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Building Blocks For Stable Paints
Building Blocks For Stable Paints
Building Blocks For Stable Paints
Dispersion
Building blocks
for stable paints
Effects of anchoring groups and copolymer structure of additives studied
W
etting and dispersing additives are used to achieve regular structure ensures that there is no bridging between
a homogeneous and stable distribution of pig- the pigment particles. This enables a lower millbase viscos-
ments in coatings. Two properties are of funda- ity to be achieved.
mental importance: on the one hand, the additives must
interact with the pigment and on the other, they must be Polymerisation route
compatible with the liquid medium (solvent, binder).
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
Figure 1: General weight distributions but also different polymeric struc-
structures of the tures, and thus affect the application properties [1, 2].
AB block copoly- The effects of the pigment-affinic groups and polymerisa-
mers studied 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.
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
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 est additive dosage (70 % s.o.p.), the differences in viscosity
polyester/melamine stoving system. behaviour between the six individual block copolymers were
Polymer 3 and, more particularly, polymer 6 exhibited not strongly pronounced (Figure 3).
high ΔE values at the lowest additive dosage, which sug- At 50 % and 30 % s.o.p., on the other hand, the lowest mill-
gests insufficient deflocculation of the pigment particles. base viscosities were achieved with the tertiary amine func-
Polymers 2 and 5 with the acid-neutralised amine func- tional polymers 1 and 4. With RAFT polymer 5, the carbon
tionalities as the pigment adsorbing units provided the black could no longer be dispersed at 30 % s.o.p.; with GTP
lowest ΔE values. polymer 2, which has a more precise structure, this was still
The pigment-affinic group in polymers 2 and 5 is a salt possible. Polymers 3 and 6 exhibited almost unchanged vis-
structure which is produced by neutralisation of the cosity behaviour at 70, 50 and 30 % s.o.p.
amine moieties with a mixture of acid-functional poly- On reducing the additive dosage to 15 % s.o.p., grinding was
mers. In contrast to polymers 3 and 6, this neutralisation only successful with polymer 1; with all other polymers, addi-
is reversible; the ion pair and dissociated form are in an tional solvent was required to reduce the increase in viscosity
equilibrium state. Accordingly, the acid groups can also during dispersion. Polymer 1 synthesised by GTP has a very
adsorb on the pigment surface. narrow molecular weight distribution; the block structure is
European Coatings correspondingly more defined than with polymer 4 (RAFT).
Conference: Tertiary amines stabilise Only polymer 1 is able to properly stabilise the acidic carbon
Furniture Coatings black at the lowest concentration. Polymer 1 also achieves the
acidic carbon blacks greatest transparency in the letdown. In the case of defloc-
Berlin/Germany
www.european- In the test systems with finely dispersed acidic-treated car- culated, finely dispersed carbon black (primary particle size ~
coatings.com/events bon black, the tertiary amine functional block copolymers 1 10 nm), a transparent full shade appears brownish, whereas
and 4 yielded the best stabilising properties. With the high- flocculated carbon black is greyish blue in colour (Figure 4).
The aminic pigment anchoring units in polymer 1 defloccu- a polyester/melamine system, all polymers yielded simi-
late the acidic carbon black better than the acid-neutralised lar results in terms of gloss and haze, apart from polymer
components in polymer 2 (made by the same polymerisation 1, containing tertiary amine groups, which gave the high-
technology). est gloss and lowest haze.
If the phthalocyanine pigment concentrate is let down with
Quaternary ammonium group a polyester/melamine/CAB system, only the polymers with
the quaternary ammonium anchoring groups (polymers 3
is best for anthraquinones and 6) effectively counteract destabilisation, while the poly-
The best viscosity-reducing properties for an amino an- mers with the tertiary amine groups and the acid-neutral-
thraquinone pigment (PR 177) were obtained with poly- ised anchoring groups lose their stabilising effect and yield
mers 3 and 6 with quaternary ammonium units. Newto- low gloss and high haze values (Figure 6).
nian flow was achieved at all dosages, especially with This behaviour was also observed for other pigments.
polymer 3, which was synthesised by GTP. Hence, only polymers with quaternary ammonium
The corresponding RAFT polymer 6, in contrast, exhibits groups are suitable for long-lasting pigment stabilisation
viscosity behaviour at the lowest concentration (10 % in polyester/melamine/CAB systems, as seen in Figure 7
block copolymer s.o.p.) that approximates to that of the for PR 177.
samples for the other polymers (Figure 6). The excellent
stabilisation of PR 177 by polymers 3 and 6 is also reflected Both anchoring groups
in high gloss and low haze values in a 2-pack system.
The GTP polymers always yielded – by comparison with
and structure are critical
their RAFT counterparts – slightly higher gloss values at The optimum dispersing additive for general pigment
all dosages, implying improved stabilisation of the pig- stabilisation in solventborne systems is thus a block
ment through the regular block structure. This ensures copolymer synthesised by GTP that carries all three an-
more effective anchoring on the pigment surface and choring groups in the pigment-affinic block, in order to
counteracts any re-agglomeration of the pigments. stabilise different pigments in different systems (with or
without CAB) effectively and durably.
Use of CAB requires The corresponding polymer synthesised by the RAFT
process can be considered to show a satisfactory com-
quaternary ammonium groups promise between efficiency and cost-effectiveness. í
In automotive coating systems, CAB is used in solvent-
borne basecoats to accelerate the drying. The higher the REFERENCES
molecular weight of the CAB used, the more likely it is
that pigment destabilisation processes will increase, es- [1] Göbelt, B., Pitture e Vernici – European Coatings 2005, Vol. 2, p. 39.
pecially in polyester/melamine systems. [2] Göbelt, B., Progress in Organic Coatings 2006, Vol. 55, p. 189.
When dispersing a phthalocyanine pigment (PG 7) with a [3] Webster, O. W., et al, Jnl. Am. Chem. Soc. 1983, Vol. 105, p. 5706.
polyester grinding resin and with subsequent letdown in [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