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Recent Developments in Crosslinking Technology For Coating Resins
Recent Developments in Crosslinking Technology For Coating Resins
in Organic
325
Review Paper
Inc., I-3
Takasago,
Abstract
Recent developments in crosslinking technology for solvent- and water-based coatings
were reviewed through a survey of patent literatures and research papers. The developments
are characterized as focused on the following demands: (i) reduction of volatile organic
compounds, (ii) replacement of hazardous poly(isocyanates) to noxious crosslinkers, (in)
acid rain resistance and scratch resistance in automotive topcoats, (iv) low temperature
cure for saving energy, (v) higher performance. A variety of new crosslinking systems
has been developed as substitutes for the existing systems such as the aminoplast cure,
the poly(isocyanate) cure and the blocked poly(isocyanate) cure. Some commercial products
based on new systems have been put into the market.
Contents
1. Introduction .....................
2. Solvent-based coatings. ..............
2.1 Amino-epoxy cure ..............
2.2 Silicon-based cure ..............
2.3 Carboxyl-epoxy cure. ............
2.4 Acid anhydride cure .............
2.5 Michael reaction. ...............
2.6 Activated esters ................
2.7 Acetoacetate ..................
2.8 Blocking of functional groups .......
2.9 Miscellaneous .................
3. Water-based coatings ...............
3.1 Ambient temperature cure .........
3.2 Baking type ..................
4. Conclusions .....................
References ........................
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1. Introduction
Crosslinking structures are generally introduced in coating films in order
to provide better properties such as durability, solvent resistance and mechanical strength. Hitherto, commonly used crosslinking systems were melamine, urea and phenolic resins, isocyanate/OH combination, air-drying
polymers containing double bonds, and epoxy/COOH and amine combination.
These systems have been properly utilized in formulating coatings with
variations of resin types (for example acrylics, poly(esters) and alkyds), state
of the resin (organic solvent solutions, aqueous solutions, aqueous dispersions
and solids), coating application areas and practical requirements. Curable
coatings based on these known systems, however, sometimes do not meet
current demands related to government regulations, safety requirements and
high performance as exemplified below:
(1) reduction of volatile organic compounds (VOC): higher solids in
solvent-based coatings and higher performance in water-based coatings;
(2) replacement of hazardous poly(isocyanates)
by non-toxic crosslinkers;
(3) acid rain resistance and scratch resistance in automotive topcoats;
(4) low temperature cure for saving energy;
These demands have necessitated the development of new crosslinking
technology, and extensive research for new crosslinking systems has been
done in various application fields of coatings in recent years.
The purpose of this review is to outline the recent developments in
crosslinking technology for solvent- and water-based coating resins by surveying the patent literature and research papers.
2. Solvent-based
coatings
327
-NHR
-I- CH.-CH-
--NR-CHz-CH-
-NRz
CH.-CH-
I
-N+-CHz-CH-
O/
Scheme
-Ii-OR
-Si-OH
I
-_Si-OH
1. Reaction
--,
ter-kne
0-
I
-V--OH
Ha-
HO-&i-
RO-.ki-
--Si-O-Si-
cd
I
-S
Scheme 2. Self-crosslinking
hy&olysis
+ RoH
i -0-S
i -
H&l
cm&nsalion
ROH
wrniensation
of alkoxysilyl-functional
acrylics.
-Ti-O-AI-
7H-cH2-N+0-
cure
Three types
328
i-
CHz-CH-
O/
Scheme 4. Reaction
-COO-CHyCH-.
bH
of epoxy
329
TABLE
2
3
4
5
6
7
3
COOH acrylics
COOH acrylics
COOH-acrylics
COOH-acrylics
COOH-acrylics
cure system
Epoxy functional
resin
epoxy acrylics
epoxy acrylics
epoxy acrylics
epoxy acrylics
epoxy acrylics/
OH acrylics blend
Co-hardener
aminoplasts
blocked NC0
aminoplasts
aminoplasts
epoxy acrylics, or
blend with OH acrylics
epoxy-OH bifunctionsl
acrylics
10
Poly(ester) or
poly(urethane) with
diacid half-ester
epoxy acrylics
(aminoplasts)
11
COOH acrylics
aminoplasts
12
COOH acrylics
epoxy acrylics
modified with &tone
epoxy acrylics
13
14
COOH acrylics
15
16
17
epoxy acrylics
Reference
40
phosphonium salts 41
42,43
44
45
phosphonium salts 46,47
phosphonium salts 48
Diacid half-ester
acrylics
Diacid half-ester
acrylics
Curing catalyst
49
50
51-54
basic compounds
55
polin complex of
organic phosphine
56
57
poly NC0
phosphonium salts 58
aminoplasts
59
quart. ammonium 60
hydroxides or
metal chelates
61
330
i-
-CH-CH-
HO-
-CH-CH-
1
!
c, At
0 0 0
HO&
ii
Scheme 5. Reaction
BI
ocked
-CH-CH-
80
AH
!!
CO8
group.
HOC
87f53
HN-
-CH-CH-
Hz--
Scheme 6. Reaction
-CHCHfiC
Amine
-CH-CH-
CHz-CHlo/
LO-
CNRa
amine.
0
-O!CH=CH.
Scheme
H-X
-O!!CH
2CH 2-X
metal alkoxide or metal chelate formation [ 73,74, SO], siloxane bond formation
[ 81, 821, the Michael reaction [ 831, and urethane formation by the reaction
of cyclocarbonate
and amino groups [85]. Furthermore, acid anhydridefunctional acrylic resins having co-reactive groups such as OH groups [87],
isocyanate groups [88] and both epoxy and OH groups [89] are described
in patents.
As a unique system, the curing of maleic anhydride copolymers with
dioxazoline compounds [ 901 or bicyclic amide acetals [ 911 has been developed.
2.5. Michael reaction
The Michael reaction, that is the addition reaction of nucleophiles having
active hydrogen atoms (Scheme 7) to activated double bonds, has been
investigated for two-package, ambient temperature curable coatings. For
coatings applications, ammo groups or blocked amino groups, such as
aldimines and ketimines, have mainly been used as the nucleophilic groups
[92-961, and the blocked amino groups have attracted more attention as
they can ensure a sufficient pot-life needed for handling. Commercial products
based on this reaction are now available for car rellnish [97].
Recently, compounds containing other nucleophilic groups have been
examined. Examples of these compounds are OH-functional compounds
[98-1001 and CH-acid compounds such as poly(enamines)
[ 1011, methanetricarboxylic acid esters [ 1021, malonate poly(esters) [96] and acetoacetatefunctional compounds (Section 2.7). In these cases, catalysts such as basic
compounds are necessary to achieve enough cure by accelerating the addition
reaction. For acceleration of the CH-acid addition, a new catalyst system
based on the mixture of a tert-amine and an epoxide has been proposed
[103]. As an activated double bond-containing compound, methyl acrylamidoglycolate methyl ether (MAGME) is described in patent [104].
331
2.6. Activated
esters
Ii
CHz=CHCNH-CH-COCHs
si
-Of,,
bCHs
methyl ether.
2i!CH 3
Scheme 9. Acetoacetate
group.
332
As blocked
OH groups,
oxazolidines,
silyl ethers
[ 120, 1211,
N-vinylcarbamate-blocked
OH [122], acetals [ 1231 or ketals [123] have been
investigated (Scheme 10). Oxazolidine-functional resins have been investigated
in combination with poly(isocyanates)
[ 124-l 26 ] and with poly(anhydrides)
as described in Section 2.4.
The blend of a silyl ether functional acrylic resin and a poly(isocyanate)
is very stable during storage in a closed container, while it cures rapidly at
ambient temperatures with the formation of urethane linkages under the
action of acid catalysts when exposed to the atmospheric moisture (Scheme
11) [ 1211. The solid content of the blend is higher than that of the OHfunctional counterpart. The silyl ether-functional acrylic resins have also been
examined in acid anhydride curing systems: combinations of silyl ether/acid
anhydride [ 1271 or silyl ether/acid anhydride-epoxy [ 128,129].
Examples of blocked COOH groups are silyl esters [ 1301, acetal esters,
ketal esters [131-1341 and tert-butyl esters [135, 1361 (Scheme 12). Curing
systems based on these groups have been investigated in combination with
functional groups, reactive with COOH [130-1361.
Acrylic resins having cyclocarbonate groups, which can be regarded as
COa-blocked epoxy groups, have been proposed as the base polymer for
acid resistant automotive topcoats with one-package stability [ 13 7-l 391. The
-CHzO--S
-N-CH2
R-C
silyl
LHn
AlO
i R3
elher
--C&O-~-OR
fiz
omzotidine
acetol
or
ketol
Hfl
-CHzO-CH&HzNCOCHz,
N-uinytcmbmat~btocked
Scheme
10. Blocked
-OSiR3
Scheme
-10s
silyl
ll+
--OH
+
l/2
R,S
R&iOH
i -0-S
i R3
O=C=N---OCONH-
11. Reaction
i R3
ester
?
7
-CO-CH-OR2
acetat
Ha
OH group.
-I/2 820
R3S i OH
-OH
otl
ester
Jo-~;,
CH3
t-butyt
ester
-CH-CHZ
b
Jo-~,,,
l
R3
ketat ester
C
a
-COOH
-m
-CH-CHF
OH
b-Ca
333
cyclocarbonate groups react with COOH to form ester linkages with the
elimination of COa (Scheme 13).
primary amines are easily converted to blocked amines, that is aldimines
or ketimines, by reactions with aldehydes or ketones. The blocked amines
are incorporated into ambient temperature cure systems as described in
Sections 2.1, 2.4, 2.5 and 2.7, and are also used in a two-package high
solids isocyanate cure system [ 1401.
2.9. Miscellaneous
The curing systems based on cationic polymerization of epoxy [ 141-l 45 ]
or vinyl ether groups [ 1461 have been reported. The oxazoline/COOH system
(Scheme 14), which was investigated earlier for powder coatings [ 1471, has
recently been reinvestigated for solvent-based coatings with low temperature
curability [148, 1491. Acrylic-urethane
coating based on p-hydroxyalkyl
carbamate/OH reactions at high temperatures have been developed [ 1501.
3. Water-based
coatings
-c
N-CH2
\O-kHz
Scheme
;C=O
Scheme
HOOC-
14. Reaction
H,N-NH--
15. Hydrazone
Q
-CNHCH&H&C-
of oxazoline
-w
and COOH.
;c=N-NH-
formation.
334
335
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