems, including hybrids, epoxies, 2K-PU, silicones, Looking at organic rheology modifiers, castor-oil derivatives were
acrylates, rubbers, polychloroprenes etc. historically the first generation of this family of rheological additives.
They were developed in the early 60’s and are still used, because of
űű These products embody the principle of achieving more their low cost and ease of activation at low temperatures (40 °C to 
by using less while contributing positively to the protection of 70 °C). They are simple to handle, give a high viscosity build and show
the environment. a good extrusion rate. One of the main limits of this technology is
that the temperature must be well controlled and the stability of the
viscosity upon storage can be an issue. This is due to their sensitivity
to processing conditions, high temperatures and temperature varia-
tions.
The amide technology is clearly the one that has grown significantly
during the last 10 years. The move from amide-modified castor oil
because the relatively fast recovery of the viscosity will lead to non- to pure amides has enabled adhesive and sealant manufacturers to
slumping properties and will prevent the sealant from flowing once reach a level of performance which was not possible with the previous
applied. The additive should not modify the other properties of the technologies.
sealant such as curing time, adhesion, tack-free time, green adhesion. By forming a dense 3D-network of fibres (Figure 1), amide derivatives
Finally the properties of the sealant after curing should not be com- provide a high body, excellent shear-thinning behaviour and very
promised. The rheological additive should no longer act at this stage good pseudoplastic properties. Amides are easy to handle and offer
of the life of the sealant by affecting the mechanical properties, the very good storage stability. They are also more temperature robust
weather-ability, etc. and have no effect on mechanical properties and can be used in both
low modulus and high modulus systems.
Existing technologies to achieve On the other hand, the first generations of amides need a high ac-
good mechanical properties tivation temperature (between 70 °C and 110 °C depending on the
grades and systems where they are used) and a relatively long pro-
cessing time to develop a proper fiber network.
Table 1: MS Sealant recipe The first generations of amides have significant advantages compared to
inorganic technologies and even to castor-oil-based products. They are
less dependent on solvent polarity and more resistant to severe condi-
Formulation
“MS Polymer S203 H“ 14.9
“MS Polymer S303 H“ 10 Table 2: Evaluated rheology modifiers
Plasticiser 17.4 Product Type Incorporation conditions
Rheological additive 3.7 Fumed silicas Inorganic 3.7 %, 2500 RPM, 30 min,
no external heating
CaCO3 fillers 49.51
Precipitated Calcium Inorganic 3.7 %, 2500 RPM, 30 min,
TiO2 pigments 2.5
Carbonates (PCC) no external heating
UV stabilizer 0.25
"Crayvallac SL" Amide (1st genera- 3.7 %, 2500 RPM, 30 min,
Light stabilizer 0.25 tion) 100°C
Dehydration agent 0.74
"Crayvallac SLX" Amide (2nd genera- 3.7 %, 2500 RPM, 30 min,
Adhesion promoter 0.5 tion) 80°C
Hardening catalyst 0.25 "Crayvallac SLT" Amide (3rd genera- 3.7 %, 2500 RPM, 30 min,
100 tion) no external heating

88 R h e ol og y M o d i f ie r
 tions. Furthermore, the first amide generations are also more efficient This new generation of amide has been developed to allow the activa-
and allow formulators to improve the viscosity stability of their products. tion step to take place between 45 °C and 60 °C depending on the
A major disadvantage is the need to activate the additive at a high formula. It has a direct impact on the processing time of the sealant.
temperature (between 90 °C and 110 °C) under high shear during the In Figure 2, the orange curve represents a regular processing time for
dispersion of pigments and fillers. a sealant using an amide which requires heat activation at 80 °C. The
Most developments during the last fifteen years were aimed at ena- full process is relatively long and takes about two hours. The main
bling sealant producers to work at lower temperatures (70 °C to 90 °C time-consuming steps are the activation and the subsequent cooling.
for an earlier product and less than 60 °C for the new material). Using the new generation of amide (Figure 2, blue curve) allows the
activation process to be carried out at a temperature of 50 °C. This
Working at low temperature means that external heating is no longer necessary, since this tem-
perature is easily and quickly achieved by shear. The full activation
The idea behind the development of this new bio-based rheology also becomes easier and faster. Only 20 to 40 minutes are necessary
modifier was to develop an amide which allows the adhesive and seal- to fully develop the 3D network of fibres. The result is that the new
ant manufacturers to work at low temperatures and achieve a shorter amide generation enables the sealant manufacturing time to be al-
processing time thereby reducing energy consumption and therefore most halved.
being more environmentally friendly. At the same time, all the benefits
of the amide technology needed to be maintained. That is to say, ex- Achieving more by using less
cellent shear-thinning behaviour providing ease of extrusion, ease of
application and excellent workability, together with the feature that This is not the only advantage of this new product. The market trend
the pseudoplastic properties prevent slumping and flow once applied. is to develop materials that can do more with less and to design mol-
Figure 3: Molteni lab mixer Figure 5: Storage stability
Figure 4: Brookfield viscosities Figure 6: Optimum activation conditions for SLT product

R h e o l og y M o d i f ie r 8 9
ecules which are more effective at the same content level and thereby cal effect. Usually, the recommended level of PCC is around 20 %. All
save energy, raw material costs and also waste. The following case amides and fumed silica provide a good viscosity and a high body.
study shows that, in that respect, this new amide fulfils all necessary Nevertheless, the level of fumed silicas would need to be increased in
requirements order to reach similar properties to the amide additives.
This case study involved a comparison of various additives in a silane
terminated polymer. Several rheology modifiers were evaluated and Improved performance, viscosity and structure
compared in a low-modulus, hybrid-sealant formulation (Table 1) at the
same addition level, using a Molteni lab mixer (Figure 3). Incorporation This latest amide development shows improved performance, viscos-
conditions were adjusted for each additive in order to achieve the opti- ity and structure. Performance is significantly improved. As this addi-
mum performance of each technology. tive is more efficient, the level at which it is used can even be reduced
The different rheological additives (Table 2) were added at 3.7 % in compared to the older generation of amides.
weight on the total formulation and were compared in terms of pro- Viscosity stability is also an important parameter for sealant manufac-
cessing time, ease of use, gunnability, viscosity, storage stability and me- turers. Especially for amide additives, this data also makes it possible
chanical properties. to verify that the activation of the rheological additive has been fully
Viscosities at low shear were measured three days after production achieved during the sealant manufacturing process.
using a Brookfield viscometer equipped with a Helipath system (usu- Figure 5 shows the viscosity stability after 15 days at 50 °C compared to
ally used for very thick materials). Results are shown on Figure 4. the viscosity measured three days after production.
All the additives tested exhibited a shear-thinning behaviour. PCC did The earlier amide (shown as SL) exhibits a significant increase of vis-
not perform so well and showed poor viscosities at this level. Actually, cosity. This means that the additive was not fully activated during the
PCC require a higher addition level to achieve a significant rheologi- manufacturing process. A higher activation temperature, or a longer
dispersion time, is needed to achieve this. This is the main disadvan-
tage of the first generation of amides due to the fact that the neces-
Figure 7: Comparison of Brookfield viscosities of different sary activation temperature is difficult to control at such a high level.
technologies The viscosity of fumed silicas also increases on storage. This is normal
with this technology.
On the other hand, the latest generations of amides, SLX and SLT,
show very good viscosity stability. Full and correct activation has taken
place. These two products are also more robust against variations of
the incorporation conditions.
Another test has been performed in order to define the optimum ac-
tivation conditions of the new additive, SLT. Therefore, it was activated
at three different temperatures (30 °C, 40 °C and 50 °C) during 15
minutes. Then, the rheological performances were measured (Figure 6).
It is clear that SLT is properly activated as from 40 °C. Performance
changes little between 50 °C and 40 °C. At 30 °C, activation is incom-
plete. The additive would require a much longer dispersion time,
around 45 to 60 minutes.
Comparing additives in epoxy adhesives
A second case study was carried out to compare various additives in

epoxy adhesives. The results were as follows.
In the past, amide-based rheological additives were often only con-
sidered suitable for use in silane based sealants, but in fact they are
Figure 8: The bio- renewable content of the family of additives compatible with many different adhesives and sealants. The following
discussed results were obtained from tests in an epoxy system. In this case the
different additives were compared in the epoxy part of a 2K epoxy ad-
hesive. SLX was measured against a previous generation of material
and with fumed silicas. The different additives were added at a level of
1.5 %. The activation step took place under the same conditions for all
samples, i.e. at a temperature of 50 °C at 2.000 RPM for one hour. The
results obtained are set out in Figure 7.
Both amide derivatives gave good results. Viscosity at low shear was
excellent and the shear thinning behaviour was good, thus guarantee-
ing excellent storage stability and application properties.
Fumed silicas possess lower viscosity at low shear than amides. Thus
more fumed silicas are needed to reach the same level of performance.
The best result is obtained with the product containing the SLX.
As shown in Figure 8, this family of amide powders is more than 90 %
bio-sourced. More specifically, the latest generation of amide, SLT, is
bio-sourced and bio-renewable at 98 %. 

90 R a d i at i o n c u r i n g
Source: demarco - Fotolia.com
The heart of the matter

Novel approaches to gloss reduction in UV coatings. By Björn Tiede, Lubrizol.
Matting of 100 % solids UV curable coatings can be difficult and several approaches to meet today’s demands on new coating materials.
film properties may also be impaired. Tests are reported on Radiation curable coatings show great potential, especially in terms of
two new products which reduce gloss in different ways from short cycle times, reduced VOC emissions and outstanding film proper-
established additives. Compared with waxes and silicas, per- ties. This technology offers coating manufacturers the option to formu-
formance is less dependent on film thickness but more de- late highly versatile coatings for almost every field of application.
pendent on oligomer reactivity. Compared to conventional coatings (i.e. waterborne
D emands on coating materials in terms of cost efficiency, opti-

mised cycle times and emission of volatile organic compounds (VOC)
have changed significantly during the last ten years. Industry has found
Figure 2: Gloss development at different addition rates of three
different additives
Figure 1: Representation of different matting mechanisms: top,

particle based; middle, internal reflection; bottom, excimer pattern

R a d i at i o n c u r i n g 91
‘concentrate’ the matting agent during physical drying. During evaporation

of volatile compounds, the applied film starts to shrink. This shrinkage can
vary from 30 % up to 60 % of the wet film volume depending on volume
Results at a glance solids. Compared to this, 100 % solids UV coatings show film shrinkage
of between 3 % and 8 % (depending on the resins and monomers used).
űű Matting of UV curable coatings can be difficult, especially In the case of 100 % solids UV coatings the absence of volatile solvents
in the case of 100 % solids systems. Film properties may also leads to various problems for the formulator. To lower the viscosity of the
be impaired if monomer levels have to be increased when the resin, especially with higher amounts of matting agents, the use of low
matting agent increases viscosity. viscosity monomers is unavoidable.
As these monomers will crosslink with the resin they will also influence the
űű A new type of matting additive produces controlled inter- final film properties. The lower the gloss level of the final coating, the more
nal film crystallisation during cure, so that the light scattering monomer is needed to obtain an acceptable viscosity. This can lead to
required for gloss reduction occurs inside the film instead of impaired film properties, flow and levelling issues, reduced reactivity and
on the surface. other problems. Solventbased systems can overcome this problem due
to the thinning ability of the volatile solvents.
űű Another new additive also creates a wrinkled surface by Another important factor is curing speed. Convention-
modifying the surface flow of the coating during cure. This is al coatings usually show open times between five and
more efficient than the internal crystallisation method alone. 30 minutes, whereas the curing process of UV coatings takes place in
seconds. This short time frame for curing in UV coatings also prevents
űű With both new additives performance is almost inde- adequate orientation / floating of the matting agents and lowers their ef-
pendent of film thickness, whereas efficiency of waxes or silicas ficiency. The result is a much lower efficiency of the matting agents, which
can decrease at high film thicknesses. However, the new ad- needs to be compensated by higher addition rates.
ditives are more affected by differences in oligomer reactivity. Below, the use of classic matting agents (silica and wax based) is com-
pared with new approaches to matting UV curable coatings. The main
focus of this article is to compare different matting technologies (com-
mercial and experimental ones) and show up the individual strengths
and weaknesses of the different technologies.
Conventional matting outlined
The traditional way of reducing the gloss of a coating is the use of a solid
1 pack or 2 pack systems) the field of radiation curable coatings bears matting agent. In general these matting agents are silica or wax powders.
different challenges on the formulation and curing side, many caused (In many applications silica is preferred due to its higher efficiency.) Using a
by the curing mechanism. classic silica or wax as matting agent means using a particle to add light
The formulation of matted clear coats in particular can become an ex- scattering to the final film.
tremely tough challenge to the formulator. In the case of 100 % solids In this approach the matting agent particles lead to a structured coating
coatings it can be complicated to find the balance between: surface that no longer reflects light directionally. The final structure can
ąą Acceptable viscosity for the targeted application method; vary between fine grain structure and a texture-like effect and is influ-
ąą Targeted gloss level; enced by particle size, porosity and chemical nature of the matting agent.
ąą Desired film properties (e.g. scratch resistance, Moving away from the classic particle-based matting approach means
hardness, chemical resistance, etc.) looking for alternative mechanisms to scatter light in a coating film. Two
novel ways to achieve light scattering will be discussed and are illustrat-
The nature of the matting mechanism ed in Figure 1.
To understand the difficulty of matting 100 % UV coatings, the classic mat- Internal scattering provides matting in clear coats
ting process must be understood in order to clarify the differences from
conventional coatings containing volatile compounds. To obtain low gloss values it is necessary to scatter the light reflected
Due to solvent evaporation, conventional coatings start to orientate and by the film. Most matting approaches focus on scattering the light on 
Figure 3: Appearance of films when using different matting additives at different addition rates: left, Matting Agent A; middle, Matting
Agent B; right, Matting Agent C

 the coating surface. In the case of clear coats, significant amounts of Alternative ways to achieve surface structuring
visible light will pass through the coating film and will be absorbed and
reflected by the substrate. By influencing the surface curing of a radiation curable coating, the
By creating light scattering structures such as defined crystal struc- final film can be forced to form a heavily structured layer. This highly
tures inside the coating film, the light that passes into the film will be wrinkled surface scatters the incoming light, which can lead to very
scattered inside and the film appears matt. In the case of this new low gloss values. In general this effect can be obtained by utilising spe-
matting additive, the matting performance is achieved via controlled cial curing equipment such as excimer devices in combination with
crystallisation during cure. This new additive technology is based on specially formulated coatings.
the synergistic effect between an acrylic-functional carrier and a spe- Here this processing equipment will not be examined, but a different
cial polymeric solid phase. way to achieve comparable structuring patterns will be considered.
The internal light scattering behaviour can be seen by looking inside Basically, the structuring effect can be caused by influencing the sur-
the coating with a laser microscope. Inside the coating a refractive face flow of a coating during the curing process.
pattern similar to those that are sometimes seen in a swimming pool In case of the novel chemistry, individual particles cause the coating to
becomes visible. Each of these structures corresponds to a crystalline flow away from them. This flow process is related to polarity changes of
border in the film. Due to the interaction of the crystals with light the the coating during the curing process and generates micro-scale waves
film becomes matt. during curing.
Figure 4: Gloss development at different film thicknesses
Table 1: Over view of matting agents used
Matting Agent A Matting Agent B Matting Agent C
General nature Proprietary Proprietary blend Untreated silica

blend of of polymers (the classic mat-
polymers ting approach)
Main matting Internal light Internal light Surface

mechanism scattering scattering plus structuring
surface structuring (particles)
(without particles)
Mean particle 6 µm 9 µm 9 µm
size
Table 2: Formulation used for comparison of matting agent Table 3: Basic formulation scheme for oligomer compatibility tests
performance
Raw material Addition Description Raw material Addition %

level %
Oligomer 65.0
“Laromer LR 9004 (BASF)” 40.0 Polyester acrylic
“Laromer LR 8986 (BASF)” 31.0 Epoxy acrylic “Irgacure 500” 5.0
“Laromer DPGDA (BASF)” 24.5 Thinning monomer
UV matting agent 5.0

“Byk A-530 0.5 Air release agent
(Byk Chemie)”
“Irgacure 186 ” (BASF) 4.0 Photoinitiator DPGDA 25.0
Total 100.0 Total 100.0

R a d i at i o n c u r i n g 93
Overview of the test procedures nology is able to effectively look into a coating film to determine the
internal light scattering behaviour of a coating.
The matting processes described above are examined to show spe- As coating viscosity and formulation costs are important drivers for
cific advantages and disadvantages of each process. The emphasis choosing the right matting agent and setting up the final formulation, the
lies on: matting agents should show maximum efficiency to keep addition rates
ąą General efficiency at different use levels at a minimum.
ąą Stability of matting effect at various film thicknesses To check the efficiency development of the different matting approach-
ąą Compatibility with various oligomers. es, the matting agents were incorporated at varying addition rates into
The materials used in this comparison are briefly a common UV curable coating system based on epoxy- and polyester
described in Table 1. acrylates. For this test the addition rates varied between 1 % and 15 %
Due to its high reproducibility and the ease of use, all application tests matting agent (supply form based on total formulation weight).
were carried out by using a drawdown application on contrast charts.
The film thickness is indicated in the different segments individually. Results with the two new additives compared
For all microscopic pictures, a Keyence “VK-X210” laser scanning micro-
scope was used. Confocal laser scanning microscopy is used to analyse Matting agents were compared in the formulation shown in Table
surface structure effects at a very high resolution. In addition, the tech- 2, and results are shown in Figure 2. With Matting Agent A, even at
low addition rates the internal light scattering shows a significantly
lower gloss compared to a particle-based approach. Interestingly, the
matting efficiency shows a maximum at approximately 5 % addition
level. After reaching this maximum the matting performance becomes
worse when matting agent content is further increased.
This phenomenon is related to the matting approach itself. The in-
ternal light scattering is caused by controlled crystal formation in the
coating film. Increasing the addition level of matting additive increases
Table 4: Property comparison of matting agents tested the number of crystals and the matting performance thus gets better.
At a certain point a maximum density of crystalline borders in the film
is reached. In this specific system this point is reached at 5 % matting
Advantages Limitations
agent content. Adding more matting agent to the system forces the
Matting Agent A High matting power at No linear correlation crystalline borders to overlap and finally to disturb each other which
low addition levels. between addition level results in less efficient light scattering – the gloss goes up (see Figure 3).
No influence on coating and gloss values. Matting Agent B utilises a multipurpose approach to reduce the gloss of
viscosity. Ideal addition range the final film. The gloss development is comparable to Matting Agent A but
Superior surface feel. varies depending on
the overall efficiency is higher. This similarity in matting behaviour at low
Mechanically stable the formulation details.
matting effect (as the Efficiency depends addition rates between Matting Agents A and B is related to internal
matting appears inside on the formulation light scattering.
the film it is not polish- details (reactivity, curing Due to the multi-functional approach of using more than one matting
able). speed, raw materials). mechanism the gloss increase at higher addition rates is significantly
Uniform matting. Limited usability in lower compared to Matting Agent A. (The loss of performance caused
pigmented systems. by overlying crystals can be compensated by surface structuring.)
On the microscopic pictures in Figure 3 it can be seen that at 1 % ad-
dition level the formation of microscopic ‘craters’ occurs around each
particle. This texture effect is related to flow effects that occur during
the curing process. The coating around each particle moves away and
leaves a small dent with the particle in the centre.
Matting Agent B High matting power at No linear correlation
The size of these dents is approximately 20-30 µm in diameter and
low addition levels. between addition level
3-4 µm deep. By increasing the amount of matting agent the texture
Low influence on coat- and resulting gloss
ing viscosity (compared values. comes closer till it starts to interconnect and form a uniform texture
to standard silica). Efficiency depends comparable to an excimer pattern.
Superior surface feel. on the formulation The classic particle-based approach leads to an almost linear matting
Broad compatibility in details (reactivity, curing curve. The more silica is added to the coating the rougher the surface
different oligomers. speed, raw materials). becomes. This can also be seen by looking at the microscopic pic-
Very uniform matting tures taken from the coating surface, again in Figure 3. In addition the
with better aesthetics.
surface structures obtained with silica tend to be more ‘rough’ with
less uniformity and a more irregular height profile compared to the
texture obtained by Matting Agent B.
Matting Agent C Efficiency develops High viscosity build up
almost linearly – easy Index of refraction How film thickness modifies matting effects
and reliable gloss prevents any light
control. scattering inside the In the field of UV curable coatings, film thickness is another important
Standard matting coating film. topic for discussion. Usually the matting efficiency depends strongly on
method with formulators Results may be the particle size of the matting agents. In general this means that increas-
having long experi- dependent on film ing the particle size of silica makes matting efficiency better. This also
ence. thickness.
means that changing the applied film thickness could have a significant
influence on the final matting performance. 

 In this comparison the influence of film thickness on the efficiency of with Matting Agent B results in two major advantages:
the different matting mechanisms was tested. The same coating was ąą broad compatibility with lower influence of oligomer reactivity;
therefore applied at different film thicknesses. ąą higher efficiency than pure internal and pure surface light scattering.
As expected, the pure particle approach shows an almost linear cor- As a significant portion of the matting performance is still linked to struc-
relation between film thickness and gloss. Once the mean particle size tural and crystalline formations, the oligomer reactivity does influence
of the chosen silica (9 µm) is exceeded, the gloss goes up significantly the final matting performance.
(see Figure 4). The silica shows a consistent performance with most of the oligom-
On the contrary, the particle approach with Matting Agents A and B ers tested. Reactivity slightly influences the final matting performance,
shows an almost stable performance over all film thicknesses tested. but not as significantly as with Matting Agents A and B. The matting
Once a sufficient film thickness is reached for internal light scattering efficiency of the silica particles is influenced more by wetting and flow
to occur, it does not matter if the film thickness changes. This leads to properties of the oligomers. The final surface roughness that gives the
a very consistent performance over a wide film thickness range. matting efficiency is in most cases almost identical, and so is the gloss.
Performance tested in various oligomers Benefits and limitations summarised
As well as efficiency, broad compatibility is a key criterion for a matting Utilising mechanisms other than the traditional ones often means
additive. To compare the efficiency of the new matting approaches a changing the way a formulation is set up to get optimum results. The
broad test series was set up including several acrylic oligomers. The matting agents discussed above are a first step into developing new
main idea behind these trials was to formulate a coating that was as ways of controlling the light scattering properties of radiation curable
simple as possible (see Table 3) and check different additives in it. coatings.
The results presented graphically in Figure 5 show that the perfor- These additives are the first and second generation of this approach
mance of Matting Agent A correlates with the reactivity of the oligom- and show that the basic principles already work well but still need
ers. The internal light scattering is based on precipitation processes further refinement.
that occur during the curing process. In general it can be said that a combination of different matting mech-
Thus, the whole matting mechanism is influenced by curing speed and anisms shows superior performance, whereas it appears that surface
most importantly by the gel time. It is clearly observable that highly reac- scattering still gives more consistent and stable matting results. The
tive systems with short gel times prevent the coordinated formation of benefits and limitations of each approach to matting are summarised
the matting crystals. The combination of different matting mechanisms in Table 4. 
Figure 5: Comparison of matting performance in different oligomers

Source: Stefan Schurr - Fotolia.com

LightWeight
Only 30 grams of paint is
used on bikes for the Tour
de France. This correlates
to merely one sixth of the
weight of a coating of a
normal bike which weighs
around 180 g.
A long Journey
The Tour de France has been
held every July since 1903,
with only a couple of inter-
missions during World War I
and II. The tour, that is among
the world‘s most prominent
sports events, is regarded to
be the hardest bycicle race.

96 S u r fa c tant
Source: Cmon - Fotolia.com
Fluorosurfactants
flourish
Combining good eco toxicological behaviour with technical performance.
By Reiner Friedrich, Elisabeth Höner and Fanny Schooren, Merck KGaA.
The control of the surface energy is a major task in high perform- Figure 1: Three stages of wetting – a) perfectly wettable, b) wet-
ing coating industries. During the coating process the properties table and c) unwettable. The contact angle Θ is measured at the
like wetting and leveling are governed by the interfacial forces meniscus of the liquid/solid interface. The spreading behaviour
within the substrate, the coating and the air. Fluorosurfactants is governed by the interfacial forces of the surface tension of
provide low surface tension. A new class of short chain fluori- the liquid gLA , the surface energy of the substrate g SA and the
nated surfactants show superior technical performance in com- interfacial tension gSL bet ween solid and liquid. Spreading coef-
bination with a better environmentally friendly profile. ficient S is the sum of the interfacial vectors gLA, gSA and gSL.
Spreading occurs only if S > 0.
I n high-performance coating technologies control of surface energy

is key. Many of the important parameters of a coating like wetting,
leveling, (anti)foaming, adhesion, recoatability, stability of dispersions
and so on are governed by the interfacial forces within the substrate/
coating/air system. Coating additives are often specially designed to
retard at the boundary of these interfaces to influence surface energy
in the desired way. To measure the effectiveness of such surface ac-
tive substance (= surfactant), a variety of different analytical instru-
ments are used. In general they are based on the concept of surface
tension or contact angle measurement [1].
For the very obvious effect of wetting, Figure 1 depicts three common
situations of how a substrate surface interacts with a coating system:
a) perfectly wettable, b) wettable and c) unwettable.

S u r fa c tan t 97
Applying waterborne coating systems on surfaces like PE or PP is a

Results at a glance challenging task, because of the huge discrepancy in surface energy of
both systems. Only powerful additives like fluorosurfactants are able
to bridge this gap sufficiently and provide reliable and cost efficient
űű In high-performance coating technologies where control solutions.
of surface energy is key fluorosurfactants provide low surface Fluorosurfactants provide low surface tension (< 20 mN/m) at smallest
tension at smallest concentration – an additional feature of ear- concentration (0.1-0.01 w%). This characteristic is due to the fact that
lier versions are its extreme stability at high temperatures and the perfluorinated alkyl chains exhibit almost no interaction with other
under harsh chemical conditions. components. An additional feature of this perfluorinated molecule part
is its extreme stability at high temperatures and under harsh chemical
űű However, these fluorosurfactants with chain length >C6 conditions [2]. The C-F bonds in fluorosurfactants are not susceptible
were found to be bio accumulative and toxic. to biodegradation and therefore regarded to be persistent in the en-
vironment. Additionally, fluorosurfactants with chain length >C6 were
űű Shorter chain C2 and C3 branched fluorosurfactants have found to be bio accumulative and toxic. This is why this group of sur-
been developed exhibiting remarkable surface tension reduc- factants is in the focus of regulatory affairs and NGOs [3].
tion. In many areas C6 Fluorosurfactants are now used as C8 replacement.
Environmental and toxicological profiles depend on the length of the
űű Characteristics include super spreading and good dewet- perfluorinated alkyl chain; the smaller the better. A decline in chain
ting resistance, which are beneficial for many coating applica- length normally leads to a lower technical performance and higher us-
tions age concentration. A new class of short chain fluorinated surfactants
which exhibit superior technical performance in combination with a
űű Importantly, the new NIO surfactants are beneficial for cus- better environmentally friendly profile than existing C6 materials have
tomers and the environment as they perform like the older C8 ma- been developed.
terial in terms effectiveness and efficacy (surface tension reduction The results were published in two recent articles about the develop-
and working concentration) and are less harmful than existing C6 ment of branched short chain fluorosurfactants [4,5]. This article aims
materials. at expanding on application results.
C2 and C3 branched Fluorosurfactants –

a synergistic couple
For anionic surfactants the best solution arose from combining environ-
Good wetting is only achieved when the spreading coefficient S be- mental friendliness and high technical performance in a branched struc-
comes positive (S>0) when gSA>(gSL+gLA). In other words the surface ture containing three fluorinated alkyl chains C2 or C3. Both versions
energy of the substrate has to exceed the combined surface ener- are now commercially available and are offered as 30% solutions, based
gies of the Liquid/Air and Liquid/Solid interface. In practice this means on C2-chains or either on C3-chains.
either to pretreat the substrate surface (rise the surface energy e.g. Despite their extremely short fluorinated chains the surface tension reduc-
though plasma treatment) or to lower the surface tension of the coat- tion is quite remarkable. Figure 2 shows the dynamic surface tension profile
ing by adding suitable surfactants. of a 0.1w% solution of the C2 and C3 surfactants and mixtures thereof. 
Figure 2: Dynamic surface tension measurement of 0.1 w% Figure 3: Wetting behavior on PTFE 60 sec after deposition of
aqueous solutions of pure C2 and C3 surfactants and mixtures a droplet. a) Pure water does not wet PTFE; b) 0.1 % aqueous
thereof measured with a bubble pressure tensiometer. The solution of a common C6 fluorosurfactants shows improved wet-
mixtures are indicated as weight % of C3 and C2, e.g. 0:100 in- ting. This effect is not time dependent (the contact angle does not
dicate 0 % C3 and 100 % C2; 20:80 indicate a mixture of 20 % become smaller over time); c) 0.1 % aqueous solution of Tivida
C2 and 80 % C3, etc. Blow up: Minimum surface tension at long FL 2500 shows super spreading behavior on PTFE. This effect is
bubble life times (~1 minute) of selected mixtures. time dependent. The solution spreads further and until the amount
of evaporated water becomes significant (not shown here).
a) Water
b) C6 Fluorosurfactants c) C3 Fluorosurfactants

98 S u r fa c tant
 The pure C2 material (100:0) shows a very steep decline in surface ten- behind the rapid spreading is still not fully understood, but it seems
sion over the first 100 ms, which indicates that this fluorosurfactant has to be correlated with a branched structure [7,8] the ability to form
a high mobility. As bubble life time becomes longer the curve flattens bilayer aggregates [9] and the Marangoni effect [10-12]. In the case
out and approaches a constant level. The surface tension at bubble of low surface energy substrates (<30 mN/m) the spreading rate of
life times of 1 minute can be regarded as “quasi” static and present trisiloxane solutions is substantially reduced [13]. There is no example
therefore the lowest achievable value. For the C2 material this level of super spreading on low energy surfaces like Teflon reported in the
is about 21 mN/m. The pure C3 material (0:100) shows a different literature [14, 15].
behavior. Up to 700 ms bubble life time the surface tension reduc-
tion lag behind the C2 values, indicating less mobility for the C3 mol- Reduce dewetting defects
ecule. On the other hand a final surface tension reduction to a value
of 16.6 mN/m is an outstanding performance which is hardly reached Another feature which is important for general coating application is
by most C6-fluorosurfactants. to prevent dewetting effects of surfaces. Especially on rough or un-
If both materials are combined synergies in speed and surface ten- even surfaces the lacquer has to level irregularities leading to an inho-
sion reduction can be seen. If only 20 % of C2 is replaced by C3 (see mogeneous thickness of the coating. This remains a major challenge
Figure 2, line 80:20) the final surface tension is as low as 18.8 mN/m in industrial wood coating industry. Surfaces here do not only differ
without sacrificing the mobility of the molecules. This allows tuning of among the types of wood used, but also vary within one wood species
speed and surface tension in a broad range and reach optimum solu- due to natural fluctuations. To demonstrate the efficacy of a coating
tions for many applications. to withstand dewetting at various thicknesses the following test was
applied.
Super spreading on PTFE A white aqueous low VOC alkyd enamel dispersion was formulated
with 0.1 % with the C2-base product and 0.1 % C-6 fluorosurfactants
As explained in Figure 1 the surface energy of the substrate gSA is of respectively. A panel was dipped into the dispersion and slowly pulled
great importance to the spreading of a coating. For “critical” surfac- out. Immediately a gradient in film thickness over the substrate oc-
es (surfaces with low surface energy) only powerful surfactants like curs, as shown in Figure 4. If the panel is kept in the upright position
fluorosurfactants can provide satisfactory solution. This becomes the dispersion continues to drip from the panel leaving behind a thin
even more relevant when the coating-system is waterborne. Table 1 layer coating.
lists the surface energy of some common polymers. Good dewetting resistance is assured if, over time, no “black spots”
The substrates which are most critical for coating applications exhibit occur on the panels. The film thickness of the coating increases from
a surface energy of 30 mN/m and below (PP, PE, FEP and PTFE). PTFE, 0 to 100 µm (top to bottom). The images in Figure 4 show that the
for example, is used as non-stick surface finish as Teflon, because the C2-based product is far superior to common C6 fluorosurfactants in
low surface energy will prevent water or even grease to adhering to it. resisting the tendency of the coating to dewet, particularly at low film
The C3 based product exhibits a very unusual behavior on these ex- thickness.
tremely low energy surfaces. Figure 3a shows a water droplet on a PTFE
surface. There is a high contact angle between liquid and surface due New class of non ionic surfactants
to the negative spreading coefficient. If a 0.1 w% standard C6 fluoro-
surfactant is applied, the contact angle is much lower (~ 45°) indicating The concept of short chain branched surfactants can also be applied
a good wetting of the surface (Figure 3b). 0.1 w% of the C3 surfactants to non ionic fluorosurfactants. The design of these surfactants con-
shows a different picture. Here the droplet spreads further apart lead- sists of two fluorinated alkyl chains -C2, C3 or C5 resp. - and a polygly-
ing to a complete spreading of the water film on the PTFE surface (Fig- col chain. Through the length of the polyglycol chain the hydrophilic-
ure 3c). This phenomenon is referred to as “super spreading”. lipophilic balance of the molecule can be tuned effectively. For the
Super spreading is only common in trisiloxane surfactants, which are investigation ethoxylation degrees of 8, 12 and 17 repeating units
used in coatings, cosmetics and agrochemical [6]. The mechanism yielding nine different surfactants (see Figure 5) were used. The CMC
Figure 4: Images of black panels coated with a white aqueous low VOC alkyd enamel dispersion via dip coating. Immediately after
pulling out the panel a photo was taken (time = 0 min) and the panel was kept in an upright position. After 5 minutes the second
picture was taken. Surfactant concentration 0.1 w% (if applicable).

S u r fa c tan t 99
(critical micelle concentration) of these compounds was estimated to References

compare them with existing C6 material and the “old” C8 level.
Figure 5 shows that C2-surfactants have the lowest impact on surface [1] Couper C., in “Physical Methods of Chemistry, 2nd ed., Rossiter B.W. and
tension reduction and also show a high CMC (for C2-EO-12 and C2- Baetzold R.C., eds., Vol. IX John Wiley Sons , New York (1993)
EO-17 no precise CMC could be determined, but seems to be > 1 g/l). [2] Kissa E., Fluorinated surfactants and Repellents, Surfactants science
It seems that the existence of only two C2 groups per molecule is not series 2001, 97; 80ff
sufficient enough to design high performing surfactants. C3 groups [3] Environmental Protection Agency (EPA), 2010/2015 PFOA Stewardship
seem to be more suitable, showing a CMC in the range of existing C6 Program
materials and a surface tension between 22 and 24 mN/m. [4] Jonschker G. et al, Europ. Coat. Jnl, 2010, No. 7-8, pp 24- 27
Best performance show branched NIO surfactants with C5 chains [5] Schellenberger S. et al, Europ.Coat. Jnl, 2012, No. 11, pp 32-36
having a very good surface tension reduction in combination with [6] Ivanova N., Starov V., Johnson D., Hilal N., Rubio R., Langmuir.,
very low CMC values (C5-EO-8; -12; -17). Since CMC reflects the ef- 2009, 25, 3564-3570
ficiency of a surfactant, the branched C5 design outperforms exist- [7] Ananthpadnamabham K. , Goddar E. D., Chandar P., Colloids Surf.,1990,
ing C6 materials because the working concentration for applications 44, 281–297.
will be much lower. Additionally these materials show a much lower [8] Shen Y., Couzis A., Koplik J., Maldarelli Ch., Tomassone S., Langmuir.,2005,
tendency to foam than existing C6 material. Therefore they are much 21, 12160–12170.
more suitable e.g. for high thoughput printing application were foam [9] Venzmer J., Wilkowski S. P., Trisiloxane surfactants – mechanisms of
is a very critical parameter. spreading and wetting. Pesticide Formulation and application Systems:
Last but not least the new NIO surfactants are beneficial for custom- 18th Volume,ASTMSTP1347; Nalewaja J. D., Goss G. R., Tann R. S., Eds.;
ers and the environment; they perform like the “old” C8 material in American Society for Testing and Materials: West Conshohocken, PA,
terms effectiveness and efficacy (surface tension reduction and work- 1998; pp 140-151
ing concentration) and are less harmful than existing C6 materials. [10] Chengara A., Nikolov A., Wasan D., Colloids Surf., A 2002, 206, 31.
[11] Nikolov A. D., Wasan D. T., Chengara A., Koszo K., Policello G. A.,
Conclusions Kolossvary I., Adv. Colloid Interface Sci. 2002, 90, 325.
[12] Chengara A., Nikolov A. D., Wasan D. T., Ind. Eng. Chem. Res. 2008, 47,
Branched short chain fluorosurfactants are a new class of environ- 3639–3644.
mentally friendly, high performing surfactants, which show a variety [13] Kumar N., Couzis A., Maldarelli C. J., Colloid Interface Sci. 2003, 267, 272.
of benefits in multiple technical applications. The main characteris- [14] Zhu S., Miller W. G., Scriven L. E., Davis H. T., Colloids Surf., A 1994,90,
tics of this surfactants group are: fast acting, high performing and low 63–78.
foaming. Additional to the technical benefits this material class can be [15] Svitova T., Hill R. M., Smirnova Yu., Stuermer A., Yakubov G., Langmuir.,
considered as the most environmentaly friendly fluorosurfactants on 1998, 14, 5023
the market due to its outstanding toxicity and non hazard profile. 
Figure 5: Comparison of the surface tension of branched short Table 1: Surface free energy of some commercial plastics
chain fluorosurfactants with standard C6 and “old” C8 mate- [source: WWW]
rial. The surfactants are grouped according to their fluorinated
chains. The crosses above the bars indicate the CMC of the par-
ticular compound in g/l. Nomenclature: E.g. C2-EO-8: Surfactant Polymer Abbreviation Surface energy at 20 °C
containing t wo C2-groups and a polyglycol chain with 8 Ethoxy- [mN/m]
repeating units. C6-1 to 3 present three different, commercially
available C6 NIO surfactants. Polyethylene tereph-
PET 42
thalate
Polymethylmeth-
PMMA 41
acrylate
Polyvinyl alcohol PVA 37
Polystyrene PS 34
Polyethylene PE 30
Polypropylene PP 30
Fluorinated PE/PP FEP 20
Polytetrafluoroethylene PTFE 19

1 0 0 D r ie r s
Source: imago pubblicità - Fotolia.com

Cutting
ketoximes
Encapsulated driers minimise skinning of air-drying
paints. By Jörg Horakh, Hugh Gibbs, Franjo Gol and
Gaby Kiepe, OMG Borchers.
Air-drying alkyds require anti-skinning agents to prevent single-component paint systems which crosslink at ambient tempera-
premature curing in the can. There is regulatory pressure in tures. The introduction of high solids binders as well as water-based
Europe to reduce exposure to these agents to levels which alkyds has been a major contribution to reduced VOC emissions of
are difficult to meet. An iron drier encapsulated so that it is paints, providing eco-friendly alternatives for paint manufacturers.
protected from oxygen during storage but released during ap- The high content of naturally based raw materials in alkyd resins pro-
plication produces minimal skinning. Good to know that they vides a promising alternative to fossil sources. Therefore, the increas-
don’t reduce the coatings performance. ing demand to use renewable raw materials will be a main driving
force towards future developments of alkyd based paints.
A ir-drying alkyd resins play a major role in DIY and professional paints
as well as in some industrial applications. This is mainly due to their
outstanding performance in terms of application properties including
Anti-skinning additives face regulatory challenges
gloss, levelling, pigment wetting and drying under adverse conditions. Paint manufacturers and their suppliers are currently facing chal-
Additionally, autoxidatively curing alkyd resins allow one to formulate lenges caused by the pending threat of hazard labelling of two key
Figure 1: SEM picture of capsules and particle size distribution of a pilot batch of the encapsulated siccative

D r ie r s 1 0 1
according to Article 57(a).

Additionally, anti-skinning agents can slow drying after application, by
Results at a glance reducing the activity of the metal driers and if their own evaporation
is too slow. In order to overcome this skinning issue, one solution is
űű Skin formation during manufacture and storage of to find ways of deactivating driers in the paint can but making them
air-drying alkyd-based paints has historically been resolved active on application.
mainly by the use of MEKO and cyclohexanone oxime, which
exhibit very similar toxic effects. Regulations may require replacement of cobalt
driers
űű There is pressure in Europe to reduce exposure to
these compounds to levels which are difficult to meet. Fu- Cobalt carboxylates are the catalysts (siccatives or driers) most fre-
ture regulations may also require replacement of cobalt dri- quently used for the oxidative curing of alkyd resins. But their use is
ers. under pressure due to their probable classification as carcinogens.
Consequently, there is great interest in possible alternatives for Co
űű A solution is to deactivate driers in the paint can but with no technical drawbacks. Only Mn- and Fe-based driers have been
make them active on application. An iron drier was encapsu- proved in commercial paints to be viable alternatives. In particular the
lated so that it is protected from oxygen during storage, but iron-based catalyst containing the polydentate ligand FeLT [2] in the
when the paint is applied the capsules break and release the “Borchi Oxy-Coat” product range shows no drawbacks with respect to
drier. paint drying activity at extremely low dosage levels. Additionally, the
notorious yellowing of alkyds is minimised with FeLT-based driers [3]
űű This system was shown to reduce the required lev- and they work exceptionally well in cold and humid weather.
els of anti-skinning agents to very low values, with no reduc-
tion in drying performance or physical properties compared Drier encapsulation can resolve skinning problems
to the non-encapsulated form of the same drier.
In order to overcome the skinning issue, it was necessary to find ways
of deactivating driers in the paint can but making them active on appli-
cation. The solution is to encapsulate the iron drier so it is protected
from oxygen during storage.
When the paint is applied, the capsules break and release the drier
ingredients of most alkyd paints: methyl ethyl ketoxime (MEKO) and so it can react with oxygen and function as a drier without loss of the
cobalt carboxylates. drying performance in oxidatively curable alkyd-based formulations.
Historically, the issue of skin formation during manufacture and stor- A microencapsulated catalyst solution is prepared by an interfacial
age of air-drying alkyd-based paints has been addressed mainly by polyaddition process and suitable microcapsule wall materials are
the use of MEKO and cyclohexanone oxime, which exhibit very similar selected from polyureas, polyurethanes and combinations of these
toxic effects. There is pressure in Europe to reduce exposure to levels materials.
which are difficult to meet. Current concerns are [1]: Microencapsulation by interfacial reaction is carried out by initially
ąą Actual working and workplace exposure levels, especially for pro- preparing an emulsion in which the disperse phase is an aqueous
fessional uses and the possible need for further risk management solution of the siccative and the continuous phase is an aliphatic sol-
measures. vent. The polymer is formed at the phase interface of the dispersed
ąą If MEKO becomes classified as carcinogen 1B, (H350 labelling) it will spherical droplets and forms the shell of the microcapsule. 
affect sales to the general public and the substance would fulfil the The result of the microencapsulation process is a dispersion of micro-
criteria for identification as SVHC (Substance of Very High Concern) capsules in an organic solvent in which each microcapsule comprises
Figure 2: Drying times of a high solid clearcoat comparing cobalt Figure 3: Skin formation of a high solids clearcoat with 0.2 %
driers and FeLT with and without encapsulation anti-skin agent during four weeks at ambient conditions

1 0 2 D r ie r s
 an aqueous solution of the metal siccative as the core within a polymer and the encapsulated FeLT-drier showed no influence of the encapsu-
wall [4]. Figure 1 shows a typical particle size distribution of a pilot batch. lation on the hardness development.
Neither oil length nor variations of the fatty acid composition of the
Application tests summarised alkyd resin revealed any significant influence of the encapsulation on
the hardness development of the applied films, indicating that the
The microcapsule dispersion (containing 1 % of the complex, which catalyst in the film is fully available for the curing process. Figure 4
corresponds to 0.09 % of iron metal) was added to oxidatively curable shows the results for hardness development of linseed oil-based al-
paints at concentration levels of 0.25 to 0.5 wt% on formulation. The kyd paint films.
concentrations of the unencapsulated FeLT were always at the same Dark-yellowing of white pigmented paint films (Figure 5) was evaluated
level for comparability reasons. by colour measurements using an “X-rite 8200” spectrophotometer.
Additionally the product was compared with standard cobalt driers. Encapsulated FeLT has a significantly lower influence on long term yel-
Calcium and zirconium were used as secondary drier metals. Wet paint lowing of the system compared to other standard driers such as co-
films were applied at 100 µm wet layer thickness in order to evaluate balt or manganese, which are noted for their strong tendency to pro-
drying times and hardness development. Pendulum hardness was de- mote discolouration [5]. The influence of the encapsulated drier on
termined according to König and drying times using BK drying record- yellowing of alkyds is comparable to the non-encapsulated product.
ers. Skin formation was evaluated visually (using grades from 0: no skin
to 6: complete skin) after four weeks storage at 40 °C and at ambient Mechanical and thermal stability are both good
conditions.
Thermal stability of the encapsulated drier dispersion was tested by
Drying speed and skin formation tests storing samples for three weeks at -18 °C, 8 °C, 23 °C and 40 °C. Eval-
uations of drying and skin-forming properties in paint formulations
Drying times of the encapsulated FeLT were slightly higher compared after storage showed no significant deviations. In the case of paints
to cobalt and to the FeLT drier without encapsulation, as shown in containing encapsulated FeLT the encapsulated drier showed no ad-
Figure 2. verse influence on the paint stability (3 weeks at 40 °C and at ambient
Drying properties were investigated in alkyds with variations in oil conditions).
lengths as well as variations of the constituent fatty acids composi- Dispersions of the capsules as well as various paints containing the
tion of the alkyds without revealing any significant drawbacks in drying dispersion were dispersed for up to one hour at high shear rates im-
times for the encapsulated drier. parting high shear stress on the capsules but resulting in no change
Skin formation of paint films was evaluated visually. Figure 3 shows skin of the drying or skin-forming properties.
formation of a high solids clearcoat with 0.2 % anti-skin agent dur-
ing four weeks at ambient conditions. Encapsulated FeLT showed no Polar solvents can however disrupt encapsulation
skinning, whereas samples containing the cobalt and unencapsulated
FeLT- displayed medium to strong skin formation. As a straightforward preliminary test of the stability of the encapsu-
The use of small amounts of anti-skinning agents is recommended, in lated FeLT, the dispersion was mixed with various solvents in the ra-
order to prevent small amounts of skin formation which could even be tio 10:1. Addition of polar, protic solvents yielded brownish sample
observed for alkyd resins without any siccative added. colours as visible in Figure 6. Table 1 summarises colour changes and
the viscosity increases. The observed increases in viscosity depend
Encapsulation does not strongly on the solvents and are apparently caused by swelling of the
affect hardness or yellowing microcapsules.
Addition of polar solvents with OH- and NH- functionalities results in
Comparison of pendulum hardness developments of standard driers FeLT and encapsulated FeLT having equal drying behaviour and equal
Figure 4: Comparison of pendulum hardness development dur- Figure 5: Yellowing of white pigmented paint films of a long-oil
ing five weeks after application of linseed oil-based alkyd paint alkyd with Co-, Mn- and Fe-driers; measured after six weeks
films containing Co-, FeLT- and encapsulated FeLT-drier storage of the applied films

D r ie r s 1 0 3
skin formation properties. REFERENCES

This is clearly because migration of small polar molecules with OH- or
NH- functionalities results in destruction of the capsule walls and re- [1] Results of the evaluation of 2-Butanone oxime (MEKO) published October 2014
lease of the drier. Formulations containing these substances will there- on the ECHA website: substance evaluation conclusion document, as required by
fore not benefit from the capsules’ advantages in reducing skin forma- REACH Article 48 for Butanone oxime (EC No 202-496-6; CAS No 96-29-7).
tion. Hage, R., Wesenhagen P. V., Liquid Hardening, Patent WO/2008/003652.
[2]
de Boer J. W. et al, The quest for cobalt-free alkyd paint driers, Eur. Jnl. Inorg.
[3]
Benefits and limitations summarised Chem., 2013, pp 3581-3591.
The encapsulated FeLT catalyst offers a sustainable alternative to the Gibbs H. W. et al, Encapsulated Catalysts, Pat. Applic. WO/2015/011430.
[4]
use of cobalt and MEKO in alkyd-based paints: Soucek M. D., Katthab T., Wu J., Review of autoxidation and driers, Prog. in Org.
[5]
ąą Drying properties of encapsulated FeLT are similar to FeLT, cobalt Coat., 2012, Vol. 73, pp 435-454.
and manganese driers;
ąą The tendency to skinning is strongly reduced even without anti-
skinning agents;
ąą MEKO is not necessary as an anti-skinning agent; low amounts of
anti-skin are sufficient, having a low impact on drying time;
ąą Encapsulation has no influence on hardness development;
ąą FeLT from capsules is, however, readily available for extraction in
low molecular solvents with OH- and NH-functionalities, yielding
drying times and skinning properties comparable to FeLT without
encapsulation;
ąą No CMR-classification;
ąą Significantly less discoloration compared to cobalt or manganese
driers 
Table 1: Effect of adding 10 % solvent to encapsulated FeLT-

dispersion: significant viscosity increase and colour change
when polar molecules with OH- and NH-functionalities are used
Solvent (10 %) Viscosity increase & colour change
Xylene no
MPA no
Water yes
Figure 6: Samples with 10 % of various solvents on the Ethanol yes

encapsulated FeLT-dispersion showing discoloration
BuAc no
White spirit no
Propylene glycol yes
DMEA yes
DPM no
MEK yes

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Additives are indispensable ingredients of each and every formulation. They

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Testing and measuring instruments from BYK can effectively evalu-

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Today the company employs around 2,000 people worldwide and

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T he property profile and the associated fields of application of a

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undesirable side-effects, leading to adverse effects on the property

Figure 2: Comparison of structural types of dispersants tested

As most pigments used in coating applications carry an acidic surface

Figure 1: Schematic representation of dispersing

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Figure 4: Influence of the different structure types on the gloss

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Figure 9: Schematic representation of the working mechanism

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BYK-2016-0010_AZ_Paint_RZ260416.indd 1 26.04.16 16:11

S electing a suitable dispersant for a filler or a pigment (solid parti-

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significantly different parameters.

High throughput formulation simplifies selection

“Finntalc M15” and a broad selection of dispersants with different chem-

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e u r op e a n co at i ngs J OURNA L 2016

Table 3: Summary of results with best dispersants shown at the

e u r op e an coat i n gs J OURNA L 2016

Source: Anyka - Fotolia.com

e u r op e a n co at i ngs J OURNA L 2016

out by introducing energy to the system, for example by high-speed

Figure 1: Sample of DSC result to determine water uptake and

e u r op e an coat i n gs J OURNA L 2016

e u r op e a n co at i ngs J OURNA L 2016

AC-2 Polyacrylate 5 5 0.9995 38.0 140 REFERENCES

e u r op e an coat i n gs J OURNA L 2016

Claude Beaubien - Fotolia.com

W etting and dispersing additives are indispensable for the pro-

e u r op e a n co at i ngs J OURNA L 2016

copolymers (b) there is a distinct accumulation of monomer units in

Table 1: Formulations of the pigment concentrates

Table 2: Colouristic properties of the 2K PU coatings based on pigment con-

Colour strength (F) 476 485 485 500

e u r op e an coat i n gs J OURNA L 2016

Test coatings and test methods

In this study, colorimetric and salt spray results are reported on a

Rheological properties of the pigment concentrates

e u r op e a n co at i ngs J OURNA L 2016

Figure 6: Water absorption (%) of a 1K acrylate filler with the PR

e u r op e an coat i n gs J OURNA L 2016

The proper dispersion stabilisation of pigments is not only im-

Figure 1: Different types of pigment stabilisation in aqueous systems

e u r op e a n co at i ngs J OURNA L 2016

Figure 2: Structure of dispersing agents designed with CFRP technology