Progress

in Organic

Coatings, 23 (1994) 325-338

325

Review Paper

Recent developments in crosslinking technology for coating

resins
M. Ooka and H. Ozawa
Coating Resins Division, Dainippm
Takaishi City, Osaka (Japan.

Ink and Chemicals,

Inc., I-3

Takasago,

(Received September 10, 1993; accepted in revised form January 4, 1994)

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.

Key woro!s: Crosslinking; Solvent-based coatings; Water-based coatings; Poly(isocyanates);

Acid rain resistance; Scratch resistance; Aminoplast; Low temperature cure

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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0300-9440/94/$07.000 1994 Elsevier Science S.A. All rights reserved

SSDI 0300-9440(94)00470-L

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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

Recent developments in crosslinking systems for solvent-based coatings

focus on the isocyanate-free, ambient temperature cure type as well as the
baking type for acid rain resistant automotive topcoats. In addition, from
the chemical point view, these developments are based on silicon, epoxy
groups, acid anhydrides, the Michael reaction, activated esters and the
acetoacetate group together with the blocking of functional groups.
2.1. Amino-epoxy
cure
As an isocyanate-free ambient temperature cure system, combinations
of amino functional acrylics and epoxy compounds such as epoxy resins
and epoxy-functional
acrylics have been investigated (Scheme 1) [l-4].
Primary amino-functional acrylic resins are prepared by the reaction of epoxyfunctional acrylics with ammonia [3] or by the reaction of COOH-functional
acrylics with alkyleneimines [ 3, 41. Commercial acrylic resins containing tertamino groups for this system are now available in Japan, and have been
used for specific applications.

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-

of amino group and epoxy group.

cat

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-

Scheme 3. Crosslink structure in Type II system.

Acrylic resins containing blocked amino groups, such as ketimines [5]

and oxazolidines [6], can also be used as base resins for epoxy cure.
2.2. Silicon-based

cure

of silicon-based ambient or low temperature cure systems

have been developed in Japan: (i) self-crosslinking of alkoxysilyl-functional
acrylic resins (Qpe I) [ 7-101; (ii) a two-package system based on the blend
of a tert-amino-functional
acrylic resin and an epoxysilane compound as
hardener (Type II) [ 11, 121, and (iii) a one-package system based on the
blend of an acrylic resin having three functional groups, that is hydroxyl,
silanol and cycloaliphatic epoxy groups, and a metal chelate as catalyst (Type
III) [ 13-171.
Alkoxysilyl-functional
acrylic resins of Type I cure by moisture in the
presence of a catalyst such as tin salts to form a crosslink network based
on siloxane bonds (Scheme 2). Cured films of the Type I system have better
weathering resistance than acrylic-urethane films. Coatings formulated with
this system, therefore, have been applied in various outdoor uses, and have
also been examined for automotive topcoats because of their excellent acid
resistance.
Two types of reactions proceed in Type II: first, the reaction of tertamino groups with epoxy groups and secondly hydrolysis--condensation
reactions of alkoxysilyl groups, to form a crosslinked structure containing
siloxane bonds (Scheme 3). Type II coatings have excellent adhesion to
various substrates and better weathering resistance than acrylic-urethane
films. They have been used in various outdoor applications.

Three types

328

In Type III systems, (called ESCA), various crosslinking reactions compete

to result in complicated crosslink structures including siloxane bonds [ 13,
141. The coatings based on this system have an excellent acid resistance
and weathering resistance comparable to those of fluoroolelin copolymers.
They have been applied to automotive topcoats as a substitute for the acrylicmelamine coatings.
Other systems similar to Type I, alkoxysilyl-functional fluoroolefln copolymers [ 18, 191, adducts of OH-functional acrylics with isocyanatosilanes
[ 20,2 11, and resins containing both alkoxysilyl and isocyanate groups [ 22-24 I,
have been developed. Systems similar to Type II, some combinations such
as amino-functional
fluoroolelln
copolymers/epoxysilanes
[25], COOHfunctional resins/epoxysilanes [ 26 ] and cyclocarbonato-functional
resins/aminosilanes [ 2 7 1, have been proposed, as have some other silicon-based systems
such as hydrosilylation [28-301, combination of OH groups and alkoxysilyl
groups [31-361, and a blend of an enol ether-containing compound and a
resin having silanol or alkoxysilyl groups [37].
2.3. Carboxyh?poxy
cure
This system has been extensively studied, and applied in many fields,
such as powder coatings formulated from epoxy-functional acrylics, ambient
temperature curable coatings based on the combination of COOH-functional
acrylics and epoxy-functional acrylics or epoxy resins [38, 391 as a substitute
for acrylic-urethane.
In recent years, requirements for improving acid resistance in automotive
topcoats have resulted in the extensive work on this system as the ester
linkage formed in this system (Scheme 4) is much more resistant to acid
attack than the linkages in acrylic-melamine cured films.
The key points for the commercial success of this cure system are 6rst,
how to get a performance balance of cured 6lms required for the topcoats
and second how to get a one-package stability/curability balance. To achieve
this balance, much research has been done, and many patents relating to
curing catalysts, co-hardeners, introduction of OH groups, and the type of
epoxy and COOH groups have been applied for (Table l), and the addition
of aminoplasts is suggested [62] for the improvement of the one-package
stability.
A new system (called NCS) based on acrylic resins containing a diacid
half-ester moiety (No. 9 in Table 1) has been commercialized in Japan for
acid- and scratch- resistant automotive topcoats [ 63).
2.4. Acid anhydride cure
Although acid anhydride-based curing systems have already been investigated to some extent, current demands for new curing systems as
-COOH

i-

CHz-CH-

O/

Scheme 4. Reaction

-COO-CHyCH-.
bH

of epoxy

group and COOH.

329
TABLE

Patent survey of COOH-epoxy

No. COOH functional
resin
1

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

COOH-OH bifunctional epoxy-OH bifunctionat

acrylics
acrylics
COOH-OH bifunctional epoxy acrylics
acrylics

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

COOH-OH bifunctional cycloaliphatic

acrylics
epoxy-OH bifunctional
acrylics

14

COOH acrylics

15

Acrylics with two groups selected

from COOH, OH and epoxy

16

COOH-OH bifunctional aliphatic poly(epoxide)

acrylics

17

epoxy acrylics

COOH-OH bifunctional cycloaliphatic

acrylics
poly(epoxide)

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

substitutes for the acrylic-urethane

and the acrylic-melamine
systems have
prompted extensive work as in the case of COOH-epoxy
system.
The development of the anhydride cure is focused on the combination
of functional groups such as anhydride/epoxy
[ 64-7 11, anhydride/OH [ 72-751,
anhydride/epoxy-OH
[76, 771 (Scheme
5), and anhydride/blocked
amino
groups (aldimines, ketimines, oxazolidines)
(Scheme 6) [75, 78-861.
Automotive topcoatmgs
(NCT) based on anhydride/epoxy-OH
have been commercialized in USA.
Also multi-crosslinking
systems have been proposed, in which the previously described systems are combined with other mechanisms
such as

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

of acid anhydride with OH and epoxy

Amine

-CH-CH-

CHz-CHlo/

LO-

CNRa

of acid anhydride and blocked

amine.

0
-O!CH=CH.

Scheme

H-X

-O!!CH

2CH 2-X

7. The Michael reaction.

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

The acrylic copolymer of methyl acrylamidoglycolate

methyl ether
(MAGME) (Scheme 8) is one of the representative resins having an activated
ester moiety, and having been investigated for coating applications [ 105-l 08 1.
As the copolymer has two reactive sites, methoxymethylamide
and active
methyl ester groups, it is crosslinked by the following reactions, characteristic
of the amide group as well as of the ester group: (i) acid catalyzed selfcondensation or reaction with OH groups at the amide moiety; (ii) the ester
exchange reaction with OH groups at the ester moiety; (iii) amide formation
with amines or blocked amines at the ester part.
Other examples are a two-package ambient temperature cure system
based on primary ammo-functional resins/dial&l oxa.late [ 1091 and onepackage baking systems based on the following combinations: OH-functional
resins/poly(oxamates)
[ 1 lo];
p-hydroxyalkyl
ester/OH group [ 1111 and
p-hydroxyalkyl ester/primary ammo group [ 111 I.
2.7. Acetoacetate
Acetoacetate groups (Scheme 9) are easily introduced in polymers by
three methods: copolymerization of acetoacetoxyethyl methacrylate; reactions
of OH-functional resins with diketene; and ester exchange reactions of OHfunctional resins with alkyl acetoacetates [ 112 1.
The basic chemistry of this group has been well investigated with the
application for coatings in mind [ 112, 1131. This group has two reactive
sites, the active methylene and the ketone carbonyl, that are capable of
reacting with various functional compounds such as aminoplasts, poly(amines),
poly(ketimines),
poly(isocyanates),
poly(acryloy1) compounds (the Michael
reaction) [ 1141, metal alkoxides and metal chelates [ 115, 1161. Commercial
products based on the acetoacetate/ketimine reaction are available for car
refinish [97].
Recently, ambient temperature cure systems based on acetoacetate/aminosilane reactions [ 117 1, acetoacetate-epoxy/poly(amine)
reactions [ 118 I, and
a baking type based on acetoacetate/vinyl ether reactions [ 1191 have been
proposed.
2.8. Blocking of functional groups
Blocking of functional groups is an important technique in developing
crosslinking systems for the following reasons: (i) the improvement of onepackage stability of coatings by reducing the reactivity; (ii) the achievement
of higher solids coatings by formulating with resins containing blocked
functional groups, which have lower polarity compared with unblocked groups.

Ii

CHz=CHCNH-CH-COCHs

si
-Of,,

bCHs

Scheme 8. Methyl acrylamidoglycolate

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

of silyl ether and isocyanate.

Jo-~;,

CH3

t-butyt

ester

-CH-CHZ
b

Jo-~,,,
l
R3

ketat ester

Scheme 12. Blocked COOH group.

C
a

-COOH

-m

-CH-CHF

OH

b-Ca

Scheme 13. Reaction of cyclocarbonate and COOH.

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

In water-based systems, research in crosslinking technology has become

active in accordance with the market growth of waterborne coatings. This
is due to the current need for high performance and easy application of
waterborne coatings comparable to those of solvent-based coatings.
Recent developments in new crosslinking systems for water-based coatings
are focused on the ambient temperature cure of emulsion polymers or water
solubilized polymers as well as the low temperature cure for cathodic
electrocoatings. A review paper [ 1511 regarding crosslinking of emulsions
is available.
3.1. Ambient temperature cure
As a one-package curing system for emulsion polymers, hydrazone
formation between a carbonyl and a hydrazine residue (Scheme 15) has been
widely investigated. Some commercial products based on this chemistry are
available. For this system a variety of combinations have been proposed.
Examples are combinations of C=O functional polymers with low molecular
weight compounds having a hydrazine residue [ 152-1571 or with polymers
containing hydrazine residues [ 158-l 6 11, and urethane-modified emulsions

-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

[ 1621 synthesized by copolymerizing a C =0 functional monomer in the

presence of a poly(urethane) having hydrazine residues.
One-package curable emulsions, whose particles are made up of an
epoxy resin-enriched inner shell and an amino-functional acrylic outer shell
have been developed [ 163-1661. Commercial products of the emulsions are
available in Japan.
Other mechanisms, which have been investigated in case of one-package
curing systems of emulsions, are the oxazoline/COOH esterification (the blend
of oxazoline-functional resins and COOH resins) [ 167, 1681, Schilf base
formation (self-crosslinking of resins having both primary amino and C=O
groups) [ 169 1, and acetoacetate/epoxy reaction (self-crosslinking of resins
containing three functional groups: acetoacetate, epoxy and COOH) [170].
As two-package systems, the following blends or acid catalyzed selfcrosslinking of MAGME-based emulsion copolymers [106, 1071 have been
investigated: (i) a COOH-functional emulsion polymer and a resin containing
halohydrin moieties which are converted to epoxy groups upon treatment
with a base [ 171, 1721; (ii) an epoxy-functional emulsion polymer and an
aminoalkoxysilane
[ 1731;
(iii)
a COOH-functional
resin and a
poly(carbodiimide) [ 174, 1751; (iv) an acrylic dispersion polymer having
electron deficient C =C double bonds and a poly(aminoamide) or a
poly(ketimine) (the Michael reaction) [9 7,176], (v) an acetoacetate-functional
acrylic dispersion polymer and a poly(aminoamide) or a poly(ketimine) [97,
1771. Application of the isocyanate cure system for waterborne coatings has
also been investigated with acrylic emulsion polymers [ 1781 and watersolubilized or dispersed acrylics [ 179, 1SO].
3.2. Baking type
Much effort has been exerted to develop low temperature cure systems
for cathodic electrocoatings. Many patents concerning new crosslinking
systems have been filed. Examples are combinations such as OH/cycloaliphatic
epoxy [181-1841, &hydroxyalkyl ester/OH or amino groups [185-1871,
P-hydroxyalkyl carbamate/OH or amino groups [ 1881, OWalkoxysilyl groups
[ 189,190 1, acetoacetate/primary ammo groups [ 19 11, amineimides/ketirnines
[ 1921, Michael adducts/amines or ketimines (Michael exchange reaction)
[ 193 I, and 3-alkoxyalkyl-3-(meth)acryloylureido
groups/OH [ 1941.
Other systems, which may be generally used for many applications, are
COOH/cyclaliphatic epoxy [ 195-l 981, COOWcyclocarbonate [ 199, 2001 and
acylamides/OH or amino groups [201, 2021.
4. Conclusions
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. Challenges in developing

335

new systems are continuing in order to realize further reduction of VOC,

lower temperature cure, safety and better performance.
The authors hope that this paper will be of some use to those who are
involved in synthesis and application of binders for organic coatings.

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