Technical Paper

Dispersion

Building blocks
for stable paints
Effects of anchoring groups and copolymer structure of additives studied

* Corresponding Author: Stefan Mößmer* In solventborne coating formulations, acid–base interactions

Dr. Stefan Mößmer Monika Roch or hydrogen bridging bonds between the pigment surface
Byk-Chemie GmbH Bernd Göbelt and the wetting and dispersing additive are normally used
T + 49 281 670 617 to achieve the desired interactions. Hence, the pigment-af-
stefan.moessmer@ Sabine Johann
altana.com
finic groups in the wetting and dispersing agent are polar.
In addition, the wetting and dispersing additive should pre-
The stabilising effect of polyacrylate block copoly- vent re-agglomeration of the homogeneously distributed
mers on pigment dispersion is shown to depend pigment particles in the coating. The stabilising effect of the
both on the chemical anchoring groups and on the wetting and dispersing additive is determined by its poly-
type of pigment dispersed. A highly regular poly- meric structure. Linear block copolymers or comb copoly-
mer architecture also helps to produce more stable mers are notably effective structures.
adsorption on the pigment surface. These structured copolymers prevent re-agglomeration
more effectively than statistical copolymers, since their

W
etting and dispersing additives are used to achieve
a homogeneous and stable distribution of pig-
ments in coatings. Two properties are of funda-
mental importance: on the one hand, the additives must
interact with the pigment and on the other, they must be
compatible with the liquid medium (solvent, binder).
Figure 1: General
structures of the
AB block copoly-
mers studied
regular structure ensures that there is no bridging between
the pigment particles. This enables a lower millbase viscos-
ity to be achieved.
Polymerisation route
affects structure of additives
Linear block copolymers based on poly(meth)acrylates
can only be obtained by controlled radical or ionic polym-
erisation processes such as ATRP (Atom Transfer Radical
Polymerisation), NMP (Nitroxide Mediated Polymerisa-
tion), RAFT (Reversible Addition-Fragmentation chain
Transfer) or GTP (Group Transfer Polymerisation).
These distinct polymerisation technologies rely on vari-
ous mechanisms that produce not only different molecular
weight distributions but also different polymeric struc-
tures, and thus affect the application properties [1, 2].
The effects of the pigment-affinic groups and polymerisa-
tion technologies on the characteristics of AB diblock co-
polymers as wetting and dispersing additives are examined
below. At the same time, products synthesised by means of
GTP technology [3] and RAFT technology [4] are compared.

GTP gives very narrow

molecular weight distribution
GTP is an ionic polymerisation technology and yields de-
fined polymers with a very narrow molecular weight distri-
bution. Since few termination reactions occur, the propor-
tion of homopolymers that contain only the monomers of
either the A block or the B block is very small.
RAFT technology, by contrast, produces a less precise
structure with a broader molecular weight distribution. Be-
Figure 2: ΔE colour cause radicals are produced from the decay of the initiator
difference values throughout the polymerisation process, the proportion of
for PR 101 in the homopolymers is much higher than with the GTP process.
acrylate/melamine AB model polymers 1 and 4 (Figure 1) were produced by
stoving system the GTP and RAFT processes respectively. Both have a

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 Technical Paper
Dispersion

molecular weight Mn of approximately 8000 g/mol and an

amine value of 45 mg KOH/g. Polymer 1 has a narrow mo-
lecular weight distribution (polydispersity) of 1.28, while
polymer 4 has a molecular weight distribution of 1.7.
A mixture of different alkyl methacrylates was chosen
as the A block, the aim being to ensure binder compat-
ibility. The B block was provided with tertiary amines as
pigment-affinic groups.
To study the effect of the pigment-affinic group on pig- Figure 3: Millbase
ment dispersion and stabilisation, the tertiary amines in viscosities for
polymers 1 and 4 were on the one hand neutralised with various dispersants
a mixture of phosphoric acid monoester and carboxylic and addition rates
acid to obtain polymers 2 (GTP) and 5 (RAFT) or on the with PBl 7 at a
other hand quaternised with an alkylating agent yielding shear rate of 1/s
polymers 3 (GTP) and 6 (RAFT) (Figure 1).

Stabilising performance
evaluated on four pigments
The effect of the different pigment-affinic groups and of
the different polymerisation technologies on pigment
stabilisation was analysed in solvent-borne systems. An
inorganic red pigment (Colour Index reference PR 101),
two organic pigments PR 177 and PG 7 (amino anthraqui-
none and phthalocyanine green) and finely dispersed
carbon black (PBl 7) were selected as pigments.
Pigment concentrates with an acrylate or polyester grind-
ing resin were produced and let down with an acrylate/
melamine stoving system, a two-pack acrylate/isocy-
anate system or a polyester/melamine/cellulose aceto-
butyrate (CAB) system. Table 1 summarises the millbase
formulations for the black pigment with varying block Figure 4: Transparency with P BI 7 in the acrylate/melamine stoving system
copolymer dosages.
To evaluate the pigment-stabilising properties, viscosity
measurements were carried out on the pigment concen-
trates, gloss and haze measurements were taken and, in
the case of the inorganic pigment, ΔE colour difference
Results at a glance
values were determined from the finished coating films. The efficiency of pigment stabilisation by poly-
The aim each time was to identify the most effective AB acrylate block copolymers is strongly affected by
block copolymer at the lowest additive dosage. both the type of anchoring groups and the polymer
microstructure.
Neutralised amines stabilise
Block copolymers with tertiary amine anchor-
inorganic pigment ing groups deflocculate phthalocyanine and acidic-
Block copolymers with acid-neutralised amine functional- treated pigments very effectively, while those with
ity (polymers 2 and 5) stabilised the inorganic iron oxide acid-neutralised amine groups appear more effective
(PR 101) best of all. With all the additive dosages tested, with inorganic pigments.
the millbase viscosities were the lowest each time for
these two polymers. Block copolymers with quaternary ammonium
The optimum additive dosage for the inorganic pigment groups are very effective with all types of pigment in
for polymers 2 and 5 is 2.5 % additive solid on pigment basecoats containing CAB.
(s.o.p.). The viscosities are lower than those obtained for
other polymers at 5 % s.o.p. The GTP process yields block copolymers with a
An increase in the additive dosage to 10 % s.o.p. led to more homogeneous structure than RAFT copolymers.
an increase in viscosity for all block copolymers used. This gives lower millbase viscosities and better pig-
This indicates an associative formation of polymeric mol- ment adsorption.
ecules that do not adsorb on the pigment surface. With “Additives for
RAFT polymer 6 (quaternary ammonium units), it was Thus, block copolymers synthesised by GTP that waterborne
not possible to obtain a stable pigment concentrate at carry all three anchoring groups should provide op- coatings”
2.5 % (s.o.p.), whereas its GTP counterpart, polymer 3, timum pigment stabilisation for all pigment types in Wernfried Heilen
yielded a flowable paste. solventborne systems, with or without CAB. www.european-
Another criterion for the stabilisation potential of the in- coatings-com/books
dividual block copolymers was determined with the aid

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 Technical Paper
Dispersion

Figure 5: Millbase viscosities at different shear rates with PR 177 (left: 30 % s.o.p.; middle: 15 % s.o.p.; right: 10 % s.o.p.)

of rub-out tests in the full shade, as seen in Figure 2 in a
polyester/melamine stoving system.
Polymer 3 and, more particularly, polymer 6 exhibited
high ΔE values at the lowest additive dosage, which sug-
gests insufficient deflocculation of the pigment particles.
Polymers 2 and 5 with the acid-neutralised amine func-
tionalities as the pigment adsorbing units provided the
lowest ΔE values.
The pigment-affinic group in polymers 2 and 5 is a salt
structure which is produced by neutralisation of the
amine moieties with a mixture of acid-functional poly-
mers. In contrast to polymers 3 and 6, this neutralisation
is reversible; the ion pair and dissociated form are in an
equilibrium state. Accordingly, the acid groups can also
adsorb on the pigment surface.
European Coatings
Conference: Tertiary amines stabilise
Furniture Coatings
acidic carbon blacks
Berlin/Germany
www.european- In the test systems with finely dispersed acidic-treated car-
coatings.com/events bon black, the tertiary amine functional block copolymers 1
and 4 yielded the best stabilising properties. With the high-
est additive dosage (70 % s.o.p.), the differences in viscosity
behaviour between the six individual block copolymers were
not strongly pronounced (Figure 3).
At 50 % and 30 % s.o.p., on the other hand, the lowest mill-
base viscosities were achieved with the tertiary amine func-
tional polymers 1 and 4. With RAFT polymer 5, the carbon
black could no longer be dispersed at 30 % s.o.p.; with GTP
polymer 2, which has a more precise structure, this was still
possible. Polymers 3 and 6 exhibited almost unchanged vis-
cosity behaviour at 70, 50 and 30 % s.o.p.
On reducing the additive dosage to 15 % s.o.p., grinding was
only successful with polymer 1; with all other polymers, addi-
tional solvent was required to reduce the increase in viscosity
during dispersion. Polymer 1 synthesised by GTP has a very
narrow molecular weight distribution; the block structure is
correspondingly more defined than with polymer 4 (RAFT).
Only polymer 1 is able to properly stabilise the acidic carbon
black at the lowest concentration. Polymer 1 also achieves the
greatest transparency in the letdown. In the case of defloc-
culated, finely dispersed carbon black (primary particle size ~
10 nm), a transparent full shade appears brownish, whereas
flocculated carbon black is greyish blue in colour (Figure 4).

Figure 6: Gloss and

haze values for PG
7 in the polyester/
melamine system
(without/with CAB)

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 Technical Paper
Dispersion

70 % additive s.o.p. 50 % additive s.o.p. 30 % additive s.o.p. 15 % additive s.o.p.

Acrylate grinding resin (65 %) 69.2 69.2 69.2 69.2
Polymers 1 to 6 (40 %) 17.5 12.5 7.5 3.8
PBl 7 10.0 10.0 10.0 10.0 Table 1: Millbase
formulations: ex-
Shellsol A / xylene 1:1 3.3 8.3 13.3 17.0 amples using black
Total 100.0 100.0 100.0 100.0 pigment

The aminic pigment anchoring units in polymer 1 defloccu-
late the acidic carbon black better than the acid-neutralised
components in polymer 2 (made by the same polymerisation
technology).
Quaternary ammonium group
is best for anthraquinones
The best viscosity-reducing properties for an amino an-
thraquinone pigment (PR 177) were obtained with poly-
mers 3 and 6 with quaternary ammonium units. Newto-
nian flow was achieved at all dosages, especially with
polymer 3, which was synthesised by GTP.
The corresponding RAFT polymer 6, in contrast, exhibits
viscosity behaviour at the lowest concentration (10  %
block copolymer s.o.p.) that approximates to that of the
samples for the other polymers (Figure 6). The excellent
stabilisation of PR 177 by polymers 3 and 6 is also reflected
in high gloss and low haze values in a 2-pack system.
The GTP polymers always yielded – by comparison with
their RAFT counterparts – slightly higher gloss values at
all dosages, implying improved stabilisation of the pig-
ment through the regular block structure. This ensures
more effective anchoring on the pigment surface and
counteracts any re-agglomeration of the pigments.
Use of CAB requires
quaternary ammonium groups
In automotive coating systems, CAB is used in solvent-
borne basecoats to accelerate the drying. The higher the
molecular weight of the CAB used, the more likely it is
that pigment destabilisation processes will increase, es-
pecially in polyester/melamine systems.
When dispersing a phthalocyanine pigment (PG 7) with a
polyester grinding resin and with subsequent letdown in
a polyester/melamine system, all polymers yielded simi-
lar results in terms of gloss and haze, apart from polymer
1, containing tertiary amine groups, which gave the high-
est gloss and lowest haze.
If the phthalocyanine pigment concentrate is let down with
a polyester/melamine/CAB system, only the polymers with
the quaternary ammonium anchoring groups (polymers 3
and 6) effectively counteract destabilisation, while the poly-
mers with the tertiary amine groups and the acid-neutral-
ised anchoring groups lose their stabilising effect and yield
low gloss and high haze values (Figure 6).
This behaviour was also observed for other pigments.
Hence, only polymers with quaternary ammonium
groups are suitable for long-lasting pigment stabilisation
in polyester/melamine/CAB systems, as seen in Figure 7
for PR 177.
Both anchoring groups
and structure are critical
The optimum dispersing additive for general pigment
stabilisation in solventborne systems is thus a block
copolymer synthesised by GTP that carries all three an-
choring groups in the pigment-affinic block, in order to
stabilise different pigments in different systems (with or
without CAB) effectively and durably.
The corresponding polymer synthesised by the RAFT
process can be considered to show a satisfactory com-
promise between efficiency and cost-effectiveness. í
REFERENCES
[1] Göbelt, B., Pitture e Vernici – European Coatings 2005, Vol. 2, p. 39.
[2] Göbelt, B., Progress in Organic Coatings 2006, Vol. 55, p. 189.
[3] Webster, O. W., et al, Jnl. Am. Chem. Soc. 1983, Vol. 105, p. 5706.
[4] Moad, G., et al, Polym. Int. 2000, Vol. 49, p. 993.

Figure 7: Illustration
of transparency
with PR 177 in the
polyester/mela-
mine/CAB system

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