THERMOSETTING COMPOSITIONS, THERMAL LATENT CARBOXYL COMPOUNDS AND METHODS OF PREPARATION THEREOF

COMPOSITIONS THERMODURCISSABLES, COMPOSES DE CARBOXYL A AGENT DE DURCISSEMENT INHIBE ET METHODES DE PREPARATION DESDITS PRODUITS

English Abstract

Thermosetting composition is excellent in storage
stability, is useful as one component thermosetting
composition, gives cured products having excellent chemical
properties, physical properties and weathering resistance
and is favorably utilized in coating compositions, ink,
adhesive and molded plastics.
The thermosetting composition comprises a compound
having in the molecule two or more carboxyl groups blocked
by a vinyl ether compound, a vinyl thioether compound or a
hetero compound having a vinyl type double bond and oxygen
or sulfur as the hetero atom, a eompound having two or more
reaetive funetional groups which can form a chemical bond
with the blocked carboxyl compound by heating and
optionally a thermal latent aeid catalyst. The blocked
carboxyl group of the first compound and the reactive
functional group of the second compound may be comprised in
the same molecule.

French Abstract

Composition thermodurcissable douée d'une excellente stabilité à l'entreposage, qui est utile comme composition thermodurcissable à un constituant, qui donne des produits durcis ayant d'excellentes propriétés chimiques et physiques ainsi qu'une excellente résistance aux intempéries et qui est utilisée avantageusement dans les compositions de revêtement, les encres, les adhésifs et les plastiques moulés. La composition thermodurcissable comprend un composé dont la molécule comprend deux groupes carboxyle ou plus bloqués par un composé d'éther vinylique, un composé de thioéther vinylique ou un hétérocomposé ayant une double liaison de type vinyle et de l'oxygène ou du soufre comme hétéroatome, un composé ayant deux groupes fonctionnels réactifs ou plus qui peuvent former une liaison chimique avec le composé ayant un carboxyle bloqué par chauffage et facultativement un catalyseur acide latent activé par la chaleur. Le groupe carboxyle bloqué du premier composé et le groupe fonctionnel réactif du second composé peuvent être situés dans la même molécule.

Claims

WHAT IS CLAIMED IS:
1. A thermosetting composition which comprises:
(A) a compound having in the molecule two or more
functional groups of the general formula [1]:
<IMG>
[I]
wherein R1, R2 and R3 are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, R4 is an organic group of 1 to 18
carbon atoms, Y1 is selected from the group consisting of
an oxygen atom and a sulfur atom and R3 and R4 may be
bonded with each other to form a heterocyclic structure
which comprises Y1 as the hetero atom component;
(B) a compound having in the molecule two or more reactive
functional groups which can form a chemical bond with the
functional groups of the compound (A) by heating; and,
optionally,
(C) a thermal latent acid catalyst which is activated
during curing of the composition by heating.
2. A thermosetting composition as claimed in Claim 1,
wherein the reactive functional groups of the compound (B)
111

are at least one kind selected from the group consisting of
epoxy group, silanol group, alkoxysilane group, hydroxyl
group, amino group, imino group, isocyanate group, blocked
isocyanate group, cyclocarbonate group, vinyl ether group,
vinyl thioether group, aminomethylol group, alkylated
aminomethylol group, acetal group and ketal group.
3. A thermosetting composition as claimed in Claim 1 or
Claim 2, wherein the thermal latent acid catalyst (C) is at
least one kind selected from the group consisting of a
compound prepared by neutralizing a protonic acid or a
Lewis acid with a Lewis base, an ester of a sulfonic acid,
an ester of phosphoric acid and an onium compound or a
compound prepared by mixing a Lewis acid with trialkyl
phosphate.
4, A thermosetting composition as claimed in Claim 1, Claim
2 or Claim 3, wherein the compound (A) and/or the compound
(B) are polymers of .alpha.,.beta.-unsaturated compounds.
5. A thermosetting composition as claimed in Claim 1, Claim
2 or Claim 3, wherein the compound (A) and/or the compound
(B) are polyester resins.
112

6. A thermosetting composition which comprises:
(D) a self-crosslinking compound having in the molecule (a)
one or more functional groups of the general formula [2];
<IMG>
[2]
wherein R5, R6 and R7 are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, R8 is an organic group of 1 to 18
carbon atoms, Y2 is selected from the group consisting of
an oxygen atom and a sulfur atom and R7 and R8 may be
bonded with each other to form a heterocyclic structure
which comprises Y2 as the hetero atom component; and (b)
one or more reactive functional groups which can form a
chemical bond with the functional groups (a) by heating;
(C) optionally, a thermal latent acid catalyst which is
activated during curing of the composition by heating;
(A) optionally, a compound having in the molecule two or
more functional groups of the general formula [1]:
<IMG>
[1]
113

wherein R1, R2 and R3 are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, R4 is an organic group of 1 to 18
carbon atoms, Y1 is selected from the group consisting of
an oxygen atom and a sulfur atom and R3 and R4 may be
bonded with each other to form a heterocyclic structure
which comprises Y1 as the heteroatom component; and/or,
(B) optionally, a compound having in the molecule two or
more reactive functional groups which can form a chemical
bond by heating with either one or both of the functional
group of the general formula [1] and the functional group
of the general formula [2].
7. A thermosetting composition as claimed in Claim 6,
wherein the reactive functional groups (b) of the compound
(D) and the reactive functional groups of the optionally
utilized compound (B) are selected from the group
consisting of epoxy group, silanol group, alkoxysilane
group, hydroxyl group, amino group, imino group, isocyanate
group, blocked isocyanate group, cyclocarbonate group,
vinyl ether group, vinyl thioether group, aminomethylol
group, alkylated aminomethylol group, acetal group and
ketal group.
114

8. A thermosetting composition as claimed in Claim 6 or
Claim 7, wherein the thermal latent acid catalyst of (C) is
at least one kind selected from the group consisting of a
compound prepared by neutralizing a protonic acid or a
Lewis acid with a Lewis base, an ester of a sulfonic acid,
an ester of phosphoric acid and an onium compound or a
compound prepared by mixing a Lews acid with triaklyl
phosphate.
9. A thermosetting composition as claimed in Claim 6, Claim
7 or Claim 8, wherein at least one of the compound (D) and
the compound (A) and/or the compound (B) is polymer of an
.alpha.,.beta.-unsaturated compound.
10. A thermosetting composition as claimed in Claim 6,
Claim 7 or Claim 8, wherein at least one of the compound
(D) and the compound (A) and/or the compound (B) is
polyester resin.
11. A thermal latent compound which is prepared by reaction
of a polycarboxyl compound having two or more carboxyl
groups in the molecule, acid equivalent of not more than
l000g/mole and number average molecular weight of not more
than 4000 with a vinyl ether compound, whereby the carboxyl
115

group is transformed into a functional group of the general
formula [3]:
<IMG>
[3]
wherein R9, R10 and R11 are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, R12 is an organic group of 1 to 18
carbon atoms, Y3 is selected from the group consisting of
an oxygen atom and a sulfur atom and R11 and R12 may be
bonded with each other to form a heterocyclic structure
which comprises Y3 as the hetero atom component.
12. A thermal latent carboxyl compound as claimed in Claim
11, wherein the polycarboxyl compound is a compound
prepared by half esterification of a polyol having two or
more hydroxyl groups in the molecule and an acid anhydride.
13, A thermal latent carboxyl compound as claimed in Claim
11, wherein the polycarboxyl compound is an addition
product of a polyisocyanate compound having two or more
isocyanate groups in the molecule and a hydroxycarboxylic
acid or an amino acid.
116

14. A thermal latent carboxyl compound as claimed in Claim 1
1, wherein the polycarboxyl compound is a polyester resin.
15. a thermal latent carboxyl compound as claimed in Claim
11, wherein the polycarboxyl compound is an acrylic resin.
16. A method of preparation of the thermal latent carboxyl
compound claimed in either one of Claim 11, Claim 12, Claim
13, Claim 14 and Claim 15 which is characterized in that a
polycarboxyl compound having two or more carboxyl groups in
the molecule, acid equivalent of not more than l000g/mole
and number average molecular weight of not more than 4000
is reacted with a vinyl ether compound.
117

Description

2040167
THERNOSETTING CONPOSITIONS, THERMAL LATENT CARBOXYL
COMPOUNDS AND METHODS OF PREPARATION THEREOF
BACKGROUND OF THE INVENTION
1. Field of the invention
The present invention relates to novel thermosetting
compositions, thermal latent carboxyl compounds and methods
of preparation thereof. More particularly, the present
invention relates to novel thermosetting compositions
having excellent chemical properties, physical properties
and weathering resistance and exceptionally excellent
storage stability and suitable for preparation of coating
compositions, ink, adhesive and molded plastics, novel
thermal latent carboxyl compounds utilized for the
preparation of the thermosetting compositions and methods
of effectively preparing the thermal latent carboxyl
compounds.
2. Description of the prior art
It is generally known that thermosetting compositions
can be prepared from compounds having carboxyl groups and
compounds having reactive functional groups which can form
chemical bonds with the carboxyl groups by heating, such as
epoxy group, silanol group, alkoxysilane group, hydroxyl
group, amino group, imino group, isocyanate group, blocked

2040167
isocyanate group, cyclocarbonate group, vinyl ether group,
vinyl thioether group, aminomethylol group, alkylated
aminomel,hylol group, acetal group and ketal group. The
thermosetting compositions give cured products having
excellent chemical properties, physical prcperties and
weathering resistance and are widely utilized in the field
of coating compositions, ink, adhesive and molded plastics.
However, the reactivity between the carboxyl groups and
the reactive functional groups is generally very high and
compositions in which compounds having carboxyl groups and
compounds having the reactive functional groups are mixed
together have prob]ems that the composition is often
gelatinized during storage or, in other words, that potlife
is short.
For the purpose of solving the problems, it was
proposed that carboxyl group was blocked by converting it
to tertiary--butyl ester and the free carboxyl group was
regenerated by eliminat.ion of isobutene by heating
~Laid-Open Japanese Patent Publication Heisei l-104646).
However, this method requires high temperatllre, such as
170-200~, for the heat decomposition of the tertiary-butyl
ester and problems remain from the point of view of
material saving and energy saving.

20~0167
SUMMARY OF TIlE I~VENTION
The present invention accordingly has an object to
provide thermosetting compositinns which give cured
products having excellent chemical properties, physical
properties and weathering resistance at relatively low
temperature, have excellent storage stability and can be
utilized as one component material. Another object of the
invention is to provide a thermal latent carboxy~ compound
useful for the preparation of the thermosetting
compositions. Still another object of the invention is to
provide methods of preparation of the thermal latent
carboxyl compounds.
Thus, the thermosetting compositions of the present
invention comprise:
(A) a compound having in the molecule two or more
functional groups of the general formula rl]
Rl
-C-O-C-Yl-R4
O HC--R3
R2 rl~
wherein Rl, R2 and R3 are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, R4 is an organic group of 1 to 18
carbon atoms, Y' is selected from the group consisting of

2040167
an oxygen atom and a sulfur atomand R3 and R4 may be bonded
with each other to form a heterocyclic structure which
comprises yl as the heteroatom component;
(B) a compound having in the molecule two or more reactive
functional groups which can form a chemical bond with the
functional groups of the compound (A) by heating; and,
optionally,
(C) a thermal latent acid catalyst which is activated
during curing of the composition by heating.
T'ne thermosetting compositiGn of the present invention
also comprises:
(D) a self--crosslinking compound having in the molecule (a)
one or more functional groups of the general formula [2]:
Rs
-C-O-c -y 2 R8
Il I
O HC-R7
Rs [2l
wherein R5, Rs and R7 are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, R~ is an or~anic group of 1 to 18
carbon atoms, y2 iS selected from the group consisting of
an oxygen atom and a sulfur atom and R7 and Rs may be
bonded with each other to form a heterocyclic structure
which comprises y2 as the heteroatom component; and (b) one

- 20~0167
or more reactive functiona] groups which can form a
chemical bond with the functional groups (a) by heating;
(C) optionally, a thermal latent acid catalyst which is
activated during curing of the composition by heating;
(A) optionally, a compound having in the molecule two or
more functional groups of the general formu]a r
R'
-c_o-c-yl-R4
O HC-R 3
R2 [l]
wherein Rl, R2 and R3 are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, R4 is an organic group of 1 to 18
carbon atoms, yl is selected from the group consisting of
an oxygen atom and a sulfur atom and R3 and R4 ma~ be
bonded with each other to form a heterocyclic structure
which comprises Y' as the heteroatom component; and/or,
(B) optionally, a compound having in the molecule two or
more reactive functional groups which can form a chemical
bond by heating with either one or both of the functional
group of the general formula rl3 and the functional group
of the general formula r2~.
The thermal latent carboxyl compounds of the invention
are prepared by reaction of a pol~carboxyl compsund having

20~0167
two or more carboxyl groups in the molecule, acid
equivalent of not more than lOOOg/mole and number average
molecular weight of not more than 4000 with a vinyl ether
compound, whereby the carboxyl groups are transformed into
a functional group of the general formula [3~:
R9
-C-o-c-Y3-R I 2
O HC-RI '
R'~ [3]
wherein R9, R~u and R'l are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, Rl2 is an organic group of 1 to 18
carbon atoms, Y3 iS selected ~rom the group consisting of
an oxygen atom and a sulfur atom and Rl' and R'Z may be
bonded with each other to form a heterocyclic structure
which comprises Y3 as the hetero atom component.
The method of preparation of the thermal latent
carboxyl compound of the invention is characterized in that
a polycarboxyl compound having two or more carboxyl groups
in the molecule, acid equivalent of not more than
lOOOg/mole and number average molecular weight of not more
than 4000 is reacted with a vinyl ether compound.
Other and further objects, features and advantages of
the invention will appear more fully from the following

21~0167
description.
DESCRIPTION OF THE PRE~ERRED EMBODIMENTS
Extensive studies were made by the present inventors to
develop a novel thermosetting composition to achieve the
objects and it was discovered that the following
compositions were effective.
One of the compositions discovered comprises: (A) a
compound having in the molecule two or more carboxyl groups
which are blocked by a specific vinyl ether group, vinyl
thioether group or heterocyclic group having vinyl type
double bond and oxygen or sulfur as the hetero atom
component; (B) a compound having in the molecule two or
more reactive functional groups which can form chemical
bond with the blocked carboxyl group by heating and,
optionally, (C) a thermal latent acid catalyst which is
activated during curing by heating.
Another of the compositions discovered comPrises: (D) a
self-crosslinking compound having in the molecule one or
more blocked carboxyl groups and one or more reactive
functional groups which can form chemical bond with the
blocked carboxyl groups by he~tin~ and, optionally, the
compound (C). The composition may optionally comprise the
compound (A) and/or the compound (B).

2~0167
It was a]so discovered that the thermal latent carboxyl
compound giving the thermosetting composition having the
advantageous properties could be prepared by reacting a
specific low molecular weight polycarboxyl compound with a
vinyl ether compound to block the carboxyl group of the
polycarboxyl compound.
The present invention was completed on the basis of the
discovery described above.
Thus, the thermosetting compositions of the present
invention comprise:
(A) a compound having in the molecule two or more
functional groups of the general formula [1]:
IRl
c o-C-Y l-R4
~I I
O HC-R3
R2 ~1~
wherein R;, RZ and R3 are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, R4 is an organic group of 1 to 18
carbon atoms, yl is selected from the group consisting of
an oxygen atom and a sulfur atom and R3 and R4 may be
bonded with each other to form a heterocyclic structure
which comprises yl as the hetero atom comPonent;
(B) a compound having in the molecule two or more reactive

20~0167
functional groups which can form a chemical bond with the
functional groups of the compound (A) by heating; and,
optionally,
(C) a thermal latent acid catalyst which is activated
during curing of the composition by heating.
The thermosetting compositions of the present invention
also comprise:
(D) a self-crosslinking compound having in the molecule (a)
one or more functional groups of the general formula ~2]:
Rl s
-C-O-C-Y 2_R8
U
O HC-R7
R5 ~2]
wherein R5, R5 and R7 are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, R8 is an organic group of 1 to 18
carbon atoms, y2 iS selected from the group consisting of
an oxygen atom and a sulfur atom and R7 and R8 may be
bonded with each other to form a heterocyclic structure
which comprises y2 as the hetero atom component; and (b)
one or more reactive functional groups which can form a
chemical bond with the functional groups (a) by heating;
(C) optionally, a thermal latent acid catalyst which is
activated during curing of the composition by heating;

20~0167
(A) optionally, a compound having in the molecule two or
more functional groups of the general formula [1]:
-C-o-c-yl-R4
Il l
O HC--R3
R~ ~1]
wherein R', RZ and R3 are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, R4 is an organic group of 1 to 18
carbon atoms, yl is selected from the group consisting of
an oxygen atom and a sulfur atom and R3 and R4 may be
bonded with each other to form a heterocyclic structure
which comprises yl as the hetero atom component; and/or,
(B) optionally, a compound having in the molecule two or
more reactive functional groups which can form a chemical
bond by heating with either one or both of the functional
group having the general formula [1] and the functional
group having the general formula [2~.
The thermal latent carboxyl compound of the invention
is prepared by reaction of a polycarboxyl compound having
two or more carboxyl groups in the molecule, acid
equivalent of not more than lOOOg/mole and number average
molecular weight of not more than 4000 with a vinyl ether
compound, whereby the carboxyl group is transformed into a
1 0

20~0167
functional group having the general formula [3~:
R9
-C-o-c-y3--R I 2
ll I
O HC-R'
R'~ [31
wherein R9, Rl~ and Rll are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, Rl2 is an organic group of 1 to 18
carbon atoms, Y3 iS selected from the group consisting of
an oxygen atom and a sulfur atom and Rll and Rl 2 may be
bonded with each other to form a heterocyclic structure
which comp~ises Y3 as the hetero atom component.
The method of preparation of the thermal latent
carboxyl compound of the invention is characterized in that
a polycarboxyl compound having two or more carboxyl groups
in the molecule, acid equivalent of not more than
lOOOg/mole and number average molecular weight of not more
than 4000 is reacted with a vinyl ether compound.
The invention is descrihed in more detail in the
following.
The compound (A) in ~he thermosetting composition of
the invention has in the molecule two or more, preferably
from 2 to 50, functional groups of the following general
formula [1]: 1 1

- 20~0167
-C-O-C-Y l-R4
Il I
O HC-R3
R2 [1]
The functional group having the general formula [1] is
easily prepared by reaction of carboxyl group with a vinyl
ether, a vinyl thioether or a heterocyclic compound having
oxygen or sulfur as the hetero atom and having a vinyl type
double bond which is described by the general formula [4]:
C=C-Yl-R4
R3 [4~
In the formula [1] and formula r43. Rl, R2 and R3 are
respectively selected from the group consisting of a
hydrogen atom and an organic group, such as alkyl group,
aryl group and alkaryl group of 1 to 18 carbon atoms. R4 is
an organic group, such as alkyl group~ aryl group and
alkaryl group of 1 to 18 carbon at~oms. The organic groups
may have substituted groups in the molecule and R3 and R4
may, by bonding together, form a heterosyclic structure
with or without substituents and having Y' as the hetero
atom component.
Examples of the compound of the formula [4] are:
aliphatic vinyl ethers, such as methyl vinyl ether, ethyl

2040167
vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether,
n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl
vinyl ether, cyclohexyl vinyl ether and the like; aliphatic
vinyl thioethers, such as methyl vinyl thioether, ethyl
vinyl thioether, isopropyl vinyl thioether, n-propyl vinyl
thioether, n-butyl vinyl thioether, isobutyl vinyl
thioether, 2-ethylhexyl vinyl thioether, cyclohexyl vinyl
thioether and the like; cyclic vinyl ethers, such as
2,3-dihydrofuran, 3,4-dihydrofuran, 2.3-dihydro-2H-pyran,
3,4-dihydro-2H-pyran, 3,4--dihydro-2-methoxy-2H-pyran,
3,4-dihydro-4,4-dimethyl-2H-pyran--2-one,
3,4-dihydro-2--ethoxy-2H-pyran, sodium
3,4-dihydro-2H-pyran-2-carboxylate and the like; and cyclic
vinyi thioethers, such as 2,3-dihydrothiophene,
3,4-dihydrothiophene, 2,3-dihydro-2H-thiopyran,
3,4-dihydro-2H-thiopyran, 3,4-dihydro-2-methoxy-
2H-thiopyran, 3,4-dihydro-4,~-dimethyl-2H-thiopyran-2-one,
3,4-dihydro-2-ethoxy-2H-thiopyran, sodium
3,4-dihydro-2H-thiopyran-2-carboxylate and the like.
The compound (A) is prepared by the reaction of a
compound having two or more carboxyl groups in the molecule
with the compound having the formula r4]. Examples of the
compound having two or more carboxyl groups in the molecule
are: aliphatic polycarboxylic acids of 2 to 22 carbon

2040167
atoms, such as succinic acid, adipic acid, azelaic acid,
sebacic acid, decamethylenedicarboxylic acid and the like;
aromatic polycarboxylic acids, such as phthalic acid,
isophthalic acid, terephthalic acid, trimellitic acid,
pyromellitic acid and the like; alicyclic polycarboxylic
acids, such as tetrahydrophthalic acid, hexahydrophthalic
acid and the like; resins having two or more carboxyl
groups in the molecule, such as polyester resins, acrylic
resins, polybutadiene resins modified with maleic acid and
the like resins all having two or more carboxyl groups in
the molecule.
The compound having two or more carboxyl groups in the
molecule is prepared by: (1) half-esterificatiorl of a
polyol having two or more hydroxyl groups in the molecule
with an acid anhydride; (2) addition of a polyisocyanate
compound having two or more isocyanate groups in the
molecule with a hydroxycarboxylic acid or an amino acid;
(3) polymerization of an a,~-unsaturated monomer having
carboxyl group or copolymerization of the a,~-unsaturated
monomer with other ~,~-unsaturated monomers; (4)
preparation of polyester resin having carboxyl groups and
the like other methods.
Examples of the polyol having two or more hydroxyl
groups are: ethylene glycol, 1,2-propylene glycol,
1 4

20~0167
1,3--propylene glycol, 1,3-butanediol, 1,4-butanediol,
2,3-butanediol, 1,6-hexanediol, diethylene glycol,
pentanediol, dimethylbutanediol, hydrogenated bisphenol A,
glycerol, sorbitol, neopentyl glycol, l,8-octanediol,
l,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol,
1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane,
trimethylolpropane, pentaeryt,hr;tol, quinitol, mannitol,
tris-hydroxyethyl isocyanurate, dipentaerythritol and the
like; addition products of the polyhydric alcohol with a
lactone, such as r-butYrolactone and ~--caprolactone and
the like, by ring opening of the lactone; addition
products of the polyhydric alcohol with an isocyanate, such
as tolylene diisocyanate, diphenylmethane diisocyanate,
hexamethylene diisocyanate, isophorone diisocyanate and the
like, in excess amount of the alcohol; addition products of
the polyol with a divinyl ether, such as ethylene glycol
divinyl ether, polyethylene glycol divinyl ether,
butanediol divinyl ether, pentanediol divinyl ether,
hexanediol divinyl ether, 1,4-cyclohexane-dimethanol
divinyl ether and the like, in excess amount of the
alcohol; addition products of the polyol with an
alkoxysilane compound, such as KR-213~, KR-217~, KR-9218~
(products of Shinetsu Chemical Co., Ltd.), in excess amount
of the alcohol; and the like other compounds.
1 5

20~0167
Examples of the acid anhydride which reacts with the
polyol having two or more hydroxyl groups in the molecule
are: acid anhydrides of polycarboxylic acids, such as
succinic acid, glutaric acid, adipic acid, azelaic acid,
sebacirlic acid, decamethylenedicarboxylic acid, phthalic
acid, maleic acid, trimellitic acid, pyromellitic acid,
tetrahydrophthalic acid, hexahydrophthalic acid and the
like.
Examples of the polyisocyanate compound having two or
more isocyanate groups in the molecule which reacts with a
hydroxycarboxylic acid or an amino acid are: p-phenylene
diisocyanate, biphenyl diisocyanate, tolylene diisocyanate,
3,3'-dimethyl-4,4'-biphenylene diisocyanate,
1,4-tetramethylene diisocyanate, hexamethylene
diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate,
methylene-bis-(phenyl isocyanate), lysine methyl ester
diisocyanate, bis-(isocyanatoethyl) fumarate, isophorone
diisocyanate, methylcyclohex~l diisocyanate,
2-isocyanatoethyl-2,6--diisocyanatohexanoate, biuret
derivatives of these polyisocyanates, isocyanurate
derivatives of these polyisocyanates and the like
compounds.
Examples of the hydroxycarboxylic acid which reacts
with the polyisocyanate compound ~re: lactic acid, citric
1 6

20~01~7
acid, hydroxypivalic acid, 12-hydroxystearic acid, malic
acid and the like. Examples of the amino acid which reacts
with the polyisocyanate compound are: DL-alanine,
L-glutamic acid, glycine, L-teanine, glycylglycine,
~-aminocaproic acid, L-aspartic acid, L-citrulline,
L-arginine, L-leucine, L-serine and the like.
Examples of the a,~--unsaturated monomer having
carboxylgroup which are polymerized or copolymerized are:
acrylic acid, methacrylic acid, itaconic acid, mesaconic
acid, maleic acid, fumaric acid and the like. Examples of
the other a,~--unsaturated monomer which is copolymerized
with the q,~-unsaturated monomer having carboxyl group
are: mcthyl (meth)acrylate, ethy] (meth)acrylate, n-propyl
(meth)acrylate, isopropyl (meth)acrylate, n-butyl
(meth)acrylate, isobutyl (meth)acrylate, sec-butyl
(meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl
a-(meth)acrylate, stearyl (meth)acrylate, styrene,
methylstyrene, p-vinyltoluene, acrylonitrile and the like.
The polyester resin having carboxyl groups is easily
prepared according to the conventional method of
preparation of polyester resins by using excess amount of
polyacid in relation to the amount of polyol.
The reaction of the compound having two or more,
preferably from 2 to 50, carboxyl group in the molecule

- 2040167
with the compound having the formula [4] is generally
performed at a temperature between the ambient temperature
and 100~ in the presence of an acid catalyst.
Either a single kind of the compound (A) or a
combination of two or more kinds Or the compound (A) may be
utilized in the invention.
The compounds (B) utilized in the thermosetting
composition of the invention are compounds having in the
molecule two or more, preferably from 2 to 50, reactive
functional groups which can form chemical bonds by the
reaction with the regenerated carboxyl group formed from
the blocked carboxyl group [1~ of the compound (A) by
heating. The kind of the reactive functional group is not
particularly limited so long as it satisfies the condition
described herein. Preferable examples of the reactive
functional group are: epoxy group, silanol group,
alkoxysilane group, hydroxyl group, amino group, imino
group, isocyanate group, blocked isocyanate group,
cyclocarbonate group, vinyl ether group, vinyl thioether
group, aminomethylol group, alkyl substituted aminomethylol
group, acetal group, ketal group and the like groups. The
compound (B) may have either a single kind or two or more
kinds of the reactive functional groups in the molecule.
Examples of the compound of (B) are: compounds
1 8

2~0167
having epoxy groups, such as epoxy resins of bisphenol
type, ~licyclic epoxy resins, homopolymers and copolymers
of glycidyl (meth)acrylatc, 3,4-epoxycyclohexylmethyl
(meth)acrylate and the like compounds, polyglycidyl
compounds obtained by the reaction of epichlorohydrine with
polycarboxylic acids or polyols and other like compounds;
compounds having silano~ group or alkoxysilane group, such
as condensation products of a compound having the formula
~5]:
(Rl 3 ) n S i ( OR'4) 4 - n [ 5]
wherein Rl3 and Rl4 are respectively selected from the
group consisting of alkyl group of l to 18 carbon atoms and
aryl group of I to 18 carbon atoms and n is 0, 1 or 2,
homopolymers and copolymers of a,~-unsaturated silane
compounds, like acryloyloxypropyltrimethoxysilane,
methacryloyloxypropyltrimethoxysilane, methacryoyloxy-
propyltri-n-butoxysilane and the like, hydrolysis products
of these compounds and the like;
compounds having hydroxyl group, such as aliphatic polyols,
phenols, polyalkyleneoxyglycols, homopolymers and
copolymers of a,~-unsaturated compounds, like
2-hydroxyethyl-(meth)acrylates, 2-hydroxypropyl
(meth)acrylate and the like, addition products of
~-caprolactone with these polyhydroxyl compounds and the
1 9

20~0167
like;
compGunds having amino group, such as aliphatic diamino
compounds, aromatic diamino compounds, polyamino compounds
prepared by cyanoethylation and reduction of the compounds
having hydroxyl group and the like;
compounds having imino group, such as aliphatic polyimino
compounds, aromatic polyimino compounds and the like;
compounds having isocyanate group, such as p-phenylene
diisocyanate, biphenyl diisocyanate, tolylene diisocyanate.
3,3'-dimethyl--4,4'-biphenylene diisocyanate,
1,4-tetramethylene diisocyana~e, hexamethylene
diisocyanate, 2,2,4-trimethyihexane-1,6-diisocyanate,
methylene-bis--(phenyl isocyanate), lysine methyl ester
diisocyanate, bis-(isocyanatoethyl) fumarate, isophorone
diisocyanate, methylcylcohexyl diisocyanate,
2-isocyanatoethyl 2,6--diisocyanatohexanoate, biuret
derivatives and isocyanurate derivatives of these
isocyanates, addition products of these isocyanates and the
compounds having hydroxyl group and the like;
compounds having blocked isocyanate group, such as
compounds prcpared by blocking the compounds having
isocyanate group with phenols, lactams, active methylenes,
alcohols, acid amides, imides, amines, imidazoles, ureas,
imines, or oximes and the like compounds;
2 0

2Q~0167
compounds having c.yclocarbonate group, such as homopolymers
and copolymers of 3-(meth)acryloyloxypropylene carbonate,
compounds having polyfunctional cyclocarbonate groups
prepared by the reaction of the compounds having epoxy
group with carbon dioxide and the like;
compounds having vinyl ether group or vinyl thioether
group, such as polyfunctional vinyl ether compounds
prepared by the reaction of the compounds having hydroxyl
group with halogenated alkyl vinyl ethers, polyvinyl ethers
prepared by the reaction of hydroxyalkyl vinyl ethers with
compounds having polyfunctional carboxyl group or with the
compounds having isocyanate group, copvlymer of
vinyloxyalkyl (meth)acrylates with a,~-unsaturated
compounds, vinyl thioethers corresponding to the vinyl
ethers and the like;
compounds having aminomethylol groups or alkyl substituted
aminomethylol groups, such as melamine formaldehyde resins,
glycolyl formaldehyde resins, urea formaldehyde resins,
homopolymers and copolymers of ~ unsaturated compounds
having aminomethylol group or alkylated aminomethylol
group and the like;
compounds having acetal groups or ketal groups, such as
polyfunctional acetal compounds prepared by the reaction of
polyfunctional ketones, polyfunctional aldehydes, or
2 1

2010167
polyfunctional vinyl ether compounds and the like compounds
with alcohols or orthoacids esters, condensation products
of the polyfunctional acetal compounds with polyols,
homopolymers and copolymers of addition products of the
vinyloxyalkyl (meth)acrylate with alcohols or orthoacid
esters; and the like other compounds.
The compound (B) utilized in the invention may be
either a compound comprising a single kind of functional
group, such as the compounds shown in the examples, or a
compound comprising two or more kinds of functional group
in the molecule. Two or more kinds of the compound (B) may
utilized together. However, when the functional groups of
two or more kinds ar~ reactive between each other, the
storage stability of the thermosetting composition is
damaged and the utilization of such combination of the
functional groups is undesirable. Examples of such
undesirable combination of functional groups are:
combination of a functional group selected from the group
of epoxy group, isocyanate group, vinyl ether group, vinyl
thioether group, cyclocarbonate group and silanol group
with amino group or imino group, combination of hydroxyl
group with isocyanate group or vinyl ether group and the
like other combinations.
The thermosetting composition of the invention may
2 2

2040167
comprise the compound (A) and the compound (B) or it may
comprise compound (D), ~ self-crosslinking compound
comprising (a) one or more, preferably from one to 50,
functional groups having the formula t2] and (b) one or
more, preferably from one to 50, reactive functional groups
which can form chemical bond with the functional group (a)
by heating. The thermosetting composition of the invention
may also comprise the compound (D) and the compound (A)
andior the compound (B) and, in this case, the functional
group of the compound (B) forms chemical bond with the
functional group of formula ~1~ and/or the functional group
of formula [2] by heating.
Examples of the functional grollp (a) having the formula
t2] of the compound (D) are the same functional groups as
the examples of the functional group having the formula [1]
in the compound (A) already described. examples of the
reactive functional group (b) are the same functional
groups as the examples of the reactive functional groups of
compound (B).
The compound (D) can be prepared from a compound
comprising one or more carboxyl groups and one or more
reactive functional groups in the molecule by using the
same reaction as the reaction utilized in the preparation
of the compound (A). The compound (D) can also be prepared
2 3

20~0167
by copolymerization of an unsa-turated compound having the
functional group of formula [2] with an unsaturated
compound having the reactive functional group.
The compound (D) comprises the functional group of
formula [2] and, furthermore, may comprise two or more
kinds of the reactive functional groups in the same
molecule. However, when the two or more kinds of the
functional groups are reactive between each other, the
storage stability of the thermosetting composition is
damaged and the utilization of such combination of the
functional groups is not desirable.
In the thermosetting composition of the invention, it
is preferable that at least one of the compounds (A) and/or
the compound (B) or at least one of the compound (D) and
the compound (A) and/or the compound (B) which are utilized
optionally is polymer of a,~-unsaturated compound or
polyester resin. It is also preferable that equivalent
ratio of the functional group of formula [1] or formula ~2]
and the reactive functional group to form chemical bond
with the former functional group by heating utilized in the
thermosetting composition is adjusted in the range from
0.2:1.0 to 1.0:0.2.
The functional groups of formulas [1], [2~ and [31 of
the compound (A) and the compound (D) regenerate free
2 4

20~0167
carboxyl group under the heating condition and form
chemical bonding with the reactive functional groups in the
compound (B) and the compound (D). It is also possible
that the functional groups have addition reactions with the
reactive functional groups of the compound (B) and the
compound (D) by acting as an active ester caused by the
polarized structure within the molecule. When the reaction
of this kind takes place, the crosslinking reaction is not
accompanied with any component leaving from the reacting
system and the reaction system can contribute to the
decrease of formation of volatile organic compounds.
In the present invention, a thermal latent acid
catalyst (C) which shows activity in the curing condition
at an elevated temperature may be optionally comprised in
the thermosetting composition for the purpose of keeping
excellent storage stability of the composition for a long
period of time, promoting the -curing reaction when the
composition is cured in a short time at a rather low
temperature and giving excellent chemical properties and
physical properties to the cured products. It is
preferable that the thermal latent acid catalyst is a
compound which exhibit the activity at the temperature
above 60~. If the thermal latent acid catalyst shows the
catalytic activity under 60~, the prepared thermosetting
2 5

20~0167
-
composition has undesirable properties, such as increase of
viscosity during storage and formation of gel.
Preferred examples of the thermal latent acid catalyst
are compounds prepared by neutralizing a protonic acid with
a Lewis base, compounds prepared by neutralizing a Lewis
acid with a Lewis base or by mixing a Lewis acid with
trialkyl phosphate, esters of sulfonic acids, esters of
phosphoric acids and onium compounds.
Examples of the compound prepared by neutralizing a
protonic acid with a Lewis base are: compounds prepared by
neutralizing halogenocarboxylic acids, sulfonic acids,
monoesters of sulfuric acid, monoesters of phosphoric acid,
diesters of phosphoric acid, esters of polyphosphoric acid,
monoesters of boric acid, diesters of boric acid and the
like compounds with ammonia, monoethylamine, triethylamine,
pyridine, piperidine, aniline, morpholine, cyclohexylamine,
n-butylamine, monoethanolamine, diethanolamine,
triethanolamine and the like other amine compounds,
trialkylphosphine, -triarylphosphine, trialkyl phosphite,
triaryl phosphite, commercial acid-base blocked catalysts,
such as Nacure 2500X~, X-47-110~, 3525K and 5225~
(products of King Industries Co., Ltd.) and other like
compounds.
Examples of the compounds prepared by neutralizing a
2 6

20~0167
Lewis acid with a Lewis base are compounds prepared by
neutralizing BF3, FeCl3, SnCl~, AlCl3, ZnCl2 and other like
Lewis acids with bases described above or by mixing Lewis
acid with trialkyl phosphate.
The esters of sulfonic acids are compounds having the
formula ~6]:
o
Rl5_S_O_R16
O ~6]
wherein Rl5 is selected from the group consisting of phenyl
group, substituted phenyl group, naphthyl group,
substituted naphthyl group and alkyl group and R' 6 iS a
group of 3 to 18 carbon atoms selected from the group
consisting of alkyl group, alkenyl group, aryl group,
alkaryl group, alkanol group and saturated or unsaturated
cycloalkyl or hydrocycloalkyl group which is bonded with
sulfonyloxy group through a primary or secondary carbon
atom. Examples of the ester of sulfonic acid are esters of
a sulfonic acid, such as methane sulfonic acid, ethane
sulfonic acid, benzene sulfonic acid, dodecylbenzene
sulfonic acid, naphthalene sulfonic acid, nonylnaphthalene
sulfonic acid and other like sulfonic acids, with a primary
alcohol, such as n-propanol, n-butanol, n-hexanol,
n-octanol and the like, or a secondary alcohols, such as

20~0167
isopropanol, 2-butanol, 2-hexanol, 2-octanol, cyclohexanol
and the like, and ~--hydroxyalkylsulfonic esters prepared by
the reaction of the sulfonic acids and compounds containing
oxirane.
The esters of phosphoric acid are, for example,
compounds having the formula [7]:
o
( R l 7 - O - ) m - P - ( O H ) 3 m [73
wherein Rl7 is a group of 3 to 10 carbon atoms selected
from the group consisting of alkyl group, cycloalkyl group
and aryl group and m is 1 or 2. ~xamples of the ester of
phosphoric acid are monoesters and diesters of phosphoric
acid with a primary alcohol, such as n-propanol, n-butanol,
n-hexanol, n-octanol, 2-ethylhexanol and the like, or a
secondary alcohol, such as isopropanol, 2-butanol,
2-hexanol, 2-octanol, cyclohexanol and the like.
The onium compound is a compound having one of the
general formulas [8] through C11]:
[R'33NR'9]+X- [83
[R'33PRI9]+X- [~]
[R'370Rl9]+X- [103
and
[Rl32SRI9]+X- [11]
wherein Rl3 is a group of 1 -to 12 carbon atoms selected
2 8

20~0167
from the group consisting of alkyl group, alkenyl group,
aryl group, alkaryl group, alkanol group and cycloalk.yl
group, two R' 8 may be bonded together to form a
heterocyclic ring in which N, P, 0 or S is the hetero atom,
R'9 is a hydrogen atom or a group of 1 to 12 carbon atoms
selected from the group consisting of alkyl group, alkenyl
group, aryl group and alkaryl group and X- is selected from
the group consisting of SbF6-, AsF6-, PF6- and BF4 .
In the thermosetting composition of the invention,
either a single kind of the thermal latent acid catalyst
(C) or a combination of two or more kinds may be utilized.
The amount utilized is usually in the range from 0.01 to 10
weight parts per 100 weight parts of the total solid
component which consists of the compound (A) and the
compound (B) or compound (D) and optionally utilized
compound (A) and/or compound (B).
Time and temperature required to cure the thermosetting
composition of the invention is different depending on
temperature at which free carboxyl group is regenerated
from the blocked functional group of formula [11 or formula
[2], kind of the reactive functional group and kind of the
thermal latent acid catalyst. In general, curing is
completed by heating at the temperature in the range from
50 to 200~ for the time in the range from 2 minutes to 10
2 9

20~0167
hours.
The thermosetting composition of the invention can be
utilized for coating compositions. ink, adhesive, molded
plastics and the like without other ingredients and,
according to the needs, it may be compounded with coloring
pigments, fillers, solvents, ultraviolet adsorbents,
al~tioxidants and other ingredients.
The present invention also provides the novel thermal
latent carboxyl compound and the novel method of
preparation thereof along with the thermosetting
composition described above. The thermal latent carboxyl
compound is a compound which is prepared by the reaction of
a polycarboxylic acid having two or more carboxyl groups in
the molecule, acid equivalent of not more than lOOOg/mole
and number average molecular weight of not more than 4000,
preferably not more than 2000, with a vinyl ether compound,
a vinyl thioether compound or a cyclic vinylether compound,
such as a heterocyclic compound having vinyl type double
bond and an oxygen atom or a sulfur atom as the hetero
atom, having the formula [12]:
Rl~ R9
C=C-Y3-R~ 2
Rll [12]
h i R9 Rl~ Rll Rl2 and Y3 are alreadY defined before,
3 O

20~0167
in the presence of acid catalyst at the temperature of
preferably in the range from the room temperature and 100~.
The carboxyl group is converted by the reaction to a
blocked carboxyl group having the formula [3]:
R9
-C-O-C-Y3-RlZ
Il l
O HC-RI 1
Rl~ [3]
wherein R~, Rl~, Rll, Rl2 and Y3 are already defined before.
When the number of carboxyl group in the molecule of
polycarboxyl compound utilized for the preparation of the
thermal latent carboxyl compound is less than two or when
the acid equivalent of the polycarboxyl compound is more
than lOOOg/mole, curing of the prepared thermosetting
composition may not proceed to a sufficient degree. When
the number average molecular weight of the polycarboxyl
compound is more than 4000, viscosity of the thermosetting
composition becomes high and processability is inferior.
The polycarboxyl compound is prepared by (1)
half-esterification of a polyol having two or more hydroxyl
groups in the molecule with an acid anhydride; (2) addition
of a polyisocyanate compound having two or more isocyanate
groups in the molecule with a hydroxycarboxylic acid or an
amino acid; (3) homopolymerization o-f a,~-unsaturated
3 1

2040167
monomer having carboxyl group in it or copolymerization of
the a,~-unsaturated monomer with o-ther ~,~-unsaturated
monomers; (4) preparation of polyester resin having
carboxyi group and other like methods.
Examples of the materia~s utilized for the method
mentioned above are the same as the examples of the
materials utilized for the preparation of the compound
comprising two or more carboxyl groups which is the
material for the preparation of compound (A).
Examples of the vinyl ether compound, the vinyl
thioether compound or the cyclic vinylether compound, such
as a heterocyclic compound having vinyl type double bond
and an oxygen atom or a sulfur atom as the hetero atom,
having the formula [12] are the same as the examples of the
compound of formula [4] which is utilized for the
preparation of the compound (A).
The potentially reactive carboxyl compound can be
advantageously utilized as the compound (A).
The invention will be understood more readily with
reference to the following examples; however these examples
are intended to illustrate the invention and are not to be
construed to limit the scope of the invention.
Properties of the coated film were evaluated by the

2041)167
following methods.
(1) Resistance to acid-1
On a test piece, 2 ml of 40 weight % sulfuric acid was
applied as spots and condition of the coated film was
observed by visual comparison after standing for 48 hour at
20~.
(2) Resistance to acid-2
On a test piece, 2 ml of 40 weight ~ sulfuric acid was
applied as spots and condition of the coated film was
observed by visual comparison after heating for 30 minutes
at 60~.
(3) Resistance to acid-3
A test piece was dipped in O.lN sulfuric acid and the
condition of coated film was observed by visual comparison
after standing for 24 hours at 60~.
(4) Impact resistance
By using an impact tester (Japanese Industrial Standard
K--5400 (1979), method of 6.13.3 B), ~ test piece was
clamped to an impact frame of 6.35 mm .adius and a weight
of 500 g was dropped from the height of 40 cm on the test
piece. Damage made on the coating film was observed by
visual comparison.
(5) Weathering resistance
By using a sunshine weathermeter (.Japanese Industrial
3 3

20~0167
Standard B-7753), a test piece was exposed for 1000 hours
or 3000 hours and 60 degree specular gloss (Japanese
Industrial Standard K-5400 (1979) 6.7 60 degree specular
gloss) of the coating film was measured. Condition of the
coating film was observed by visual comparison or compared
with the condition before the exposure by using the
measured values of gloss.
(6) Knoop hardness
Measurement was made by using M type
micro-hardnessmeter (manufactured by Shimazu Seisakusho,
Ltd.) at 20~. A larger value shows a higher hardness.
(7) Non-volatile matter
Non-volatile matter was measured by treating the sample
in vacuo of 0.1 mmHg at 50~ for 3 hours.
(8) Gardener viscosity
Gardener viscosity was measured by the method of
Japanese Industrial Standard K-5400 (1979) 4.2.2 (bubble
tube viscometer).
Abbreviations and trade names used in the examples are
listed in the following.
AIBN: 2,2'-azo-bis-isobutyronitrile
BMA: n-butyl methacrylate
EMA: 2-ethylhexyl acrylate
GMA: glycidyl methacrylate
3 4

20~0167
I~M: isocyanatoethyl methacrylate
MMA: methyl methacrylate
PMA: methacrylate containing vinyl ether group prepared
by the following method: In a flask equipped with a
stopper, a mixture of 130 weight parts of 2-hydroxyethyl
methacrylate, 224 weight parts of 3,4-dihydro-2H-yl-
methyl-3,4-dihydro-2H-pyran-2-carboxylate and 0.3 weight
part of dodecylbenzene sulfonic acid was stirred for 24
hours at the room temperature.
TMSPMA: methacryloyloxypropyltrimethoxysilane
PTSA: p-toluene sulfonic acid
DDBSA: dodecylbenzene sulfonic acid
10% PTSA: l0 weight % solution of p--toluene sulfonic
acid in isopropyl alcohol.
10% pyridine: 10 weight % so;ution of pyridine in
xylene.
Acid catalyst A: xylene solution of (1-methylethyl)
p-toluene sulfonate in Example of preparation of material
14.
Acid catalyst B: xylene solution of (1-methylheptyl)
p-toluene sulfonate in Example of preparation of material
Acid catalyst C: xylene solution of (1-methylethyl)
p-toluene sulfonate in Example of preparation of material
3 5

20~0167
16.
Acid catalyst D: 10 weight % solution in isobutanol of
di-2-ethylhexyl phosphate (a product of Wako Junyaku Co.,
Ltd.).
Acid catalyst E: a 10 weight % solution in
dimethylsufoxide of triethylamine salt of %inc chloride.
Acid cata]yst F: a 50 weight % solution in
dichloroethane of 3--methyl-2-butinyltetramethylenesulfonium
hexafluoroantimonate.
Acid catalyst G: a 20 weight % solution in
acetone of 4-methoxybenz,ylpyridinium hexafluoroantimonate.
Compound B-8 was prepared from a mixture of monomers
co~prising 28.4 weight % of glycidyl methacrylate, 13.0
weight % of hydroxyethyl methacrylate, 10.0 weight % of
butyl methacrylate, 24.7 weight % of methyl methacrylate
and 23.9 weight % of 2-ethylhexyl acrylate by the same
method as compound B-1 in Example of preparation of
material 5 and had 50 weight % of non-volatile matter and
Gardener viscosity W.
Compound B-9 was prepared from a mixture of monomers
comprising 28.4 weight % of glycidyl methacrylate, 8.3
weight % of methacryloyloxypropyltrimethoxysilane, 20.0
weight % of butyl methacrylate, 27.7 weight % of methyl
methacrylate and 15.6 weight % of 2-ethylhexyl acr~rlate by
3 6

~0~0167
the same method as the compound B-1 in Example of
preparation of material 5 and had 50 weight % of
non-volatile matter and Gardener viscosity U.
C-1203~: Vesturit Catalyst 1203, a product of Impecs
Chemicals Co., Ltd., nonionic thermal latent acid catalyst,
non-volatile matter 50 weight ~.
Chemitite pz-336 a product of Nippon Shokubai Kagaku
Kogyo Co., Ltd., polyaziridine, content of aziridine
6.2mole/kg.
Coronate EH6: a product of Nippon Polyurethane Industry
Co., Ltd., trimer of hexamethylene diisocyanate, content of
isocyanate 21 weight %.
Coronate 2513~: a product of Nippon Polyurethane
Industry Co., Ltd. (blocked polyisocynate of no yellowing,
low temperature dissociation type, non-volatile matter 80
weight %, isocyanate content lO.2 weight %).
Cymel 303~: a product of Mitsui Cyanamide Co., Ltd.,
methylated melamine resin, non--volatile matter 98 weight %.
Denacol LX-4216: a product of Nagase Kasei Kogyo Co.,
Ltd., a polyepoxy compound having epoxy equivalent of 155.
Flexorez UD 320~: a product of King Co., Ltd., urethane
diol, non-volatile matter 97.5 weight %, hydroxyl value 350.
K-Flex 188-50~: a product of King Co., Ltd., polyester
diol, non-volatile matter 96 wcight %, hydroxyl value 235.
3 7

- 2040167
KR-214~: a product of Shinetsu Chemical Co.,Ltd.,
silicone vanish, hydroxyl equivalent 490, non-volatile
matter 70 weight %.
MAGME: MAGME 100~, a product of Mitsui Cyanamide Co.,
Ltd., methylacrylamide glycolate methyl ether
Modaflow6: a product of Monsanto Co., a leveling agent.
NZ-11: Chemitite MZ~ , a product of Nippon Shokubai
Kagaku Kogyo Co., Ltd., 2-(1-aziridinyl)ethyl methacrylate
Praccel E-488~: a product of Daicel Chemical
Industries Co., Ltd., caprolactone polyol, hydroxyl value
579.
Silicone KR-213~: a product of Shinetsu Chemical
Co., Ltd., a methoxysilicone compound, methoxy group
equivalent 160.
Titanium dioxide JR--602~: a product of Teikoku Kako Co.,
Ltd., titanium dioxide of rutile type.
Example of preparation of material 1-3
Three kinds of the compound (A), A-1, A-2 and A-3, were
prepared.
(1) Preparation of ~ unsaturated compound
A mixture shown in Table 1 was charged into a
four-necked flask which is equipped with a thermometer, a
reflux condenser and a stirrer and stirred at 50~. The

2040167
reaction was finished when the acid value of the mixture
decreased to a value less than 30 and the reaction mixture
was transferred to a separating funnel after cooling by
standing. The reaction mixture was washed with 100 weight
part of alkaline water containing 10 weight ~ of sodium
bicarbonate in the funnel and then washed with 200 weigh
parts of deionized water repeatedly until the pH of the
washing water became below 7. The organic layer was dried
by adding Nolecular Sieve 4Al/16 (a product of Wako Junyaku
Co., Ltd.) and standing for 3 days at the room temperature.
The a,~-unsaturated compounds obtained by this process,
A-l(a), A-2(a) and A-3(a), contained effective components
in the amount shown in Table 1. The content of the
effective components were determined by gas chromatography.
(2) Preparation of compounds A-l, A-2 and A-3
Into a four-necked flask equipped with a thermometer, a
reflux condenser, a stirrer and a dropping funnel, an
initial portion of solvent which was xylene was charged in
an amount shown in Table 2, heated under stirring and kept
at 80~. A mixture of monomers and a polymerization
initiator shown in Table 2 ('component of dropped mixture')
was added by dropping to the solvent at 80~ at a constant
rate for 2 hours. When the addition of the dropping
component was finished, the mixture was kept at 80~ for
3 9

20~0167
further 1 hour and, then, an additional amount of initiator
solution shown in Table 2 ('additional catalyst') was added
to the mixture. The mixture was kept at 80~ for 4 hours
before finishing the reaction and finally the compounds
A-l, A-2 and A-3 having the properties shown in Table 2
were obtained.
Example of preparation of material 4
One kind of the compound (A), A-4, was prepared.
(1) Preparation of polycarboxylic acid
Into a four-necked flask equipped with a thermometer, a
reflux condenser, a stirrer and a dropping funnel, the
following components were charged and the mixture was
heated under stirring until the temperature reached to
120~.
pentaerythritol 136.0 weight parts
methyl isobutyl ketone 538.7 weight parts
To the mixture kept at 120~, 67~.0 weight parts of
methylhexahydrophthalic anhydride was added by dropping for
2 hours and the mixture was kept stirring under heating
until acid value of the mixture decreased to a value not
more than 170. The acid value was measured by diluting the
sample 50 times by weight with a mixture of pyridine and
water (pyridine/water 9/1 by weight), heating for 30
4 0

20~0167
minutes at 90~ and titrating with a standard solution of
potassium hydroxide. Thus, a solution of a tetrafunctional
polycarboxyl compound was prepared.
(2) Preparation of compound A-~
Into a flask of the same kind as the above, a mixture
of the following composition including the solution of the
polycarboxyl compound prepared above was charged and kept
stirring at 50~.
the solution of polycarboxyl compound of (1) 336.7
isobutyl vinyl ether 120.2
hydrochloric acid, 35 weight % 0.2
methyl isobutyl hetone 46.3
(quantity in weight parts)
The reaction was finished when acid value of the mixture
decreased to a value not more than 12 and the mixture was
transferred to a separating funnel after cooling by
standing. The reaction mixture was washed with 100 weight
parts of alkaline water containing 10 weight ~ of sodium
bicarbonate in the funnel and then washed with 300 weight
parts of deionized water repeatedly until the pH of the
washing water became below 7. The organic layer was dried
by adding Nolecular Sieve 4A1/16 (a product of Wako Junyaku
Co., Ltd.) and standing for 3 days at the room temperature.
The solution of the compound A-4 thus prepared had 60
41

20~0167
weight % of non--volatile matter and Gardener viscosity of
E-E at 25~.
Example of preparation of material 5 through 10
Six kinds of the compound (B), compounds B-1 through
B-6, were prepared by the following method.
Into a four-necked flask equipped with a thermometer, a
reflux condenser, a stirrer and a dropping funnel, 40.0
weight parts of solvent which was xylene was charged,
heated under stirring and kept at 100~. A mixture of
monomers and a polymerization initiator shown in Table 3
('component of dropped mixture') was added by dropping to
the solvcnt at 100~ at a constant rate for 2 hours. When
the addition of the dropping component was finished, the
mixture was kept at 100~ for further 1 hour and, then, an
additional amount of initiator solution shown in Table 3
('additional catalyst') was added to the mixture. The
mixture was kept at 100~ for 2 hours before finishing the
reaction and finally the compounds B-1 through B-6 having
the characteristics shown in Table 3 were obtained.
Example of preparation of material 11
One kind of compound (B), compound B-7, was prepared by
the following method.
4 2

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Into a four-necked flask equipped with a thermometer, a
reflux condenser, a stirrer and a dropping funnel, 206.
weight parts of methyl orthoformate and 0.3 weight part of
boron trifluoride diethyl etherate were charged and the
mixture was kept at 0-5~ by stirring under cooling by ice.
To the mixture, 87.7 weight parts of butyl vinyl ether were
added by dropping from a dropping funnel at a constant rate
for 2 hours while temperature of the mixture was kept below
5~. The mixture was kept below 5~ for further 1 hour after
finishing the dropping and, then, 0.4 weight parts of 30
weight % methanol solution of sodium methylate were added
to the mixture to flnish the reaction. The acetal product
obtained by distillation of the reaction product at 75-80
(4 mmHg) contained 98 weight % of the effective component.
Into a four-necked flask equipped with a thermometer, a
reflux condenser inserted with a Dienstag trap, a stirrer
and a dropping funnel, 618 weight parts of the purified
acetal product, 134 weight parts Gf trimethylolpropane and
4 weight parts of p-toluene sulfonic acid were charged and
the mixture was kept at 90~ by stirring under heating.
Methanol was continuously removed while the reaction
proceeded. When 96 weight parts of methanol were
recovered, the reaction was finished and compound B-7 was
obtained.
4 3

- 2040167
~xample of preparation of material 12 and 13
Two kinds of compound (D), compounds D-1 and D--2, were
prepared by the following method.
Into a four-necked flask equipped with a thermometer, a
reflux condenser, a stirrer and a dropping funnel, an
initial portion of solvent which was xylene was charged in
an amount shown in Table 4, heated under stirring and kept
at 80~. A mixture of monomers and a polymerization
initiator shown in Table 4 ('component of dropped mixture')
was added by dropping to the solvent at 80~ at a constant
rate for 2 hours. When the addition of the dropping
component was finished, the mixture was kept at 80~ for
further 1 hour and, then, an additional amount of initiator
solution shown in Table 4 ('additional catalyst') was added
to the mixture. The mixture was kept at 80~ for 4 hours
before finishing the reaction and finally the compounds D-1
and D-2 having the properties shown in Table 4 were
obtained.
~xample of preparation of material 14
Thermal latent acid catalyst (C) was prepared by the
following method.
Into a flask equipped with a stirrer, a thermometer, a
dropping funnel and a reflux condenser, 315 weight parts of
4 4

2040167
2-propanol were charged and the flask was cooled by an ice
bath. Potassium t-butoxide, 44.9 weight parts, was added
to 2-propanol to disso~ved in it and a solution of 53.4
weight parts of p-toluene sulfonyl chloride in 300 weight
parts of diethyl ether was added to the solution by
dropping in 30 minutes. After one hour, the ice bath was
removed from the flask and the reaction was continued for
further 1 hour. After the reaction was finished, the
reaction mixture was washed with 300 weight parts of water
three times and dried with Molecular Sieve 4A1/16 (a
product of Wako Junyaku Co., Ltd.). After removing the
solvent by using an evaporater, 40 weight parts of
1--methylethyl p-toluenesulfonate were obtained (yield 67%).
The thermal latent acid catalyst thus prepared was
dissolved in 238 weight parts of xylene to form a solution
of 10 weight % based on p-toluene sulfonic acid.
Example of preparation of 15 and 16
In Example of preparation of material 15, 2-octanol was
used in place of 2-propanol in Example of preparation of
material 14. In Example of preparation of material 16,
dodecylbenzene sulfonyl chloride was used in place of
p-toluene sulfonyl chloride in Example of preparation of
material 14. Other procedures were made in the same way as
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20~0167
Example of preparation of material 14. In Example of
preparation of material 15, l-methylheptyl
p-toluenesulfonate was obtained in the yield of 72% and, in
Example of preparation of material 16, l-methylethyl
dodecylbenzene sulfonate was obtained in the yield of 83%.
The thermal latent acid catalysts thus prepared were
dissolved in xylene to form a solution of 10 weight % based
on p-toluene sulfonic acid and dodecylbenzene sulfonic acid
in the same way as Example of preparation of material 14.
Preparation of thermal latent polycarboxyl compounds
are shown in Rxamples 1 through 8.
~xample 1
(1) Preparation of polycarboxyl compound
Into a flask equipped with a thermometer, a reflux
condenser and a stirrer, 134.0 weight parts of
trimethylolpropane, 462.0 weight parts of hexahydrophthalic
anhydride and 149.0 weight parts of methyl isobutyl ketone
were charged and the mixture was heated with stirring to
the refluxing temperature for 6 hours. The mixture was
kept stirring under heating until acid value of the mixture
decreased to a value not more than 226 and a solution of a
polycarboxyl compound was prepared. The acid value was
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measured by diluting the sample 5n times by weigh-t with a
mixture of pyridine and water (pyridine/water 9/1 by
weight), heating for 30 minutes at 90~ and titrating with a
standard solution of potassium hydroxide.
(2) Preparation of thermal latent carboxyl compound
Into a flask of the same kind as the above, a mixture
of the following composition ;ncluding the solution of the
polycarboxyl compound prepared above was charged and kept
stirring at the rnom temperature.
the solution of polycarboxyl coMpound of (1) 248.3
ethyl vinyl ether 108.0
monooctyl phosphate 0.6
xylene 76.4
(quantity in weight parts)
The reaction was finished when acid value of the mixture
decreased to a value not more than 3 and 10 weight parts of
Kyowaad 500~ (a synthetic acid adsorbent, a product of
Kyowa Chemical Industry Co., Ltd.) was added to the
reaction mixture. The mixture was stirred for 48 hours at
the room temperature and filtered. After 36.0 weight parts
of the solvent were removed from the filtrate by using an
evaporater, a solution of the thermal latent carboxyl
compound [l] having 50 weight % of effective component and
Gardener viscosity of F-G was obtained
4 7

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Examples 2, 3 and 4
(1) Preparation of polycarboxyl compound
Into a flask similar to the flask in Example 1 (1), a
mixture having the composition shown in Table 5 was charged
and treated in the same way as in Example 1 (1). Heating
under stirring was made until ac;d value of the mixture
deceased to 170 in Example 2, to 117 in Example 3 and to
145 in ~xample 4 and a solution of polycarboxyl compound
was prepared in each example.
(2) Preparation of thermal latent carboxyl compound
Mixtures having the compositions shown in Table 6 were
treated in the same way as in Example 1 (2) and solutions
of thermal latent carboxyl compollnds [2], [3] and [4] having
properties shown in Table 6 were prepared.
Example 5
(1) Preparation of polycarboxyl compound
Into a four-necked flask equipped with a thermometer, a
reflux condenser fitted with a Dienstag trap and a stirrer,
480.0 weight parts of Silicone KR-213~, 312.0 weight parts
of neopentyl glycol and 0.8 weight part of p-toluene
sulfonic acid were charged and the mixture was heated to
160~ under stirring and kept at the temperature. When the
reaction started, the reaction was kept going by
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- 2010167
elimination of methanol above 140~ until 96 weight parts of
methanol were recovered. Then, Dienstag trap was removed
and 462.0 weight parts of hexahydrophthalic anhydride and
288.7 weight parts of methyl isobutyl ketone were added to
the flask. In the procedures similar to the one in Example
1 (1), heating under stirring was continued until acid
value of the mixture decreased to a value not more than 117
to obtain a solution of polycarboxyl compound.
(2) Preparation of thermal latent carboxyl compound
A mixture having the following composition was treated
by the same procedure as in Example 1 (2). ~hen 43 weight
parts of solvent were removed by an evaporater, a solution
of thermal latent carboxyl compound [5] having 50 weight %
of effective component and ~ardener viscosity J-K was
prepared.
the solution of polycarboxyl compound of (1) 479.6
n-propyl vinyl ether 129.0
monooctyl phosphate 1.2
xylene 200.6
(quantity in weight parts)
Example 6
(1) Preparation of polycarboxyl compound
Into a flask similar to the one in Example 1 (1), 200.0
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20gO167
weight parts of Coronate EH~, 300.0 weight parts
of 12-hydroxystearic acid and 125 weight parts of butyl
acetate were charged and the mixture was kept at 100~ under
stirring. The reaction was finished when the content of
isocyanate in the mixture decreased to not more than 0.1
weight % and a solution of polycarboxyl compound was
prepared.
(2) Preparation of thermal latent carboxyl compound
A mixture having the following composition was treated
by the same procedure as in Example 1 (2). ~hen 43 weight
parts of solvent were removed by an evaporater, a solution
of thermal latent carboxyl compound [6] having 50 weight %
of effective component and Gardener viscosity L-M was
prepared.
the solution of polycarboxyl compound of (1) 625.0
n--propyl vinyl ether129.0
monooctyl phosphate1.5
xylene 287.5
(quantity in weight parts)
Example 7
(1) Preparation of polycarboxyl compound
Into a flask similar to the one in Example 1(1), 200.0
weight parts of Coronate EH~, 75.1 weight parts of
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2040167
glycine and 68.8 weight parts of N-methylpyrrolidone were
charged. A solution of polycarboxyl compound was prepared
by the same method as in Example 6 (1)
(2) Preparation of thermal latent carboxyl compound
A mixture having the following composition was treated
by the same procedure as in Example 1 (2). When 42 weight
parts of solvent were removed by an evaporater, a solution
of thermal latent carboxyl compound [7] having 50 weight %
of effective component and Gardener viscosity S-T was
prepared.
the solution of polycarboxyl compound of (1) 343.9
3,4-dihydro-2H-pyran 126.0
monooctyl phosphate 0.8
methyl isobutyl ketone 121.5
(quantity in weight parts)
Example 8
(1) Preparation of ~,a-unsaturated compound
Into a flask similar to the one in Example 1 (1), 86.0
weight parts of methacrylic acid, 100.9 weight parts of
3,4-dihydro-2H-pyran, 0.2 weight part of hydroquinone
monomethylether and 0.1 weight part of 35 weight %
hydrochloric acid were charged and the mixture was kept at
50~ under stirring. The reaction was finished when acid

20401t~7
.
value of the mixture decreased to a value not more than 30
and the reaction product was transferred to a separating
funnel after cooling. The reaction product in the
separating funnel was washed with ]00 weight parts of 10
weight % aqeous solution of sodium bicarbonate and then
with 200 weight parts of deionized water repeatedly until
pH of the washing liquid decreased to not more than 7.
Molecular Sieve 4Al/16 (a product of Wako Junyaku Co.,
-Ltd.) was added to the organic layer and dried for 3 days
at the room temperature to obtain a,~-unsaturated
compound containing 95.1 weight % of effective component.
(2) Preparation of thermal latent carboxyl compound
~ nto a four-necked flask equipped with a thermometer, a
ref]ux condenser, a stirrer and a dropping funnel, 200
weight parts of xylene were charged, heated and kept at 100~
under stirring. Then, a mixture of the following
composition was added by dropping at a constant rate in 2
hours while the temperature was kept at 100~. When the
dropping was finished, the mixture was kept at 100~ for
further 30 minutes and then a solution in which 3.0 weight
parts of 2,2'-azo-bis-isobutyronitrile was dissolved in
57.0 weight parts of n-butyl acetate was added to the
mixture. The reaction was finished after the reaction
mixture was kept at 100~ for 2 hours and thermal latent
5 2

20~0167
carboxyl compound [8] having 50 weight % of effective
component and Gardener viscosity 0-P was prepared.
the ~ unsaturated compound of (1) 178.8
n--butyl methacrylate 100.0
methyl methacrylate 178.6
2-ethylhexyl acrylate 135.4
n-butyl acetate 115.0
2,2'-azo-bis-isobutyronitrile 32.2
(quantity in weight parts)
Results of Examples 1 through 8 are summarized in Table
Comparative example of preparation of material 1
Compound A-5 was prepared by the following method.
~ nto a four-necked flask equipped with a thermometer, a
reflux condenser, a stirrer and a dropping funnel, 200
weight parts of xylene were charged, heated and kept at 80~
under stirring. Then, a mixture of the following
components were added from the dropping funnel by dropping
at a constant rate in 2 hours while the temperature was
kept at 80~.
t-butyl methacrylate 142.0 weight parts
n-butyl methacrylate 100.0 weight parts
methyl methacrylate 178.6 weight parts
5 3

20~G167
2-ethylhexyl acrylate 105.~ weight parts
n-butyl acetate 192.2 weight parts
2,2'-azo-bis-isobutyronitrile 21.8 weight parts
After the dropping was finished, the reaction mixture was
kept at 80~ for further 1 hour and 57.0 weight parts of
n-butyl acetate and 3.0 weight parts of 2,2'-azo-bis-
isobutyronitrile were added. When the mixture was kept at
80~ for 4 hours, compound A-5 having 52.8 weight % of
non-volatile matter and Gardener viscosity S-T.
Examples 9 through 19
These examples show application of the composition to
one coat solid color coating.
(1) Preparation of coating composit;ons
Components summarized in Table 8 were utilized for the
preparation of the coating compositions. A part of or all
materials were charged into a sand mill and dispersed until
the particle size decreased to not more than 10~m.
Materials excluding following components were charged into
the sand mill: Denacol EX-421~ in Example 9, the compound
B-2 in Example 10, Chemitite PZ-33~ in Example 11, the
compound A-4 in Example 12, Coronate EH~ in Example 13,
Cymel 303~ in Example 14, the compound B-1 in Example 15,
KR-214~ in Example 16, the compound B-7 in Example 17
5 4

20~0167
and Cymel 303~ in ~xample 19. All the raw materials were
charged into the sand mill in Fxample 18. In ~xamples 9
through 17 and ~xample 19, one component coating
compositions were prepared by adding the materials which
were not treated by the sand mill to the materials treated
by the sand mill. In Example 18, the materials treated by
the sand mill were utilized for the preparation of one
component coating compositions. The coating compositions
prepared were diluted by a thinner (a mixture of xylene and
butyl acetate in 8 to 2 weight ratio) to the viscosity of 1
poise (measured by Brookfield type viscometer at 20~) and
stored in a sealed condition at 50~. After the coating
compositions were stored for 30 days at 50~, viscosity was
measured. The results summarized ;n Table 9 show that the
increase of viscosity was very slight in all cases and that
the coating compositions had excellent storage stability.
(2) Preparation of test piece
Cationic electro coating paint AQUA No.4200~ (a
product of Nippon Oil and Fats Co., Ltd.) was applied by
electrodeposition to a soft steel plate treated with zinc
phosphate in an amount to ~orm a film having dried
thickness of 20~m and the coated plate was baked at 175
for 25 minutes. Intermediate coating paint ~PICO No.
1500CP Sealer~ (a product of Nippon Oil and Fats Co.,
5 5

20~0167
Ltd.) was applied to the prepared plate by air spraying in
an amount to form a film having dried thickness of 40~m and
the plate was baked at 140~ for 30 minutes to obtain a base
test piece.
The raw coating compositions prepared in (1) were
diluted with thinner (a mixture of xylene and butyl acetate
in 8 to 2 ratio) to a viscosity required for spraying (25
seconds at 20~ by Ford cup No. 4) and applied to the base
test piece prepared before by air spray coating. Test
pieces were prepared by curing the coated pieces in the
conditions shown in Table 9.
Results of the evaluation of coatings are shown in
Table 9. In all cases, uniform coating having good gloss
were prepared. All the coatings showed excellent acid
resistance, impact resistance, weathering resistance and
hardness when they were cured at 140~.
Weathering resistance was evaluated by exposure for
1000 hours.
Comparative examples 1 and 2
Components listed in Table 10 were utilized for the
preparation of the coating compositions. The components
were dispersed and made into coating compositions by the
same method as in Fxamples 9 through 19. The materials
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20~0167
excluding Denacol EX-421~ in Comparative example 1 and the
materials excluding polycarboxylic acid of Example of
preparation of material A-4 (a) in Comparative example 2
were dispersed by using a sand mill and utilized for
preparation of coating compositions.
The coating compositions thus prepared were evaluated
on the storage stability in the same way as in Examples 9
through 19. In the case of Comparative example 2 shown in
Table 11, viscosity increased remarkably with the period of
storage, leading finally to gellation after 5 days, because
neither carboxyl group or epoxy group was blocked to
prevent crosslinking reaction of the both functional groups
under the storage condition.
Test pieces were prepared by the same method as in
Examples 9 through 19 by using coating compositions
prepared in the present comparative examples and evaluated.
The test piece of Comparative example l which corresponded
to the material disclosed in Japanese Laid-open Patent
Publication Heisei 1-104646 did not give cured film having
satisfactory properties even when it was cured at 140~ but
gave a film having inferior acid resistance, impact
resistance, weathering resistance and hardness as clearly
shown in Table 11.
5 7

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Examples 20 through 23
These examples show application of the composition to
two coat one bake metallic color coating.
(1) Preparation of clear coating
One component clear coating compositions were prepared
by mixing raw materials shown in Table 12. The clear
coating compositions prepared were evaluated on storage
stability by the same method as in Example 9 through 19.
Increase of viscosity was very slight in all cases tested
and the coating compositions were shown to have excellent
storage stability as shown in Table 13.
2) Preparation of test piece
Raw coating compositions thus prepared were diluted in
the same method as in Examples 9 through 19. Base test
pieces were also prepared in the same method as in Examples
9 through 19. A silver metallic base coating composition,
BELCOAT No.6000~ (a product of Nippon 0il and Fats Co.,
Ltd.) was applied to the base test piece by air spraying
with interval of 1 minute 30 secon~s in 2 stages in an
amount to form a film having dried thickness of 15~m.
After the test pieces were set at 20~ for 3 minutes, the
diluted raw clear coating compositions were coated by air
spray coating and the test pieces were cured in the
condition shown in Table 13 to prepare final test pieces.
5 8

2040167
Results of the evaluation listed in Table 13 show that,
in all cases, uniform coatings having good gloss were
prepared and the coating showed excellent acid resistance,
impact resistance, weathering resistance and hardness when
they were cured at 140~.
Weathering resistance was evaluated by exposure for
3000 hours.
Comparative examples 3 and 4
Clear coating compositions were prepared by using raw
materials listed in Table 14 and storage stability was
evaluated in the same method as in Examples 9 through 19.
In the case of Comparative example 4 shown in Table 15,
gellation took place after 5 days because neither carboxyl
group or epoxy group was blocked to prevent the
crosslinking reaction under the storage condition.
Test pieces were prepared by using coating compositions
prepared above and evaluated in the same method as in
Examples 20 through 23. The test piece of Comparative
example 3 which corresponded to the material disclosed in
Japanese Laid-open Patent Publication Heisei 1-104646 did
not give cured film having satisfactory properties even
when it was cure at 140~ but gave a film having inferior
acid resistance, impact resistance, weathering resistance
5 9

2040167
and hardness as clearly shown in Table 15.
Examples 24 through 34
These examples show application of the composition to
one coat solid color coating.
(1) Preparation of coating material
Component,s summarized in Table 16 were utilized for the
preparation of the coating materials. A part of or all
materials were charged into a sand mill and dispersed until
the particle size decreased to not more than 10~m.
Naterials excluding following components were charged into
the sand mill: Denacol EX-421~ in Example 24, the
compound B-2 in Example 25, Chemitite PZ-33~ in Example 26,
the compound A-4 in Example 27, Coronate EN~ in Example 28,
Cymel 303~ in Example 2~, the compound B-1 in Example 30,
KR-214~ in Example 31, the compound B-7 in Example 32 and
Cymel 303~ in Example 34. All the raw materials were
charged into the sand mill in Example 33. In Examples 24
through 32 and Example 34, one component coating
compositions were prepared by adding the materials which
were not treated by the sand mill to the materials treated
by the sand mill. In Example 33, the materials treated by
the sand mill were utilized for the preparation of one
component coating composition. The coating compositions

20~0167
prepared were diluted by thinner (a mixture of xylene and
butyl acetate in 8 to 2 weight ratio) to the viscosity of 1
poise (measured by Brookfield type viscometer at 20~) and
stored in a sealed condition at 50~. After the coating
compositions were stored for 30 days at 50~, viscosity was
measured. The results summarized in Table 17 show that the
increase of viscosity was very slight in all cases and that
the coating materials had excellent storage stability.
(2) Preparation of test piece
Cationic electro coating paint AQUA No.4200~ (a
productof Nippon Oil and Fats Co., Ltd.) was applied by
electrodeposition to a soft steel plate treated with zinc
phosphate in an amount to form a film having dried
thickness of 20&m and the coated plate was baked at 175
for 25 minutes. Intermediate coating paint EPICO No.
1500CP Sealer~ (a product of Nippon Oil and Fats Co.,
Ltd.) was applied to the prepared plate by air spraying in
an amount to form a film having dried thickness of 40&m and
the plate was baked at 140~ for 30 minutes to obtain a base
test piece.
The raw coating materials prepared in (1) were diluted
with thinner (a mixture of xylene and butyl acetate in 8 to
2 ratio) to a viscosity required for spraying (25 seconds
at 20~ by Pord cup No. 4) and applied to the base test
6 1

20~û167
piece prepared before by air spray coating. Test pieces
were prepared by curing the coated pieces in the conditions
shown in Table 17.
Results of the evaluation of coatings are shown in
Table 17. In all cases, uniform coating having good gloss
were prepared. All the coatings showed excellent acid
resistance, impact resistance, weathering resistance and
hardness.
Heathering resistance was evaluated by exposure for
lOOO hours.
Comparative example 5
Components listed in Table 18 were utilized for the
preparation of the coating compositions. The components
were dispersed and made into coating compositions by the
same method as in Examples 24 through 34. The materials
excluding polycarboxylic acid of Example of preparation of
material A-4 (a) were dispersed by llS ing a sand mill and
utilized for preparation of coating compositions.
The coating materials thus prepared were evaluated on
the storage stability in the same way as in Examples 24
through 34. As shown in Table 19, viscosity increased
remarkably with the period of storage, leading finally to
gellation in the fifth daY, because neither carboxyl group
6 2

20~0167
or epoxy group was blocked to prevent crosslinking reaction
of the both functional groups under the storage condition.
~ eathering resistance was evaluated by exposure for
1000 hours.
Examples 35 through 41
These examples show application of the composition to
two coat one bake metallic color coating.
(1) Preparation of clear coating compositions
One component clear coating compositions were prepared
by mixing raw materials shown in Table 20. The clear
coating compositions prepared were evaluated on storage
stability by the same method as in Rxample 24 through 34.
As shown in Table 21, increase of viscosity was very slight
in all cases tested and coating materials were shown to
have excellent storage stability.
2) Preparation of test pieces
Raw coating materials thus prepared were diluted in the
same method as in Examples 24 through 34. Base test pieces
were also prepared in the same method as in Rxamples 24
through 34. A silver metallic base coating composition
BELCOAT No.6000~ (a product of Nippon Oil and Fats Co.,
Ltd.) was applied to the base test piece by air spraying
with interval of 1 minute 30 seconds in 2 stages in an
6 3

2040167
amount to form a film having dried thickness of 15~m.
After the test piece was set at 20~ for 3 minutes, the
diluted raw clear coating compositions were coated by air
spray coating and the test pieces were cured in the
condition shown in Table 21 to prepare final test pieces.
Results of evaluation listed in Table 21 show that, in
all cases, uniform coating films having good gloss were
prepared and the coating showed excellent acid resistance,
impact resistance, weathering resistance and hardness.
Neathering resistance was evaluated by exposure for
3000 hours.
Comparative example 6
Clear coating compositions were prepared by using raw
materials listed in Table 22 and storage stability was
evaluated in the same method as in Rxamples 24 through 34.
As shown in Table 23, in the case of Comparative example 6,
gellation took place after 5 days because neither carboxyl
group or epoxy group was blocked to prevent the
crosslinking reaction under the storage condition.
Weathering resistance was eveluated by exposure for
3000 hours.
Rxample 42 through 50
6 4

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These examples show application of the composition to
two coat one bake metallic color coating.
(1) Preparation of clear coating compositions
One component clear coating compositions were prepared
by mixing raw materials shown in Table 24. The coating
compositions prepared were diluted by thinner (a mixture of
xylene and butyl acetate in 8 to 2 weight ratio) to the
viscosity of 1 poise (measured by Brookfield type
viscometer at 20~) and stored in a sealed condition at 50~.
After the coating compositions were stored for 30 days at
50~, viscosity was measured. The results summarized in
Table 25 show that the increase of viscosity was very
slight in all cases and that the coating compositions had
excellent storage stability.
(2) Preparation of test pieces
Cationic electro coating paint AQUA No.4200~ (a product
of Nippon Oil and Fats Co., Ltd.) was applied by
electrodeposition to a soft steel plate treated with zinc
phosphate in an amount to form a film having dried
thickness of 20~m and the coated p]ate was baked at 175
for 25 minutes. Intermediate coating paint ~PICO No.
1500CP Sealer~ (aproduct of Nippon Oil and Fats Co., Ltd.)
was applied to the prepared plate by air spraying in an
amount to form a film having dried thickness of 40~m and
6 5

2040167
the plate was baked at 140~ for 30 minutes to obtain a base
test piece.
A silver metallic base coating composition BELCOAT
No.6000~ (a product of Nippon Oil and Fats Co., Ltd.) was
applied to the base test piece by air spraying with
interval of 1 minute 30 seconds in 2 stages in an amount to
form a film having dried thickness of 15~m. After the test
pieces were set at 20~ for 3 minutes, the clear coating
compositions prepared in (1) and diluted to a viscosity
required for spraying (25 seconds by ~ord cup No.4 at 20~)
were coated by air spray coating and the test pieces were
cured in the condition shown ;n Table 25 to prepare final
test pieces.
Results of evaluation listed in Table 25 show that, in
all cases, uniform coating fi]ms having good gloss were
prepared and the coating showed excellent acid resistance,
impact resistance, weathering resistance and hardness.
Weathering resistance was evaluated by exposure for
3000 hours.
Comparative example 7
Clear coating composition was prepared from 33.1 weight
parts of solution of polycarboxyl compound prepared in
Example 2 (1), 100 weight parts of compound B-2, 2.0 parts
6 6

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of acid catalyst-B, 0.3 weight part of Modaflow, 100 weight
parts of xylene and 2.0 weight parts of n-butyl acetate and
evaluated on storage stability by the same method as in
Example 42 through SO. The clear coating composition
prepared here gelatinized after 3 days because it did not
comprise thermal latent carboxyl compound unlike the
material in Example 43.
Example 51 through 53
These examples show application of the composition to
two coat one bake metallic color coating.
(1) Preparation of clear coating compositions
One component clear coating compositions were prepared
by mixing the materials shown in Table 26. The coating
compositions prepared were diluted with thinner (a mixture
of xylene and n-butyl acetate in 8/2 ratio) to the
viscosity of 1 poise (measured by Brookfield type
viscometer at 20~) and stored at 50~ in a sealed condition.
After the storage for 30 days at 50~, viscosity of the
compositions was measured again. Results listed in Table
27 show that the increase of viscosity was very slight in
all cases and exhibited excellent stora~e stability of the
coating compositions.
(2) Preparation of test pieces
6 7

2040167
A silver metallic base coating composition BELCOAT
No.6000~ (a product of Nippon Oil and Fats Co., Ltd.) was
applied to the base test piece, which was prepared by the
same method as in Example 9 through 19 (2) and coated with
intermediate coating colnposition, by air spraying with
interval of 1 minute 30 seconds in 2 stages in an amount
to form a film having dried thickness of 15~m. After the
test pieces were set at 20~ for 3 minutes, the diluted raw
clear coating compositions were coated by air spray coating
and the test pieces were cured in the condition shown in
Table 27 to prepare final test pieces.
Results of evaluation listed in Table 27 show that, in
all cases, uniform coating films having good gloss were
prepared and the coating showed excellent acid resistance,
impact resistance, weathering resistance and hardness.
Weathering resistance was evaluated by exposure for
3000 hours.
While the invention has been particularlY shown and
described with reference to preferred embodiments thererof,
it will be understood by those skil]ed in the art that the
foregoing and other changes in form and details can be made
therein without departing from the spirit and scope of the
invention.
6 8

2~40167
To summarize the advantages obtained by the invention,
the thermosetting composition of the invention gives cured
products having excellent chemical properties, physical
properties and weathering resi-stance and is favorably
utilized in coating compositions, ink, adhesive and molded
plastics.
The thermal latent carboxyl compound of the invention
is favorably utilized to provide the thermosetting
composition having the above excellent characteristics and
efficiently prepared by the method of preparation of the
invention.
6 9

20~0167
T a b 1 e
Example of preparation of material 1 2 3
unsaturated compound A-l(a) A--2(a) A-3(a)
methacrylic acid 86.0 86.0 86.0
composition ethyl vinyl ether 86.5 - -
of the isobutyl vinyl ether - 120.2
material, 3,4-dihydro-2H-pyran - -- 100.9
weight hydroquinone monomethyl 0.2 0.2 0.2
part ether
hydrochloric acid, 0.1 0.1 0.1
35 weight %
content of the effective g4.5 95.3 95.1
component,
weight %

20~0167
T a b l e 2
Example of preparation of material 1 2 3
compound A A-1 A-2 A-3
xylene 200.0 200.0 200.0
compound A-l(a) 167.2
compound A-2(a) ~ 5.2
composition compound A-3(a) - - 178.8
of dropped n-butyl methacrylate 100.0 100.0 100.0
mixture, methyl methacrylate 178.6 178.6 178.6
2--ethyl hexyl 135.4 135.4 135.4
weight part acrylate
n--butyl acetate 135.9 106.8 123.8
AIBN 22.9 24.0 23.4
additional n--butyl acetate 57.0 57.0 57.0
catalyst, AIBN 3.0 3.0 3.0
weight part
properties non-volatile 57.2 60.1 58.5
matter,
weight %
Gardener viscosity ~-S W-X U

- 2040167
T a b l e 3
Example of preparation of 5 6 7 8 9 10
material
compound (B) B-1 B-2 B-3 B-4 B-5 B-6
GMA 28.40 -~
TMSPMA - 16.60
MZ-11 - - 31.00 - - -
composition MAGME - -- - 19.22
of dropped IEM - - - - 31.00
mixture, PMA - - - - - 35.40
weight part BMA 20.00 20.00 20.00 20.00 20.00 20.00
MMA 27.70 51.19 25.10 33.80 25.10 19.20
EHA 23.90 12.21 23.90 28.90 23.90 25.40
AIBN 2.00 2.00 2.00 2.00 2.00 2.00
n-butyl acetate 54.00 54.00 54.00 52.08 54.00 54.00
additional n-butyl acetate 3.80 3.80 3.80 3.80 3.80 3.80
catalyst, AIBN 0.20 0.20 0.20 0.20 0.20 0.20
weight part
properties non-volatile 50.8 50.5 51.0 50.2 51.3 51.1
matter,
weight %
Gardener S P-Q S-T V-W R 0
viscosity
72

20~0167
T a b 1 e 4
Example of preparation of material 12 13
compound (D) D-l D-2
xylene 40.0 40.0
compound A-3(a) 36.0
compound A-2(a) - 19.5
GMA 14.2 --
component 2-hydroxyethyl methacrylate - 32.5
of dropped BMA 20.0 20.0
mixture, MMA 18.5 18.8
EHA 13.5 20.1
weight part TMSPNA 16.6
n-butyl acetate 28.7 36.6
AIBN 4-5 4-5
additional n-butyl acetate 7.6 7.6
catalyst, AIBN 0.4 0.4
weight part
properties non-volatile 58.5 55.3
matter,
weight %
Gardener viscosity V-W Y-Z

2~0167
T a b l e 5
Example 2(1) 3(1) 4(1)
Praccel E-488~ 387.6 - -
K-Flex 188-50~ - 477.5
composition Flexorez UD-320~ - - 321.0
of charged methylated 672.0
mixture, hexahydrophthalic
anhydride
weight part hexahydrophthalic - 308.0 308.0
anhydride
methyl isobutyl 264.9 172.5 147.2
ketone
74

- 2040167
T a b 1 e 6
Example 2(2) 3(2) 4(2)
solution of polycarboxyl 330.1 - -
compound of Example 2(1)
composition solution of polycarboxyl - 479.6
of charged compound of Example 3(1)
mixture, solution of polycarboxyl - - 387.0
compound of Exa~ple 4(1)
weight part ethyl vinyl ether 108.0
isobutyl vinyl ether - 150.0 150.0
monooctyl phosphate 0.8 1.2 0.9
xylene 125.3 186.6 131.3
removed solvent in vacuo, 36.0 59.0 50.0
weight part
solution of thermal latent [2] [3~ ~4]
carboxyl compound
properties effective component, % 50.1 49.8 50.0
Gardener viscosity J-K G-H I-J

2040167
T a b l e 7 (Part ])
Example 1 2 3 4
average number of 3 4 2 2
properties of functional group
polycarboxyl acid equivalent, 199 255 383 310
compound g/mole
number average 596 1060 766 621
molecular weight
blocking agentl' EVE EVE IBVE IBVE
solution of thermal latent [1] [2] [3] [4]
carboxyl compound
properties effective component, 50.0 50.1 49.8 50.0
weight %
Gardener viscosity F-G J-K G-H I-J
1) EVE: ethyl vinyl ether
IBVE: isobutyl vinyl ether
(Table 7 continued)
76

20401~7
T a b l e 7 (Part 2)
Example 5 6 7 8
average number of 3 3 3 3.7
properties of functional group
polycarboxyl acid equivalent, 386 500 275 500
compound g/mole
number average 1157 1500 825 1850
molecular weight
blocking agentl~ PVE PVE DHP DHP
solution of thermal latent [5] ~6] [7] [8]
carboxyl compound
properties effective component, 50.0 50.0 50.0 50.0
weight %
Gardener viscosity J-K L-M S-T 0-P
1) PVE: n-propyl vinyl ether
DHP: 3,4-dihydro-2H-pyran
(End of Table 7)

2~10167
T a b l e 8 (Partl)
Example 9 10 11 12 13 14
compounding recipe in weight parts
compound A-1 100 - - - 100
compound A-2 - 100 - - - 100
compound A-3 - - 100
compound A-4 - - - 50.0
compound B~ 100
compound B-2 - 100
compound B-7
compound D-1
compound D-2 - -- - - - -
EX-421~ 15.5
PZ-33~ - - 16.1
Coronate EH~ - - - - 20.0
Cymel 303~ - - - - - 14.0
KR-214~ - - - _
titanium dioxide 52.4 80.0 52.9 56.0 56.0 51.2
Modaflow~ 0.3 0.5 0.3 0.3 0.3 0.3
10% PTSA - - - - - 1.9
10% pyridine - - - - 0.9
xylene 10 20 10 15 10 10
n-butyl acetate 2 4 2 3 2 2
(Table 8 continued)
78

20~0167
T a b 1 e 8 (Part 2)
Example 15 16 17 18 19
compounding recipe in weight parts
compound A~
compound A-2 - -~
compound A-3 100 100 100
compound A-4
compound B-1 100
compound B-2
compound B-7 - - 10.9 --- -
compound D-1 - -- - IQ0
compound D-2 -- - - - 100
EX-421~ - - - - -
PZ-33
Coronate EH~
Cymel 303~ - -- - - 10.5
KR-214~ - 49 0
titanium dioxide80.0 67.4 48.7 40.0 48.4
Modaflow~ 0.5 0.3 0.3 0.3 0.3
10% PTSA - - 1.8 - 1.8
10% pyridine - - 0.9 - 0.9
xylene 20 15 10 10 10
n-butyl acetate 4 3 2 2 2
(End of Table 8)
79

21~40167
T a b l e 9 (Part 1)
Rxample 9 10 11
compound (A) A-1 A-2 A-3
compound (B) EX-421 B-2 PZ-33
epoxy group alkoxysilane group imino group
compound (D) - - --
ratio of mixing (A) 78.7 54.3 78.4
solid components (B) 2I.3 45.7 21.6
(D)
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity 1.1 1.2 1.3
at 50~ after 30
days,
poise
curing condition 120~ 140~ 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min 30 min 30 min
resistance good good good good good good
properties of to acid 1
coatingl~ resistance stain good stain good stain good
to acid 2
resistance good good good good cloud good
to acid 3
impact good good good good good good
resistance
weathering 83% 87% 90% 94% 81% 85%
resistance
Knoop 8.8 10.8 10.0 11.0 9.1 10.5
hardness
1) good: no change was observed.
stain: slight stain was observed
cloud: surface was slightly cloudy
(Table 9 continued)

20401~7
T a b l e 9 (Part ~)
~xample 12 13 14
compound (A) A-4 A-1 A-2
compound (B) B-1 Coronate EH Cymel 303
epoxy ~roup isocyanate group alkylated amino-
methylol group
compound (D) - - -
ratio of mixing (A) 37.l 74.1 81.1
solid components (B) 62.9 25.9 18.9
(D) - - -
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity l.1 1.1 1.1
at 50~ after 30
days,
poise
curing condition 120~ 140~ 120~ lA0~ 120~ 140~
30 min 30 min 30 min 30 min 30 min 30 min
resistance good good good good good good
properties of to acid 1
coatingl~ resistance stain good stain good good good
to acid 2
resistance good good good good good good
to acid 3
impact good good good good good good
resistance
weathering 83% 86% 84% 87% 82% 86%
resistance
Knoop 7.7 9.9 9.5 11.2 10.0 10.7
hardness
1) good: no change was observed.
stain: slight stain was observed
(Table 9 continued)
81

20~0167
T a b 1 e 9 (Part 3)
Example 15 16 17
compound (A) A--3 A-3 A--3
compound (B) B-1 KR-214 B-7
epoxy group silanol group acetal group
compound (D)
ratio of mixing (A) 53.5 63.0 84.3
solid components (B) 46.5 37.0 15.7
(D)
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity 1.1 1.2 1.1
at 50~ after 30
days,
poise
curing condition 120~ 140~ 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min 30 min 30 min
resistance good good good good good good
properties of to acid 1
coatingl~ resistance stain good stain good good good
to acid 2
resistance good good cloud good good good
to acid 3
impact good good good good good good
resistance
weathering 8]% 85% 88% 93% 84% 88%
resistance
Knoop 8.2 10.4 8.7 11.5 10.7 11.1
hardness
1) good: no change was observed.
stain: slight stain was observed
cloud: surface was slightly cloudy
(Table 9 continued)
82

2040167
T a b 1 e 9 (Part 4)
Example 18 19
compound (A) - -
compolmd (B) - Cymel 303
- alkylated amino-
methylol group
compound (D) D--1 D-2
epoxy group hydroxyl group
alkoxy silane
group
ratio of mixing (A)
solid components (B) - 16. 0
(D) 100 84.0
initial 1.0 1.0
Vi SCOS i ty,
storage poise
stability viscosity 1.2 1.2
at 50~ after 30
days,
po ise
curing condition 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min
resistance good good good good
properties of to acid 1
coatingl~ resistance stain good good good
to acid 2
resistance good good good good
to acid 3
impact good good good good
resistance
weathering 82% 87% 81% 85%
resistance
Knoop 9.5 11.3 10.2 10.8
hardness
1) good: no change was observed.
stain: slight stain was observed
(End of Table 9)

2040167
T a b l e 10
Comparative example 1 2
compounding recipe in weight parts
Compound A-5 100
polycarboxylic acid A-4(a) - 33.3
Denacol EX-421 15.5
compound B-1 - 100
titanium dioxide JR-602 52.4 56.0
Moda~low 0.3 0.3
xylene 10 10
n-butyl acetate 2 2
84

2040167
T a b l e 11
Comparative example 1 2
compound (A) A--5 polycarboxylic
acid A-4(a)
compound (B) EX-421 B-1
epoxy group epoxy group
ratio of mixing (A) 76.9 28.6
solid components (B) 23.1 71.4
initial 1.0 1.0
viscosity,
storage poise
stability viscosity 1.2 gel
at 50~ after 30 after 5 days
days,
poise
curing condition 140~ 140~
30 min 30 min
resistance coating dissolvedgood
properties of to acid 1
coatingl~ resistance coating dissolvedgood
to acid 2
resistance coating dissolvedgood
to acid 3
impact coating broken good
resistance by dropping of
10 cm
weathering chalking after 87
resistance 200 hours
Knoop 0.4 11.8
hardness
1) good: no change was observed.

20~0167
T a b l e 12
Example 20 21 22 23
compounding recipe by weight parts
compound A-2 100 - - -
compound A-4 - 50 - -
compound B-l - 100
compo~ld B-2 100
compound D-l - - 100
compound D-2 - - - 100
Cymel 303 . - - - 10.5
Modaflow 0.2 0.1 0.1 0.1
10% PTSA - - - 1.8
10% pyridine - - - 1.9
xylene 5 4 3 3
n--butyl acetate
86

20~016~
T a b l e 13 (Part 1)
Example 20 21
compound (A) A-2 A-4
compound (B) B-2 B-1
alkoxysilane epoxy group
group
compound (D)
ratio of mixing (A) 54.3 37.1
solid components (B) 45.7 62.9
(D)
initial 1.0 1.0
viscosity,
storage poise
stability viscosity 1.2 1.2
at 50~ after 30
days,
poise
curing condition 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min
resistance good good good good
properties of to acid 1
coating" resistance stain good stain good
to acid 2
resistance cloud good good good
to acid 3
impact good good good good
resistance
weathering good good good good
resistance
Knoop 8.8 10.9 9.0 11.2
hardness
1) good: no change was observed.
stain: slight stain was observed
cloud: surface was slightly cloudy
(Table 13 continued)
87

20~0167
T a b 1 e 13 (Part 2)
Example 22 23
compound (A) -- -
compound (B) - Cymel 303
alkylated amino-
methylol group
compound (D) D-1 D-2
epoxy group hydroxyl group
alkoxysilane
group
ratio of mixing (A) - -
solid components (B) -- 16.0
(D) lOO 84.0
initial 1.0 1.0
viscosity,
storage poise
stability ~iscosity - 1.2 1.2
at 50~ after 30
days,
poise
curing condition 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min
resistance good good good good
properties of to acid 1
coatingl~ resistance stain good good good
to acid 2
resistance good good gocd good
to acid 3
impact good good good good
resistance
weathering good good good good
resistance
~noop 8.1 10.3 10.8 11.5
hardness
1) good: no change was observed.
stain: slight stain was observed
(~Id of Table 13)
88

20~0167
T a b 1 e 14
Comparative example 3 4
compounding recipe by weight parts
compound A-5 100
polycarboxylic acid A-4(a) - 33.3
Denacol EX-421 15.5
compound B-1 - 100
Modaflow 0.1 0.1
xylene 5 5
n-butyl acetate

20401~7
T a b l e 15
Comparative example 3 4
compound (A) A-5 polycarboxylic
acid A--4(a)
compound (B) EX-421 B-1
epoxy group epoxy group
ratio of mixing (A) 76.9 28.6
solid components (B) 23.1 71.4
initial 1.0 1.0
viscosity,
storage poise
stability viscosity 1.2 gel
at S0~ after 30 after 5 days
days,
poise
curing condition 140~ 140~
30 min 30 min
resistance coating dissolvedgood
properties of to acid 1
coatingl~ resistance coating dissolvedgood
to acid 2
resistance coating dissolvedgood
to acid 3
impact coating broken good
resistance by dropping of
10 cm
weathering cracking after good
resistance 600 hours
Knoop 0.2 12.0
hardness
1) good: no change was observed.

2040167
T a b 1 e 16 (Part 1)
Example 24 25 26 27 28 29
compounding recipe by weight parts
compound A-l 100 - - - 100
compound A-2 - 100 - - - 100
compound A-3 - - 100 -- - -
compound A-4 - - - 50.0
compound B-l - - - 100
compound B-2 - 100
compound B-7
compound D-l
compound D-2 - - - - - -
EX-421~ 15.5 - -- - - -
PZ-33~ - - 16.l
Coronate EH~ - - - - 20.0
Cymel 303~ - 14.0
KR-214~ - - - - - -
titanium dioxide 52.4 80.0 52.9 56.0 56.0 51.2
ModaflowH 0.3 0.5 0.3 0.3 0.3 0.3
10% PTSA - - - - - 1.9
10% pyridine - - - - - 0.9
C-1203~ 1.0 - - - - -
acid catalyst A - 3.0 - - -
acid catalyst B - - 2.0
acid catalyst C - - - 4.2 4.2
acid cata]yst D - - - - -- -
xylene 10 20 10 15 10 10
n-butyl acetate 2 4 2 3 2 2
(Table 16 continued)
91

2040167
T a b l e 16 (Part 2)
Example 30 31 32 33 34
compounding recipe by weight parts
compound A~
compound A-2 - - - - -
compound A-3 100 100 lO0
compound A-4
compound B-l 100
compound B--2 - - - - -
compound B-7 - - 10.9
compound D-l - - - 100
compound D-2 - - - - 100
EX-4210
PZ-330
Coronate EH0
Cymel 3030 - - - - 10.5
KR-2140 - 49.0 - - -
titanium dioxide 80.0 67.4 48.7 40.0 48.4
Modaflow~ 0.5 0.3 0.3 0.3 0-3
10% PTSA - - 1.8 - 1.8
10% pyridine - - 0.9 - 0.9
C-1203~ - - - - -
acid catalyst A - 2.5 - 1.5
acid catalyst B
acid catalyst C - - - - -
acid catalyst D 5.0
xylene 20 15 10 10 10
n-butyl acetate 4 3 2 2 2
~End of Table 16)
92

2~40167
T a b l e 17 (Part 1)
Example 24 25 26
compound (A) A-1 A-2 A-3
compound (B) EX-421 B-2 P~-33
epoxy group alkoxysilane group imino group
compound (D) - - --
thermal latent Vesturit 1-methylethyl l-methylheptyl
catalyst (C) Catalyst 1203 ester of PTSA ester of PTSA
ratio of mixing (A) 78.7 54.3 78.4
solid components (B) 21.3 45.7 21.6
(D) - - -
content of (C), weight % 0.76 0.37 0.50
=(C)/~(A)+(B)+(D)}X100
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity 1.2 1.3 1.3
at 50~ after 30
days,
poise
curing condition 120~ 110~ 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min 30 min 30 min
resistance good good good good good good
properties of to acid 1
coatingl~ resistance good good good good good good
to acid 2
resistance good good good good good good
to acid 3
impact good good good good good good
resistance
weathering 87% 88% 94% 95% 85% 85%
resistance
Knoop 10.2 10.4 11.3 11.3 10.8 10.9
hardness
1) good: no change was observed.
(Table 17 continued)
93

20~0167
T a b 1 e 17 (Part 2)
~xample 27 28 29
compound (A) A-4 A-1 A-2
compound (B) B-1 Coronate EH Cymel 303
epoxy group isocyanate group alkylated amino-
methylol group
compound (D)
thermal latent 1-methylethyl l-methylethyl pyridine salt
catalyst (C) ester of DDBSA~' ester of DDBSA of PTSA
ratio of mixing (A) 37.1 74.1 81.1
solid components (B) 62.9 25.9 18.9
(D)
content of (C), weight % 0.67 0.67 0.44
=(C)/{(A)+(B)+(D)}X100
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity 1.2 1.1 1.1
at 50~ after 30
days,
poise
curing condition 120~ 140~ 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min 30 min 30 min
resistance good good good good good good
properties of to acid 1
coatingl) resistance good ~ood good good good good
to acid 2
resistance good good good good good good
to acid 3
impact good good good good good good
resistance
weathering 86% 88% 87% 89% 86% 87%
resistance
Knoop 12.3 12.2 10.9 11.0 11.0 11.2
hardness
1) good: no change was observed.
(Table 17 continued)
94

2040167
T a b l e 17 (Part 3)
~xample 30 31 32
compound (A) A-3 A-3 A-3
compound (B) B-1 KR-214 B-7
epoxy group silanol group acetal group
compound (D) - - _
thermal latent di-2-ethylhexyl 1-methylethyl pyridine salt
catalyst (C) phosphate ester of PTSA of PTSA
ratio of mixing (A) 53.5 63.0 84.3
solid components (B) 46.5 37.0 15.7
(D) - - -
content of (C), weight % 0.50 0.37 0.44
=(C)/{(A)+(B)+(D)}X100
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity 1.2 1.3 1.1
at 50~ after 30
days,
poise
curing condition 120~ 1~0~ 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min 30 min 30 min
resistance good good good good good good
properties of to acid 1
coatingl) resistance good good good good good good
to acid 2
resistance good good good good good good
to acid 3
impact good good good good good good
resistance
weathering 85% 87% 93% 93% 88% 89%
resistance
Knoop 10.7 10.9 10.0 10.2 10.1 10.4
hardness
1) good: no change was observed.
(Table 17 continued)

20~016'7
T a b 1 e 17 (Part 4)
~xample 33 34
compound (A) - -
compound (B) - Cymel 303
alkylated amino-
methylol group
compound (D) D-l epoxy groupD-l
alkoxysilanehydroxyl group
group
thermal latent l-methylethylpyridine
catalyst (C) ester of PTSAsalt of PTSA
ratio of mixing (A)
solid components (B) - 16.0
(D) 100 84.0
content of (C), weight % 0.37 0.44
=(C)/~(A)+(B)+(D)}xlOO
initial 1.0 1.0
viscosity,
storage poise
stability viscosity 1.3 1.2
at 50~ after 30
days,
poise
curing condition 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min
resistance good good good good
properties of to acid 1
coatingl) resistance good good good good
to acid 2
resistance good good good good
to acid 3
impact good good good good
resistance
weathering 87% 89% 85% 87%
resistance
Knoop 11.3 11.5 10.9 11.0
hardness
1) good: no change was observed (End of Table 17)
96

204011~ 7
T a b 1 e 18
Comparative example 5
compounding recipe by weight parts
polycarboxylic acid A-4 (a) 33.3
compound B-l 100
titanium dioxide JR-602 56.0
Modaflow 0.3
xylene 10
n-butyl acetate 2
acid catalyst A 2.1
97

2040167
T a b 1 e 19
Comparative example 5
compound (A) polycarboxylic acid A-4 (a)
compound (B) B-1
epoxy group
thermal latent 1-methylethyl ester of PTSA
catalyst (C)
ratio of mixing (A) 28.6
solid components (B) 71.4
content of (C), weight % 0.37
=(C)/{(A)+(B)}X100
initial 1.0
viscosity,
storage poise
stability viscosity ~el after 5 days
at 50~ after 30
days,
po ise
curing condition 120~ 30 min
resistance good
properties of to acid 1
coating') resistance good
to acid 2
resistance good
to acid 3
impact good
resistance
weathering 87%
resistance
Knoop 11.5
hardness
1) good: no change was observed.
98

20~01~7
T a b l e 20
Example 35 36 37 38 39 40 41
compol~ding recipe by weight parts
compound A-2 100 - - - - - -
compound A-4 - 50 - - 50 50 50
compound B-l - 100 - - 100 100 100
compound B-2 100
compound D-l - - 100 - - - -
compound D-2 - - -- 100
Cymel 3036 - - -10.5
Modaflow~ 0.2 0.1 0.10.1 0.1 0.1 0.1
10% PTSA - - - 1.8
10% pyridine - - - 1.9
xylene 5 4 3 3 4 4 4
n-butyl acetate
acid catalyst A 3.0
acid catalysy B - 2.4
acid catalyst C - - 1.5 - - - --
acid catalyst E - - - - 4.0
acid catalyst F - - - - - 3.2 --
acid catalyst G - - - - - - 8.0
99

20~0167
T a b 1 e 21 (Part 1)
Example 35 36 37
compound (A) A-2 A-4
compound (B) B--2 B-1
alkoxysilane epoxy group
group
compound (D) -- - D-l
epoxy group
alkoxysilane group
ratio of mixing (A) 54.3 37.1
solid components (B) 45.7 62.9
(D) - - 100
thermal latent l-methylethyl 1-methylheptyl 1-methylethyl
catalyst (C) ester of PTSA ester of PTSA ester of DDBSA
content of (C), weight % 0.37 0.50 0.67
=(C)/{(A)+(B)+(D)}X100
initial 1.0 1.0 1.0
ViSCOS ity,
storage poise
stability viscosity 1.3 1.2 1.3
at 50~ after 30
days,
po ise
curing condition 120~ 140~ 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min 30 min 30 min
resistance good good good good good good
properties of to acid 1
coatingl) resistance good good good good good good
to acid 2
resistance good good good good good good
to acid 3
impact good good good good good good
resistance
weathering good good good good good good
resistance
Knoop 11.0 11.2 11.4 11.5 11.2 11.4
hardness
1) good: no change was observed (Table 21 continued)
100

20~0167
T a b 1 e 21 (Part 2)
Example 38 39
compound (A) - A-4
compound (B) Cymel 303 B-1
alkylated amino- epoxy group
methylol group
compound (D) D-2
hydroxyl group
thermal latent pyridine triethylamine
catalyst (C) salt of PTSAsalt of 7,nC12
ratio of mixing (A) _ 37.1
solid components (B) 16.0 62.9
(D) 84.0
content of (C), weight % 0.44 0.50
=(C)/{(A)+(B)+(D)}X100
initial - 1.0 1.0
viscosity,
storage poise
stability viscosity 1.2 1.3
at 50~ after 30
days,
poise
curing condition 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min
resistance good good good good
properties of to acid 1
coatingl~ resistance good good good good
to acid 2
resistance good good good good
to acid 3
impact good good good good
resistance
weathering good good good good
resistance
Knoop 10.7 11.0 11.5 11.7
hardness
1) good: no change was observed (Table 21 continued)
101

2040167
T a b l e 21 (Part 3)
Example 40 41
compound (A) A-4 A-4
compound (B) B-l B--l
epoxy group epoxy group
compound (D) --
thermal latent 3-methyl-2- 4-methoxybenzyl-
catalyst (C) butynyltetramethylene pyridinium
sulfonium hexafluoro- hexafluoro-
antimonate antimonate
ratio of mixing (A) 37.1 37.1
solid components (B) 62.9 62.9
(D)
content of (C), weight % 2.00 2.00
-(C)/{(A)-i(B)+(D)}xloo
initial 1.0 1.0
viscosity,
storage poise
stability viscosity 1.2 1.1
at 50~ after 30
days,
poise
curing condition 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min
resistance good good good good
properties of to acid 1
coatingl~ resistance good good good good
to acid 2
resistance good good good good
to acid 3
impact good good good good
resistance
weathering good good good good
resistance
Knoop 11.3 11.4 11.4 11.6
hardness
1) good: no change was observed (End of Table 21)
102

2040167
T a b 1 e 22
Comparative example 6
compounding recipe by weight parts
polycarboxylic acid A-4 (a) 33.3
compound B-l 100
Modaflow 0.1
xylene 5
n-butyl acetate
acid catalyst A 2.1
103

20~016~
T a b 1 e 23
Comparative example 6
compound (A) polycarboxylic acid
A-4 (a)
compound (B) B-1
epoxy group
thermal latent 1-methylethyl ester
catalyst (C) of PTSA
ratio of mixing (A) 28.6
solid components (B) 71.4
content of (C), weight % 0.37
=(C)/{(A)+(B)}X100
initial 1.0
viscosity,
storage poise
stability viscosity gel
at 50~ after 30 after 5 days
days,
poise
curing condition 12Qr
30 min
resistance good
properties of to acid 1
coatingl) resistance good
to acid 2
resistance good
to acid 3
impact good
resistance
weathering good
resistance
Knoop 11.4
hardness
1) good: no change was observed
104

2040167
T a b I e 24
Example 42 43 44 45 46 47 48 49 50
compounding recipe of clear coating compositions by weight parts
solution1~ [1] 39.8 - - - _ _ 39.8
solutionl' [2] - 53.0 - - -- - - - -
solutionl~ [3] - - 76.6 -- - - - - -
solutionl' r4] - - - 62.0
solution" [5] - - - -- 77.2
solution1~ [6] - - - - - 100.0 - - ~-
solutionl' r7] - - -- - - - 55.0 - --solutionl~ [8] - - - - - - - 100.0
compound B-1 lO0.0 - - - - - 100.0 - 100.0compound B-2 - 100.0 - - - - - 100.0
compound B-3 - - 100.0 - - - - - -
compound B-4 - - - 200.0
compound B-5 -- - - - 100.0
compound B-6 - -- - - - 100.0
acid catalyst-B ~.0 4.0 4.0 6.0 4.0 4.0 4.0 4.0
acid catalyst--E - - - - - - - - 3.5Modaflow 0.3 0.3 0.3 0.3 0.3 0.4 0.3 0.4 0,3
xylene 10 10 10 10 10 10 10 10 10
n-butyl acetate 2 2 2 2 2 2 2 2 2
1) solution of thermal latent polycarboxylic acid.
105

20401~7
T a b l e 25 (Part 1)
~xample 42 43 44
thermal latent ~1] [2] ~3]
carboxyl compound
compound (B) B-l B-2 B-3
epoxy group alkoxysilane imino group
group
mixing ratio, mole/mole 1/1 1/1 1/1
thermal latent l-methylheptyl l-methylheptyl l-methylheptyl
catalyst (C) ester of PTSA ester of PTSA ester of PTSA
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity 1.2 1.3 1.1
at 50~ after 30
days,
poise
curing condition 120~ 140r 120~ 140~ 120r 140~
30 min 30 min 30 min 30 min 30 min 30 min
resistance good good good good good good
properties of to acid 1
coatingl~ resistance good good good good good good
to acid 2
resistance good good good good good good
to acid 3
impact good good good good good good
resistance
weathering good good good good good good
resistance
Knoop 10.8 11.0 11.1 11.2 10.7 10.9
hardness
1) good: no change was observed.
(Table 25 continued)
106

20~01~i7
T a b l e 25 (Part 2)
Example 45 46 47
thermal latent [4~ [5] ~6
carboxyl compound
compound (B) B-4 B-5 B-6
alkylated amino- isocyanate group vinyl ether
methylol group group
mixing ratio, mole/mole 1/1 1/1 1/1
thermal latent l-methylheptyl 1-methylheptyl 1-methylheptylcatalyst (C) ester of PTSA ester of PTSA ester of PTSA
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity 1.2 1.1 1.2
at 50~ after 30
days,
poise
curing condition 120~ 140~ 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min 30 min 30 min
resistance good good good good good good
properties of to acid 1
coating" resistance good good good good good good
to acid 2
resistance good good good good good good
to acid 3
impact good good good good good good
resistance
weathering good good good good good good
resistance
Knoop 11.4 11.8 10.9 11.3 11.2 11.5
hardness
1) good: no change was observed.
(Table 25 continued)
107

204016'7
T a b 1 e 25 (Part 3)
Example 48 49 50
thermal latent [7] [8] [1]
carboxyl compound
compound (B) B-1 B-2 B-l
epoxy group alkoxysilane epoxy group
group
mixing ratio, mole/mole 1/1 1/1 1/1
thermal latent l-methylheptyl l-methylheptyl triethylamine
catalyst (C) ester of PTSA ester of PTSA salt of ZnCl~
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity 1.3 1.3 1.3
at 50~ after 30
days,
poise
curing condition 120~ 140~ 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min 30 min 30 min
resistanee good good good good good good
properties of to acid 1
coatingL) resistance good good good good good good
to acid 2
resistance good good good good good good
to acid 3
impact good good good good good good
resistance
weathering good good good good good good
resistance
Knoop 10.5 10.8 10.9 11.3 10.9 11.1
hardness
13 good: no change was observed.
(End of Table 25)
108

2040167
T a b l e 26
~xample 51 52 53
compounding recipe of clear coating by weight parts
solution of thermal latent 39.8 39.8 59.7
carboxyl compound [1l
compound B-8 100.0 100.0
compound B-9 - - 100.0
Cymel 303~ 12.8
Coronate 25138 - 20.6
acid catalyst-B 4.5 4.8 4.5
Modaflow~ 0.4 0.4 0.4
xylene 11 12 11
n-butyl acetate 2 3 2
109

2040167
T a b 1 e 27
Example 51 52 53
thermal latent [1] [1] rl]
carboxyl compound
compound (B) B--8 B-8 B-9
epoxy group epoxy group epoxy group
hydroxyl group hydroxyl group alkoxysilane
group
Cymel 303 Coronate 2513
alkylated amino- blocked
methylol group isocyanate group
thermal latent 1-methylheptyl l-methylheptyl 1-methylheptyl
catalyst (C) ester of PTSA ester of PTSA ester of PTSA
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity 1.2 1.1 1.3
at 50~ after 30
days,
poise
curing condition 120~ 140~ 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min 30 min 30 min
resistance good good good good good good
properties of to acid 1
coatingl~ resistance good good good good good good
to acid 2
resistance good ~ood good good good good
to acid 3
impact good good good good good good
resistance
weathering good good good good good good
resistance
Knoop 13.9 14.4 14.0 14.7 14.5 14.9
hardness
1) good: no change was observed.
110