The recent progress in anti-burnish performance for dead matted GMA

acrylics powder coatings

By Naibin-Tong* AHA International

Abstract
The use of the combination of a toughening agent with co-reactants such as TGIC
or HAA, the dead-matted, exterior durable GMA acrylic powder coating is
improved effectively for performing anti-scratch or anti-burnish. In a rule, this
successful solution is recommended to use in designing for meeting requirements
of dead matted, especially, black or dark GMA powder coatings.

Introduction
Dead matt is defined as gloss ranges 5% 60of coating film. For exterior
durable dead matted powder coating systems, the recent solutions are forced to
select between polyurethane (PUR) and GMA resin/polyester hybrid powder
coatings. The former is based on a special PUR crosslinker Crelan VP LS2181/1[1],
which is developed and available by Bayer. Crelan VP LS2181/1 is a condensate
containing both carboxyl functional groups and blocked isocyanate functional groups
(seen in the following fig.):

Fig.1: Ideal chemical structure of Crelan VP LS2181/1

thus in the presence of TGIC or HAA co-reactants, the both parallel competitive
reactions from TGIC or HAA vs. carboxyl groups as well as OH groups from
polyester vs. isocyanate groups respectively will be happened simultaneity and
contribute about less than 5% of low gloss and excellent technical performance as a
consequence of severed shrinkage on film surface. However, in China so far such
solution could not be widely acceptable due to high cost, supply chain and the
significant difference of Chinese product line with mainly powder coating markets
such as European and North American.

Another feasible alternative is using glycidyl methacrylate containing poly-acrylics,

herein abbr. as GMA resin. GMA resin could offer dead matte such as less than
3% as well as quite good technical performance, but very poor anti-scratch or
anti-burnish issues in terms of black or dark powders makes it application to be
restricted. Although the use of combination of both GMA resins with different Tg[3] or
bis-functional polyester resins[4,5] resp. had been proposed, the matted solution
based on GMA resin could not obtain substantial progress due to problem similar to
above matted PUR as well.

On the contrary, the matted technology for polyester/TGIC system had obtained
great progress in China, for example, from the earliest JietondaSA2067[6] to recent
AHA2019[7], the lowest gloss of 20% or less as well as very good performance had
been achieved. However, increasing force to environment protection and pursuing

1
 The recent progress in anti-burnish performance for dead matted GMA
acrylics powder coatings
By Naibin-Tong* AHA International

for TGIC-free powder coatings, moreover, and restricted to no dead matte effect
issue the future of thus matted system looks still suspenseful.

Cytec[8]proposed an advanced one shot matted HAA based powder coatings, this
technology used the combination of HAA as sole curative with both carboxylic
polyester binders with significant incompatibilities each other, specially developed
and trademarked recently, achieved approx. 8% (min) of low gloss by extruded
process. Obviously, this technology is also difficult to offer dead matted finish.
Because key materials are patented and controlled by multinational the problems
like as above said supply chain, high costs and un-ready use should be unavoidable
as well. Therefore it would be desirable to continuous innovative and development in
exterior durable powder coatings that is capable of offering dead matted, esp. for
black or dark finishes and also, it is very important to have a solution once and
forever in terms of above dead matted powder coatings.

Matte chemistry
GMA resins are recognized as to be GMA containing acrylics, which are, in general,
made by free radical solution copolymerization of GMA with other acrylic or vinyl
aromatic co-monomers such as alkyl (meth)acrylate, i.e. preferably methyl
methacrylate (MMA), butyl acrylate (BuA), butyl methacrylate (BuMA) and styrene
and so on:
Fig.2: Chemical reaction equation 1

Depending on designed parameters and some considering such as monomer types,

GMA concentration, Mn, Tg and melt viscosities and so on, it is found that GMA
concentration and whether MMA is present or not in said copolymer composition will
determine matte effect greatly.

Hoebeke et al[9] indicated the matted performance of said powder coating is mainly
controlled by the designed GMA resin after study on the curing behavior of GMA
resin with acid polyester. As a rule, in order to achieve dead matt the basic
requirements should be satisfied as follows:

The concentration of GMA should be maintained within ranges from 5% to

30%, once over the upper limit, in fact, glossy finish will be obtained.
MMA monomer is essential to GMA resin, which use levels are within
ranges from 70% to 95%. MMA can be replaced partly by other monomers
such as styrene and/or BuA, however, the replacement contents should not
be over 25% otherwise glossy finish obtainable.
2
 The recent progress in anti-burnish performance for dead matted GMA
acrylics powder coatings
By Naibin-Tong* AHA International

Mn of the copolymer should be within ranges of 4000 -10000. Under the

4000 the resulting gloss is increasing but over 10000, although dead matted
finish can be obtainable the other performances such as coating surface
flow and adherent to substrate are unacceptable.
Also, the resin viscosity should be preferably considerable when designed. Table 1
showed the viscosity characteristics of two kinds of GMA resins, which one is
suitable for DDDA as curative used mainly in glossy and clear top coatings, while
another used in polyesters to provide low gloss:

Table 1[10] The main difference of performance parameters derived from

both GMA resins with different usages

In above table, the red oval curves covered technical data stand for the latter
suitable to use as matting hardeners while the former covered with blue curve,
exhibiting features with lower EEW, viscosity and Tg, mainly designed for glossy
purpose.

Crosslink of GMA resin with acid polyester is based on addition reaction of epoxy
group with carboxylic group. The typical chemical reaction equation may be
described as below:

Fig.3: Chemical reaction equation 2

O

(CH2CH)n O O
PE
CH2 + HO
O
CH3

O
O
(CH2CH)n O
CH2 PE
O
CH2

[II]
CH3 OH

Kristin M. Bartlett carried ever out a study on the cure behavior of acrylics reacted
with epoxy resin matte system but he just looked into the system based on acid
acrylics against bisphenol A epoxy resin. He found that dead matted film appears to
distinct biscontinuous morphology observed by the hand of scanning electron
microscope. So he proposed such morphology from both film-forming resin and
curing agent was in two-phase separation. In consequence, low gloss would be
emerged from coating film. It may be seen that cure behavior based on GMA
resin/acid polyester should be very similar to above said case. The resulting chance

3
 The recent progress in anti-burnish performance for dead matted GMA
acrylics powder coatings
By Naibin-Tong* AHA International

of so calledphase separate biscontinuous morphologyon film surface should be

higher than acid acrylics vs. bisphenol A epoxy resin in respect to chemical structural
characteristics of both GMA and polyester. Therefore, the result will lead to micro
rough and corrosional valley texture structure appeared on film surface so as to
cause scattering and diffusing of incident light, consequently the resultant dead
matte accompanying with strongly gloss reduction effect.

However, micro roughed surface is generally liable to defects from scratching or

burnishing. In the field of powder coatings it is accustomed to use termroughness
for describing microcosmic surface uneven structure. It is believed that size big and
small between wave crests and denseness are two key criterions affecting gloss. For
example, there is the minimal size on PUR matted surface so that it can offer
super-flow and excellent decorative performance. On the contrary, GMA resin
seems to lack compatible with acid polyester one another due to phase separation,
therefore generation of polymer interpenetrating networks in film forming resin when
cure, thus, more sizes and roughness would be generated on film surface. In
addition, because the absolute hardness based on GMA resin is distinctly higher
than the most existing coating systems, as a result, poor pigment dispersion as well
as above said effects was leading to irregular color shades or blurriness as well as
anti-scratch and/or anti-burnish performance down.

Fig.4 showed that surface effect of black dead matted powder based on standard
GMA+ TGIC + polyester against rubbing back and forth by nail.

Table 2
Starting formulation
CC2241-2 450 PolyesterCytec.
AHA7700 180 GMA resin
TGIC 7.5 Anshan Runde
AHA1088P 10 Flow modifier
Benzoin 5
BaSO4 300
Carbon black 7 MA100
Total 959.5
Gloss% 2.2
Gel time (s) 31
Impact (50Kgcm ) +/pass, -/fail

The poor anti-scratch and/or anti-burnish performance is, in general, regarded as

coating film lacking of enough hardness, therefore there has a tendency to use some
hardened solutions for eliminating above said defects in the art. However this may
be a misunderstanding. Perhaps you had ever much failure experience, that is, if
you were trying to incorporate a few curing accelerator into above said standard
starting formulation, as a rule, it would be far from improving the mechanical strength
of coating, on the contrary, the coating film would be embrittled, potentially leading to
mechanical strength loss. In fact, most curing accelerators and/or catalysts such as
imidazoles, triphenylphosphine, quaternary ammonium salts and/or quaternary
phosphonium compounds and so on, which are widely used in most existing powder
coatings currently, are difficult to application in above said GMA matted powder
4
 The recent progress in anti-burnish performance for dead matted GMA
acrylics powder coatings
By Naibin-Tong* AHA International

coating system, this reason may attribute to GMA resin-self being not lack of
functional groups, enough reactivity and possible high crosslinking density as well,
therefore overuse of catalysts may be harmful. On the other hand, GMA resin is a
comb copolymer with distinct from acid polyester (cf. reaction equation I and
structure [1]). Although functional groups, random dispersed over polymer backbone
of GMA resin rather than terminated position, have quite high reactivity, in fact
crosslinkage has started from 140accompanying with increase of viscosities
drastically during curing:

However, severed steric hindered effect would be possible to obstruct further

crosslinkage course so that reaction is difficult to go to final completion. Based on
above knowledge, phase separated biscontinuous morphology should be improved
towardsoftorcompatible each otherchange in the perspective of technology.
Such technologies can usually be achieved by two solutions as follows:

Inducing soft segments or linkage moieties into polymer backbone in designing

GMA resins, this work should be done by designer or manufacturer of GMA acrylic
resins and another
Incorporating such an additive or solid solvent into coating composition that it can
be facilitate to dissolve between two cured polymer segments each other, usually
that is so calledtougheningmeans.

AHA international has rich experiences in the aspect of toughening technology of

powder coatings. AHA8100, a novel toughener developed by AHA and recently
available in global markets, has been used to toughen GMA resin for offering powder
coating with excellent scratch resistance and/or burnish resistance, esp. for black
formulation.
AHA8100 is a polyester oligomer condensated by long chain aliphatic polycarboxylic

5
 The recent progress in anti-burnish performance for dead matted GMA
acrylics powder coatings
By Naibin-Tong* AHA International

acids with cycloaliphatic and/or alicyclic polyalcohols. As compared with existing

commercial polyester resins, AHA8100 has extremely low Tg and excellent flexibility.
Therefore it is recommended to use in black dead matted GMA acrylic powder
coatings to provide desired flexible moiety and helps both GMA and polyester
interpenetrated miscibility each other.

AHA8100 has the following typical properties:

Table 3Typical properties of AHA8100[11]
Appearance [visual] Pale yellow powder
Acid equivalent weight (g/eq.) 550
Soft Point (C) ca.116
Volatiles (%) 1.5

Thus, the mix weight ratios of AHA8100 to epoxy based co-reactants based on their
chemical equivalent weights are recommended as follows:

GMA resinEEW550-700 1/1-1.5

TGICEEW110 1/0.25
HAAOHEW, g/eq.=83 1/0.18-0.2

Here we will introduce briefly the mainly progress used AHA8100 as toughening
agent in the aspect of dead matted GMA acrylic powder coatings.

Primary Results
The two kinds of black powders based on the both combination of TGIC+ GMA and
HAA +GMA resins as AHA 8100 co-reactants respectively were designed for testing
purpose. These powders were formulated by means of usual way. Thus the
resultants were firstly crushed into fine powders and sieving pass through 120-160
meshes, then the powders were sprayed electrostatically onto metal panels and
baked in air-circulated oven at 200 for 15min, examined and checked various
coating performances.

Table 4: the typical powder formulation containing AHA8100 with co-reactants

Composition I (part by wt.) II III IV Remark
CC2240-2 450 450 / / Polyester
from Cytec.
Uralac P847 / / 450 450 DSM
AHA7700 180 180 180 180 GMA resin
AHA8100 50 50 50 50
TGIC 20 / 20 /
HAA / 15 / 15 AHA6552
AHA1088P 10 10 10 10 Flow modifier
Blanc Fix 300 300 300 300
Carbon black 7 7 7 7
Benzoin 4.8 4.8 4.8 4.8
Amide wax 8 8 8 8 AHA4000
AHA6314 2.4 2.4 2.4 2.4

6
 The recent progress in anti-burnish performance for dead matted GMA
acrylics powder coatings
By Naibin-Tong* AHA International

Film thickness(m) 80-85 80 85 80

Flow (PCI grade) 6 6 6 6
Gloss %, 60 2.8 2.2 3.1 2.7
Impacts+/- pass/fail pass/fail pass/fail pass/fail
50Kgcm
Gel time (s) 13 10 21 20
Anti-scratch Excellent Good Excellent Good
It should be noted that formulation II and IV was designed for meeting the
requirement of TGIC-free. Meanwhile this kind of GMA dead matted powder coating
system could also meet requirements of higher grade of environmental-friendly as
evidenced by the above result listed in table 4. However, as comparable TGIC
seems to give better technical performance than HAA, such as better anti-scratch
and/or antimar as well as anti-burnish by nail rubbing back and forth besides slight
higher gloss. However, this GMA matted finish also showed slight coarse surface or
non-slip against most low gloss coating finishes.

For above stated issues from rough surface structure, herein has a recommendation
to add a few pigment dispersant AHA5116 into formulations so as to improve flow
and surface fineness, use level usually is 1% by weight based on total formulation.
However, in the case gloss might be increased to 5-6%.

The following photos showed the improved panel distinguished with control panel on
appearance.

Improved
Control

* Author, Technical Director of Coating Chemicals, AHA International

7
The recent progress in anti-burnish performance for dead matted GMA
acrylics powder coatings
By Naibin-Tong* AHA International

Key words
GMA acrylics powder coating, GMA resin, dead matt, anti-burnish,
anti-mar, progress

Reference
[1] James. W. Rawins et al., New crosslinkers for polyurethane powder coatings,
International water-borne, high solids, and powder coatings symposium; New Orleans,
LA, USA, Feb.6-8, 2002
[2] Eric Dumain (Reichhold), Novel acrylic cure polyester powder coating resin technology,
gained by google
[3] Sekido Takayoshi et al.(Mitsui) Eur.pat.0480120 (1991)
[4] ReichholdProduct bulletin,Fine-Clad M-8402, Product Code: 91062, Bi-functional
polyester(2004)
[5] Reichhold Powder Coating Matte Finish Systems
[6] JietondaSA20672006
[7] AHA InternationalTechnical Data SheetAHA20192010
[8] Supunnee Supeerapat et al. 2009

[9] Jean-Marie Hoebeke et al.(UCB)US pat.5436311(1995)
[10] Cytec.Binder Resins, Hardeners and Additives Pub. No. 220104E, Version A US
[11] AHA InternationalTechnical Data SheetAHA81002011