Note: Descriptions are shown in the official language in which they were submitted.
- 2 ~ 2
THERMOSETTING COMPOSlTIONS, THERMAL LATENT HYDROXYL
CONPOUNDS, THRRNAL LATENT THIOL CONPOUNDS AND NETHODS OF
PREPARATION THEREOF
BAC~&ROUND OF THE INVENTION
1. Field of the invention
The present invention relates to novel thermosetting
compositions, thermal latent hydroxyl compounds, thermal
latent thiol compounds and methods of preparation thereof.
More particularly, the present invention relates to novel
thermosetting compositions having excellent chemical
properties, physical properties and weatherbility and
exceptionally excellent storage stability and suitable for
preparation of coating compositions. ink, adhesive and
molded plastics, novel thermal latent hydroxyl compounds
and novel thermal latent thiol compounds are utilized for
the preparation of the thermosetting compositions and
methods of effectivelY preparing the thermal latent
compounds.
2. Descrition of the prior art
It is generally known that thermosetting compositions
can be prepared from compounds having hydroxyl groups or
thiol groups and compounds having reactive functional
groups which can form chemical bonds with the hydroxyl
- ~.
2 ~ 2
.
groups or thiol groups by heating, such as epoxy group,
carboxyl group, acid anhydride group, silanol group,
alkoxysilane group, isocyanate group, blocked isocyanate
group, cyclocarbonate group, vinyl ether group, vinyl
thioether group9 acryloyloxy group, methacryloyloxy group,
aminomethylol group, alkylated aminomethylol group, acetal
group and ketal group. The thermosetting compositions give
cured products having excellent chemical properties,
physical properties and weatherbility and are widely
utilized in the field of coating compositions, ink,
adhesive and molded plastics.
However, the reactivity between the hydroxyl groups or
thiol groups and the reactive functional groups is
generally very high and compositions in which compounds
having the hydroxyl groups or thiol groups and compounds
having the reactive functional groups are mixed together
have problcms that the composition is often gelatinized
during storage and the period in which the composition can
be utilized is short. Therefore, the composition is
actually utilized by the form of two components
thermosetting composition in which components containing
the said different kind of functional group each other are
stored separately in individual vessels and the two
components are mixed together immediately before use.
2 ~ 2
It is described in U. S. Patent 3,530,167 that a
compound in which hydroxyl group is made into acetal group
can be utilized. However, acetal group is used for the
reaction of curing by itself in this method and utilization
of thermal latent catalysts is not mentioned at all.
SUNMARY OF THE INVENTION
The present invention accordingly has an obiect to
provide thermosetting compositions which give cured
products having excellent chemical properties, physical
properties and weatherbility at relatively low temperature,
have excellent storage stability ~nd can be utilized as one
component compositions. Another object of the invention is
to provids thermal latent hydroxyl compounds and thermal
latent thiol compounds useful ~or the preparation of the
thermosetting compositions. Still another object of the
invention is to provide methods of preparation of the
thermal latent hydroxyl compounds and the thermal latent
thiol 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 L1]:
2 ~
R2
-R'-Y'-C-Y2-R5
HC-R4
R3 [1]
wherein R' is a bivalent organic group of 1 to 18 carbon
atoms, R2, R3 and R4 are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, Rs is an organic group of 1 to 18
earbon atoms, Y' and y2 are respectively selected from the
group eonsisting of an oxygen atom and a sulfur atom and R3
and R~ or R~ and R5 may be bonded with each other to form a
heteroeyelie strueture which eomprises y2 as the hetero
atom eomponent;
(B) a eompound having in the molecule two or more reaetive
funetional groups whieh ean form a ehemieal bond with the
funetional groups of the eompound (A) by heating; and
(C) a thermal latent aeid eatalyst which is aetivated
during euring of the eomposition by heating.
The thermosetting eompositions of the present invention
also comprige:
(D) a self-erosslinking eompound having in the molee1l1e (a)
one or more funetional groups of the general formula [2~:
2 ~ 2
R7
-R6-Z' -C-z2-Rl o
HC-R9
RK ~2]
wherein R6 is a bivalent organic group of I to 18 carbon
atoms, R7~ R8 and R9 are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, Rl~ is an organic group of 1 to 18
carbon atoms, Z' and Z2 are respectively selected from the
group consisting of an oxygen atom and a sulfur atom and R8
and R'~ or R~ and Rl~ may be bonded with each other to form
a heterocyclic structure which comprises Z2 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) essentially, 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 rl-l
1 2
î
Hl-R 4
R3 Ll]
wherein R' is a bivalent organic group of' l to 18 carbon
2 ~ 2
atoms, R2, R3 and R4 are respectively selected from the
group consisting of a hydrogen atom and an organ-ic ~roup of
1 to 18 carbon atoms, R5 is an organic group of 1 to 18
carbon atoms, yl and y2 are respectively selected from the
group consisting of an oxygen atom and a sulfur atom and R3
and R5 or R4 and Rs may be bonded with each other to form a
heterocyclic structure which comprises YZ 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 of the general formula [1] and the functional group
of the general formula C2].
The thermal latent compounds which are either the
thermal latent hydroxyl compounds or ths thermal latent
thiol compounds are prepared by reaction of a polyol
compound or a polythiol compound having two or more
hydroxyl groups or thiol groups in the molecule, hydroxyl
equivalent or thiol equivalent of not more than lOOOg/mole
and number average molecular weight of not more than 4000
with a vinyl ether compound, whereby the hydroxyl groups or
the thiol groups are transformed into blocked hydroxyl
groups or blocked thiol groups of the general formula [3]:
1 12
-R'l-y3-c y4-Rls
HC-RI4
R~3 L3]
wherein Rl' is a bivalent organic group of 1 to 18 carbon
atoms, Rl 2, Rl3 and R'4 are respectively se]ected from the
group consisting of a hydrogen atom and an organic group
consisting of 1 to 18 carbon atoms, R'5 is an organic group
of 1 to 18 carbon atoms. Y3 and Y4 are respectively
selected from the group consisting of an oxygen atom and a
sulfur atom and Rl3 and R'5 or R'4 and R's may be bonded
with each other to form a heterocyclic structure which
comprises Y4 as the hetero atom component
The method of preparation of the thermal latent
compounds is characterized in that a polyol compound or a
polythiol compound havin~ two or more hydroxyl groups or
thiol groups in the molecule, hydroxyl equivalent or thiol
equivalent of not more than 1000g/mole and number average
molecular weight of not more than 4000 is made to react
with a vinyl ether compound.
Other and further objects, features and advantages of
the invention will appear more fully from ttle following
description.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
~ xtensive 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, as the
essential components: (A) a compound having in the molecule
two or more hydroxyl groups and/or thiol groups, which are
blocked by a specific vinyl ether group, vinyl thioether
group or heterocyclic compound having a 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 a chemical bond with the
bloched hydroxyl groups or thiol groups and (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 hydroxyl groups and/or blocked thiol groups
and one or more reactive functional groups which can form a
chemical bond with t,he blocked hydroxyl and/or thiol groups
by heating and the said compound (C) as the essential
components, The composition may optionally comprise the
said compound (A) and/or the said compound (B).
It was also discovered that the thermal latent hydroxyl
compound and/or thiol compound giving the thermosetting
composition having the advantageous properties could be
prepared by reaction of a specific low molecular weight
polyol compound and/or polythiol compound with a vinyl
ether compound to block the hydroxyl group and/or thiol
group of the polyol compound and/or polythiol 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]:
Rl ?,
-R'-yl-c y
HC - R ''
R:' [1]
wherein Rl is a bivalent organic group of 1 to 18 carbon
atoms, R2, Ra and R~ are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, Rr' is an organic group of 1 to 18
carbon atoms, Y' and YZ are respectively selected from the
group consisting of an oxygen atom and a sulfur atom and R~
and Rr' or R~ and R~ Inay be bonded with each other to form a
heterocyclic structure which comprises y2 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
(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]:
Rt 7
-R~-Z'-C-ZZ-R'~
HC-R~
RH ~2]
wherein R~ is a bivalent organic group of i to 18 carbon
atoms, R7, R~ and RD are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, Rl~ is an organic group of 1 to 18
carbon atoms, Z' and Z2 are respectively selected from the
group consisting of an oxygen atom and a sulfur atom and RH
and R'~ or RD and Rl~ may be bonded with each other to form
a heterocyclic structure which comprises Z2 as the hetero
atom component; and (b) one or more reactive functional
1 0
groups which can form a chemical bond with the functional
groups (a) by heating;
(C) essentially, 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]:
Rl 2
-R'--Y'-C Y2-Rs
HC-R~
R3 [1~
wherein R~ is a bivalent organic group of 1 to 18 carbon
atoms, R2, R~ and R~ are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, R~ is an organic group of 1 to 18
carbon atoms, Y' and YZ are respectively selected from the
group consisting of an oxygen atom and a sulfur atom and R~
and R~ or R~ and R~ may be bonded with each other to form a
hetsrocyclic structure which comprises y2 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 hsating with either one or both of the functional
group of the general formula [1] and the functional group
of the general formula [2~.
2 ~ 2
The therma] latent compounds which are either the
thermal latent hydroxyl compounds or the thermal latent
thiol compounds are prepared by reaction of a polyol
compound or a polythiol compound having two or more
hydroxyl groups or thiol groups in the molecule, hydroxyl
equivalent or thiol equivalent of not more than 1000 g/mole
and number average molecular weight of not more than 4000
with a vinyl ether compound, whereby the hydroxyl groups or
the thiol groups are transformed into blocked hydroxyl
groups or blocked thiol groups of the general formula [3]:
Rl~2
-Rl l-Ya-C-Y''-R'
HC-R
R':' [3~
wherein R " is a bivalent organic group of 1 to 18 carbon
atoms, R'Z, R'3 and R'~ are respectively selected from the
group consisting of a hydrogen atom and an organic group of
1 to 18 carbon atoms, R'~' is an organic group of 1 to 18
carbon atoms, ya and Y~ are respectively selected from the
group consisting of an oxygen atom and a sulfur atom and Rl3
and Rl~ or Rl~ and R' r~ may be bonded with each other to
form a heterocyclic structure which comprises Y~ as the
hetero atom component
The method of preparation of the thermal latent compound
1 2
is characterized in that a polyol compound or a polythiol
compound having two or more hydroxyl groups or thiol groups
in the molecule, hydroxyl equivalent or thiol equivalent of
not more than lOOOg/mole and number average molecular
weight of not more than 4000 is made to react with a vinyl
ether compound.
The invention is described in more detail in the
following.
The compound (A) in the thermosetting composition of
the invention has in the molecule two or more, preferably 2
to 50, more preferably 2 to 20, functional groups of the
following general formula [1~:
Rl 2
-Rl-YI-c y2-RD
HC-R~
R~ [1~
~herein Rl, RZ, R~, R~, Rfi, Y' and y2 are the same as
described before,
The functional group of the general formula [1] is
easily prepared by reaction of a hydroxyl group and/or a
thiol group of the formula [4]:
-Rl-YIH [4]
~herein Rl and yl are the same as described before, with a
vinyl ether, a vinyl thioether or a heterocyclic compound
having a vinyl type double bond and having oxygen or sulfur
as the hetero atom which has the general formula [5]:
C=C-Y2 --Rs
R4 [5]
wherein R2, R3, R~, R5 and y2 are the same as described
before.
In the formula [1] and formula [~], Rl is a bivalent
group of I to 18 carbon atoms. such as alkylene group,
arylene group, alkarylene group and the like, and may have
substituted groups in the molecule.
In the formula [1] and formula [5], R2, R3 and R~ 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, R~ is
an organic group, such as alkyl erouP, aryl group and
alkaryl group of 1 to 18 carbon atolns. The organic groups
may have substituted groups in the molecule and Ra and R~
or R~ and R~ may be bonded together to form a heterocyclic
structure with or without substituents and having y2 as the
hetero atom component.
~ xamples of the compound of the formula C5~ are:
aliphatic vinyl ethers, such as methyl vinyl ether, ethyl
vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether,
21~4~5~2
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 vinyl 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-
4,4-dimethyl-2H-thiopyran-2-ono, 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, preferably 2 to 50, more
preferably 2 to 20, hydroxyl groups and/or thiol groups in
the molecule with the compound baving the formula r5].
examples of the compound having two or more hydroxyl erouPS
which will be called the compound having polyfunctional
2~
hydroxyl groups and the compound having two or more thiol
groups ~hich will be called the compound having
polyfunctional thiol groups are: ~olols, such as ethylene
glycol, 1,2-propylene glycol, 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, 1,8-octanediol,
1,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol,
1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane,
trimethylolpropane, pentaerythritol, quinitol, mannitol,
tris-hydroxyethyl isocyanurate, dipentaerythritol and the
like; addition products of the polyols with a lactone, such
as ~ butyrolactone and ~-caprolactone and the like, by
ring opening of the lactone; addition products of the
polyols 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 polyhydric alcohol
with a vinyl ether, such as ethylene elYcol divinyl ether,
polyethylene glycol divinyl ether, butanediol divinyl
ether, pentanediol divinyl ether, hexanediol divinyl ether
and the like, in excess amount of the alcohol; addition
products of the polyhydric alcohol with an alkoxysilicone
1 6
compound, such as KR-213~, KR-217~, KR-9218~ (products of
Shinetsu Chemical Co., Ltd.), in excess amount of the
alcohol; compounds having a structure in which all or a
part of hydroxyl groups of the compounds having
polyfunctional hydroxyl groups are substituted by thiol
groups; polyester resins, polyacrylic resins and polyvinyl
alcohol resins which comprise two or more hydroxyl groups
and/or thiol groups in the molecule: and the like other
compounds.
The compound (A) can also be prepared by polymerization
of the reaction product of the compound [5] with an a,~-
unsaturated hydroxyl compound, such as 2-hydroxyethyl
acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl
acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl
acryJate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl
acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl
acrylate, 3-hydroxybutyl Methacrylate, 4-hydroxybutyl
acrylate, 4-hydroxybutyl methacrylate, dipentaerythritol
hexa(meth)acrylate, hexa(meth)acrylate of a compound formed
by addition of dipentaerythritol with e-caprolactone and
the like, or with a corresponding a,~-unsaturated thiol
compound. The compound (A) can also be prepared by
copolymerization of the reaction product with an
unsaturated compound having no functional groups.
1 7
Examples of the a,~-unsaturat~d compound having no
functional groups are: methyl (meth)acrylate, ethyl
(meth)acrylate, n-propyl (meth)acrylate, isopropyl
(meth)acrylate, n-butyl (meth)acrylate, isobutyl
(meth)acrylate, sec-butyl (meth)acrylate, t-butyl
(meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, lauryl (meth)acrylate, stearyl
(meth)acrylate, styrene, a-methylstyrene, p-vinyltoluene,
acrylonitrile and the like.
The reaction of the compound ~5] with the compound
having polyfunctional hydroxyl groups or with the compound
having polyfunctional thiol groups is generally performed
at a temperature in the range from the room temperature to
100~ in the presence of an acid catalgst.
~ ither a single kind of the compound (A) or a
combination of two or more kinds of the compound (A) may be
utilized in the invention,
The compound~ (B) ùtilized in the thermosetting
composition of the invention are compounds having in the
molecule two or more, preferably from 2 to S0, more
preferably 2 to 20, reactive functional groups which can
form chemical bonds by the reaction with the regenerated
free hydroxyl group or thiol group formed from the
functional group [I] of the compound (A) by heating. The
1 8
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, carboxyl group, acid anhydride
group, silanol group, alkoxysilane group, isocyanate group,
blocked isocyanate group, cyclocarbonate group, vinyl ether
group, vinyl thioether group, acryloyloxy group,
methacryloyloxy group aminomethylol group, alkYl
substituted aminomethylol group, acetal group, ketal group
and the like ~roups. The compounds (B) may have either a
single kind or two or more kinds of the reactive functional
groups in the molecule.
~ xamples of the compound of (B) are: compounds having
epoxy ~roups, such as epoxy resins of bisphenol type,
alicyclic epoxy resins, homopolymers and copolymers of
glycidyl (meth)acrylate, 3,~-epoxycyclohexylmethyl
(meth)acrylate and the like compoullds, polyglycidyl ether
compounds and polyglycidyl ester compounds obtained by the
reaction of epichlorohydrine with polycarboxylic acids or
polyols and other like compounds;
compounds having polyfunctional carboxyl groups, such as
aliphatic polyfunctional carboxyl;c acids, aromatic
polyfunctional carboxylic acids, alicyclic polyfllnctional
carboxylic acids, copolymers and copolymers of acrylic
1 9
acid, methacrylic acid, itaconic acid and the like,
polyester resins having two or more carboxyl groups in the
molecule, polybutadiene resins modified with maleic acid
and the like other compounds;
compounds comprising polyfunctional acid anhydride groups,
such as polymers and copolymers of a,~-unsaturated acid
anhydrides like maleic anhydride, itaconic anhydride and
the like;
compounds having silanol group or alkoxysilane group, such
as condensation products of a compound of the formula [6]:
(Rl~)nSi(ORI 7)~ - n [6.1
wherein Rlff and Rl7 are res~ectivsly selected from the
group consisting of alkyl group of 1 to 18 carbon atoms and
aryl group of I to 18 carbon atoms and n is O, 1 or 2,
homopolymers and copolymers of a,~ unsaturated silane
compounds, like acryloyloxypropyltrimethoxysilane,
methacryloyloxypropyltrimethoxysilane, methacryloyloxy-
propyl-tri-n-butoxysilane and the ]ike, hydrolysis products
of these compounds and the like;
compounds having isocyanate group, such as p-phenylene
diisocyanate, biphenyl diisocyanate, tolylene diisoGYanate,
3,3'-dimethyl-4,4'-biphenylene diisocyanate,
1,4-tetramethylene diisocyanate, hexamethylene
diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate,
2 O
~ 7~2
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, adducts of these isocyanates and the compounds
having polyfunctional hydroxyl groups and the like;
compounds having blocked isocyanate group, such as
compounds prepared by blocking the compounds comprising
isocyanate group with phenols, lactams, active methylenes,
alcohols, acid amides, imides, amines, imidazoles, ureas,
imines, or oximes and the like compounds;
compounds having cyclocarbonate group, such as homopolymers
and copolymers of 3-(meth)acryloyloxypropylene carbonate,
compounds having polyfunctional cyclocarbonate group
prepared by the reaction of the compounds having epoxy
group with carbon dioxide and the like;
compounds having polyfunctional vinyl ether groups or
polyfunctional vinyl thioether groups, such as compounds
having polyfunctional vinyl ether groups prepared by the
reaction of the compounds having polyfunctional hydroxyl
groups or the compounds havlng polyfunctional carboxyl
groups with halogenated alkyl vinyl ethers, polyfunctional
vinyl ether compounds prepared by the reaction of
$ 2
hydroxyalkyl vinyl ethers with compounds having
polyfunctional carboxyl groups or with the compounds having
isocyanate group, copolymer of vinyloxyalkyl
(meth)acrylates with a,~-unsaturated co~pounds, vinyl
thioethers corresponding to the vinyl ethers and the like;
compounds having polyfunctional (meth)acryloyloxy groups,
such as ethyleneglycol di(meth)acrylate, diethylene glycol
di(meth)acrylate, triethyleneglycol di(meth)acrylate,
polyethyleneglycol di(meth)acrylate, l,4-butanediol
di(meth)acrylate, 1,6~hexanediol di(meth)acrylate,
neopentylglycol di(meth)acrylate, tetraethyleneglycol
di(meth)acrylate, tetrapropyleneglycol di(meth)acrylate,
tripropyleneglycol di(meth)acrylate, di(meth)acrylate of
neop~ntylglycol hydroxypivalate, acetalglycol
di(meth)acrylate, trimethylolpropane tri(meth)acrylate,
pentaerythritol tetra(meth)acrylate, dipentaerythritol
hexa(meth)acrylate, hexa(meth)acrylate of adduct between
dipentaerythritol and e-caprolactone and the like;
compounds having aminomethylol groups or alkyl substituted
aminomethylol ~roups, such as melamine formaldehyde resins,
glycolyl formaldehyde resins, urea formaldehyde resins,
homopolymers and copolymers of a,~-unsaturated compounds
having aminomethylol group or alkylated aminomethylol
group and the like;
2 2
compounds having acetal groups or ketal groups, such as
polyfunctional acetal compounds or polyfunctional ketal
compounds prepared by the reaction of polyfunctional
ketones, polyfunctional aldehYdes, polyfunctional vinyl
ether compounds and the like compounds with alcohols or
ortho acid esters, condensation products of the
polyfunctional acetal compounds with polyols, homopolymers
and copolymers of addition products of the vinyloxyalkyl
(meth)acrylate with alcohols or ortho acid esters; and the
like other compounds.
The compound (B) 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 be utilized in combination.
The thermosetting composition of the invention may
comprise the compound (A) and the compound (B) or it may
comprise compound (D) which is a self-crosslinking compound
having (a) one or more, preferably from one to 50, more
preferablY from one to 20, functional groups of the formula
C2]:
2 3
l7
-Rfi-Z' C-Z2-R' n
H~_RD
R8 t2]
wherein R~, R7, R8, R9, Rl~, Zl and Z2 are the same as
described before, and (b) one or more, preferably from one
to 50, more preferably from one to 20, reactive functional
groups which can form a 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) and/or the compound (B).
Examples of the functional gro~p (a) of the formula [2]
of the compound (D) are the same as the examples of the
functional group of the formula [1~ irl the compound (A)
already described. Examples of the reactive functional
group (b) are the same as the examples of the reactive
functional groups of compound (B).
The compound (D) can be prepared from a compound having
one or more, preferably from one to 50, more preferably
from one to 20, hydroxyl groups and/or thio~ groups and one
or more, preferably from one to 50, more preferably from
one to 20, of the reactive functional groups in the
molecule by using the same reaction as the reaction
utilized in the preparation of the compound (A). The
24
compound (D) can also be prepared by copolymerization of
the a,~-unsaturated compound having the functional group
of the formula [2] and the a,~-unsaturated compound having
the reactive functional group.
The compound (D) has the functional group of formula
[2] and, furthermore, may have two or more kinds of the
reactive functional groups in the same molecule.
The functional groups of formulas C1] and [2~ of the
compound (A) and the compound (D) regenerate free hydroxyl
groups and/or thiol groups under the heated condition and
form chemical bonds with the reactive functional groups in
the compound (B) and the compound (D). It is also possible
that the functional groups of formulas [1~ and [2] have
addition reactions with the reactive functional groups of
the compound (B) and the compound (D) caused by the highly
polari~ed structure of the functional groups of formulas
[1~ and [2~. ~hen the reaction of this kind takcs place,
the crossl;nking reaction is not accompanied with anY
component leaving from the reacting system and the reaction
system can contribute to the decrease of formation of
volatiled organic compounds.
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
2 5
2 ~ 2
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 blocked functional group in the composition
and the reactive functional group to form a 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.
In the present invention, it is necessary that a
thermal latent acid catalyst (C) which shows activity in
the curing condition at an elevated temperature is
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 exhibits the activity at the temperature
above 60~. If the thermal latent acid catalyst shows the
catalytic activity under 60~, the prepared thermosetting
composition has undesirable properties, such as increase of
viscosity during storage and formation of gel.
Prefsrred examples of the thermal latent acid catalyst
2 6
are compounds prepared by neutrali~.ing a protonic acid with
a Lewis base, compounds prepared by neutral izing a l,ewis
acid with a Lewis base or by mixing a Lewis acid with
trialkyl phosphate, compounds of esters of sulfonic acids,
compounds of esters of phosphoric acid and onium compounds.
Examples of the compound prepared by neutralizin~ a
protonic acid with a Lewis base are: compounds prepared by
neutralizing halogenocarboxylic acids, su]fonic 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, monoeth~ylamine, triethylamine,
pyridine, piperidine, anilirle, morpholine, cyclohexylamine,
n-butylamine, monoethanolamine, d;ethanolamine,
triethanolamine and the like other amine compounds,
trialkylphophine, triaryl phosphine, trialkyl phosphite,
triarylphosphite, commercial acid-base blocked cata]ysts,
such as Nacure 2500X~, X-47-110~, 3525~ and 5225~ (products
of King Industries Co., Ltd.) and other like compounds.
Fxamples of the compounds prepared by neutralizing a
Lewis acid with a L,ewis base are compounds prepared by
neutralizing BFa, FeCl3, SnCl~, AlCl~" ZnCl~ and other like
Lewis acids with Lewis bases described above or by mixing
Lèwis acid with trialkyl phosphate.
2 7
The esters of sulfonic acids are compounds having the
formula [7~:
o
Rl8-S_o-Rls3
O [7]
wherein Rl8 is selected from the grcup consisting of phenyl
group, substituted phenyl group, naphthyl group,
substituted naphthyl group and alkyl group and Rl~ is a
group of 3 to 18 carbon atoms selected from the group
consisting of alkyl group, alkenyl group, aryl group,
alkary~ group, alkanol group and saturat,ed or unsaturated
cycloalkyl or hydrocycloalkyl group which is bonded with
sulfonyloxy group through a primary or secondary carbon
atom. ~xamples 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
isopropanol, 2-butanol, 2-hexanol, 2-octanol, cyclohexanol
and the like, and ~-hydroxyalkylsulfonic esters prspared
by the reaction of the sulfonic acids and compounds
containing oxirane.
2 8
2 ~ 2
The esters of phosphoric acid are, for example,
compounds of the formula [8]:
11
(R2~-O-)m-P-(-OH)3 m [8]
wherein R20 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 C~] through [12]:
[R2 ' ~NR22]+X- [~3]
[R2 1 3pR22]~X- Clo]
[R2 1 20R22]~X- [11]
and
[R2l2SR22]+X- [12]
wherein R2l is a group of 1 to 12 carbon atoms selected
from the group consisting of alkyl group, alkenyl group,
aryl group, alkaryl group, alkanol group and cycloalkyl
group, two RZI may be bonded together to form a
heterocyclic ring in which N, P, O or S is the hetero atom,
R22 is a hydrogen atom or a group of 1 to 12 carbon atoms
selected from the group of alkyl group, alkenYl group, aryl
group and alkarYl group and X~ is selected ~rom the group
of SbPG-, AsF6-, PF~- and BF~-.
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
temperaturo at which free hydroxyl group or thiol group is
regenerated from the blocked functional group of formula
Cl] or formula C2]. kind of the reactive functional 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 hours.
The thermosetting composition of the invention can be
utilized for coating compositions, ink, adhesive, molded
plastics and the like without other ingredients and,
3 O
according to the needs, it may be compounded with coloring
pigments, fillers, solvents, ultraviolet light absorbents,
antioxidants and other ingredients.
The present invention also provides the novel thermal
latent hydroxyl compounds or thermal latent thiol compounds
and the novel method of preparation thereof along with the
thermosetting compositions described above. The thermal
latent hydroxyl compounds or the thermal latent thiol
compounds are compounds which are prepared by the reaction
of a polyol compound or a polythiol compound having two or
more, preferably 2 to 50, more preferably 2 to 20, hydroxyl
groups or thiol groups in the molecule, hydroxyl equivalent
or thiol equivalent of not more than lOOOg/mole and number
average molecular weight of not more than 4000, prèferably
not more than 2000, with a vinyl ether compound, a vinyl
thio~ther compound or a cyclic vinyl ether compound, such
as a heterocyclic compound having vinyl type double bond
and an oxy~en atom or a sulfur atom as the hetero atom, of
the formula C13]:
R'; Rl 2
C=C-Y4-R~s
R~4 C13]
~herein R'2, R'~, R'4, R'~ and Y4 are already defined
~efore, in the presence of acid catalyst at the temperature
3 1
,,
of preferably in the range from the room temperature to
100~. The hydroxyl group or thiol group is converted by the
reaction to a blocked hydroxyl group or thiol group of the
formula [3]:
Rll 2
-R''-y3-c y4-Rls
HC_RI 4
R'3 [3]
wherein Rll, R'2, Rl3, R'4, R''', y2 and Y4 are already
defined before.
When the number of hydroxyl group or thiol group in the
molecule of polyol compound or polythiol compound utilized
for the preparation of the thermal latent hydroxyl
compounds or thiol compounds is le~s than two or when the
hydroxyl equivalent or thiol 0quivalent of the polyol
compound or polythiol 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 polyol compound or polythiol
compound is more than 4000, viscosity of the thermosetting
composition becomes high and processability is inferior.
Rxamples of the polyol compound and polythiol compound
are the same as the examples of the compound (A) of the
thermosetting composition.
3 2
Examples of the vinyl ether compound, the vinyl
thioether compound or the cyclic vinyl ether compound, such
as a heterocyclic compound having vinyl type double bond
and an oxygen atom or a sulfur atom ~s the hetero atom, of
the formula [13] are the same as the examples of the
compound of formula [S] which is utilized for the
preparation of the compound (A).
The thermal latent hydroxyl compound and the thermal
latent polythiol 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
constru0d to limit the scope of the invention.
Properties of the coated film were evaluated by the
following methods,
(1) Resistance to acid-l
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 ~ hour at
20~.
(2) Resistance to acid-2
3 3
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 40~.
(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 40~.
(4) Impact resistance
By using an impact tester (Japanese Industrial Standard
K-5400 (1979), method of 6.13.3 B), a test piece was
clamped to an impact frame of 6.35 mm radius and a weight
of 500 g was dropped from the height of 40 cm on the test
piecs. Damage made on the coating film was observed by
visual comparison.
(5) ~eatherin~ resistance
By using a sunshine weathermeter (Japanese Industrial
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.
3 4
2~
(6) Knoop hardness
Measurement was made by using N type micro-
hardnessmeter (manufactured by Shimazu Seisakusho, Co.,
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
Cardener viscosity was measured by the method of
Japanese Industrial Standard K-5400 (1979)) 4.2.2 (bubble
tube viscometer).
(~) Yield of a reaction product was calculated from the
value.s of analysis of the unreacted vinyl ether by gas
chromatography.
Abbreviations and trade nalnes l~sed in the examples are
listed in the following.
AIBN: 2,2'-azo-bis-isobutyronitrile
BMA: n-butyl methacrylate
RHA: 2-ethylhexyl acrylate
GMA: glycidyl methacrylate
lAAn: itaconic acid anhydride
IRM: isocyanatoethyl methacrylate
MMA: methyl methacrylate
~.3~3
TMSPMA: methacryloyloxypropyltrimethoxysilane
PTSA: p-toluene sulfonic acid
DDBSA: dodecylbenzene sulfonic acid
10% PTSA: 10 weight % solution of p-toluene
sulfonic acid in isopropyl alcohol.
10% pyridine: 10 weight % solution of pyridine
in xylene.
Acid catalyst A: xylene solution of (1-methylethyl)
p-toluene sulfonate in Example of preparation of material
17.
Acid catalyst B: xylene solution of (1-methylheptyl)
p-toluene sulfonate in Example of preparation of material
18.
Acid catalyst C: xylerle solution of (1-methylethyl)
dodscylbenzene sulfonate in example of preparation of
material 1~.
Acid catalyst D: 10 wsiKht % solution of
di-2-ethylhexyl phosphate (a product of Wako Junyaku Co.,
Lt,d,) in isobutanol.
Acid catalyst e: lo weight % solution of triethylamine
salt of zinc chloride in dimethylsùlfoxids.
Acid catalyst F: 50 weight % solution of
3-methyl-2-butinyltetramethylenesulfonium hsxafluoro-
antimonate in dichloroethane.
3 6
~ h~
Acid catalyst G: 20 weight % solution of~-methoxybenzylpyridinium hexafluoroantimonate in acetone.
C-1203~: Vesturit Catalyst 1203, a product of Impecs
Chemicals Co., Ltd., nonionic thermal latent acid catalyst,
non-volatile matter 50 weight %.
Coronate EH~: a product of Nippon Polyurethane
Industry Co., Ltd., trimer of hexamethylene diisocyanate,
content of isocyanate 21 weight %.
Cymel 303~: a product of Mitsui Cyanamide Co.,
Ltd., methylated melamine resin, non-volatile matter 98
weight %.
Denacol RX-421~: a product of Nagase Kasei Kogyo Co.,
Ltd., a polyepoxy compound having epoxy equivalent of 155.
Plexorez UD 3206: a product of King Co., Ltd.,
urethanediol, non-volatile matter 97,5 weight %, hydroxyl
value 350
K-~lex 188-509: a product of King Co., Ltd.,
polyesterdiol, non-volatile matter 96 weight %, hydroxyl
value 235
KR-214~: a product of Shinetsu Chemical Co.,l.td.,
silicone vanish, hydroxyl equivalent ~0, non-volatile
matter 70 weight %,
MAGML: MAGNP lOOe, a product of Nitsui Cyanamide
Co,,Ltd., methylacrylamide glycolate methyl ether
Nodaflow~: a product of Monsanto Co., a leveling agent.
Penraerythritol tetrakis(thioglycolate): a product of
Yodo's Chemical Co., Ltd., mercaptane equivalent 1l9.
Praccel 305~: a product of Daicel Chemical Industries
Co., Ltd., polycaprolactone polyol, non-volatil~ matter
100%, hydroxyl value 235.
Praccel E-4886: a product of Daicel Chemical Industries
Co,, Ltd., caprolactone polyol, hydroxyl value 579.
Titanium dioxide JR-602~: a product of Teikoku Kako
Co.,Ltd., titanium dioxide of rutile type.
Three kinds of the compound (A), A-1, A-2 and A-3, were
prepared.
Rxample of preparation of material l through 3
A mixture shown in Table 1 was charged into a
four-necked flask equipped with a thermometer, a reflux
condenser, a stirrer and a dropping funnel and a mixture of
vinyl ethers shown in Table 1 was dropped from the dropping
funnel in 1.5 hours at a constant rate while the
temperature of the charged mixture in the flask was kept at
35~. After the reaction mixture was kept at 35~ for
further 4 hours under stirring, 21 g of sodium bicarbonate
was added and the reaction was kept going for further 5
hours at 35~. Excess amount of sodium bicarbonate was
removed by filtration and excess amount of vinyl ethers was
removed by distillation in vacuo. Thus, the compounds A-l
through A-3 were prepared as summarized in Table l.
Example of preparation of material 4 through 6
Three kinds of the compound (A), A-4 through A-6, were
prepared in the following examples.
(l) Preparation of a,~-unsaturated compound
Into a four-necked flask equipped with a thermometer, a
reflux condenser, a stirrer and a dropping funnel, 9ll.0
weight parts of 2-hydroxylethyl methacrylate and l.8 weight
part of 35 weight % hydrochloric acid were charged and the
mixturo was kept at 35~ ur1deI heating and stirring. Then,
618.2 weight parts of 3,4-dihydro-21-1-pyran in Example of
preparation material 4, 529.9 weight parts of ethyl vinyl
ether in example of preparation of material S and 736.5
weight parts of butyl vinyl ether in Rxample of preparation
of material 6 were dropped into the mixture in l.5 hours at
a constant rate from the dropping funnel. After the the
reaction mixture was kept at 35~ under stirring for further
4 hours, 21 weight parts of sodium bicarbonate were added
to the mixture and the mixturc was kept at 35~ for 5 hours.
~hen the reaction was finished, the reaction mixture was
3 9
treated by the same method as in Example of preparation of
material 1 through 3 and a,~-unsaturated compounds were
prepared by the following yields: A-4 (a) 92.3%; A-5 (a)
93.3%; and A-6 (a) 91.8%.
(2) Preparation of compounds A-4, A-5 and A-6
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 as
shown in Table 2 and kept at 80~ under heating and
stirring. A mixture of monomers and the initiator (shown in
Table 2 as 'composition of dropped mixture') was dropped
into the mixture from the dropping funnel in 2 hours at
80~. After finishing the dropping, the mixture was kept at
80~ for 1 hour, Then, a solution of the initiator (shown
in Table 2 as 'additional catalyst') was added to the
reaction mixture and the reaction mixture was kept at 80~
for 4 hours. ~hen the reaction was finished, compounds
A-4, A-S and A-6 having the properties shown in Table 2
were prepared.
~xample of preparation of material 7 through 1~
~ ive kinds of compound (B), compound M-1 through B-5
were prepared by the following method.
Into a four-necked flask equipped with a thermometer, a
4 O
~3J j~
reflux condenser, a stirrer and a dropping funnel, 40.0
weight parts of solvent which was n-butyl acetate were
charged and kept at 100~ by heating under stirring. A
mixture of monomers and the initiator (shown in Table 3 as
'composition of dropped mixture') was dropped into the
mixtllre from the dropping funnel in 2 hours at lO0~. After
finishing the dropping, the mixture was kept at 80~ for 1
hour. Then, a solution of the initiator (shown in Table 3
as 'additional catalyst') was added to the reaction mixture
and the reaction mixture was kept at 100~ for 2 hours.
When the reaction was finished, compounds B-l through B-5
having the properties shown in Table 3 were prepared.
example of preparation of material 12
~ ne kind Oe compound (B), compound B-6, was prepared by
the following method.
Into a four-necked flask equipped with a thermometer, a
reflu% condenser and a stirrer, the following components
were charged and kept under 100~ and stirring. Acid value
of the reaction mixture in the flask was measured from
time to time and the reaction was finished when the acid
value decreased to a value not more than 2. The compound
B-6 having content of non-volatile matter 50,8~ and
Gardener viscosity Y-Z was prepared.
4 1
Compound B-5 of Example oflOO.O weight parts
preparation of material 11
acrylic acid7.2 weight parts
hydroquinone0.1 weight parts
N,N-dimethylbenzylamine0.1 weight parts
xylene 7.0 weight parts
Example of preparation of material 13
One kind of compound (B), compound B-7, was prepared by
the following method.
Into a four-necked flask equipped with a thermometer, a
reflux condenser, a stirrer and a dropping funnel, 206.0
weight pàrts of methyl orthoformate and 0.3 weight part of
boron trifluoride diethyl etherate were charged and the
mixture was kept at 0-5~ with stirring under cooling in an
ico bath. To the mixture, 87.7 weight parts of butyl vinyl
ether were added by droppinK ~rolD a dropping funnel at à
constant rate for Z 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.~
weight part of 30 weight % methanol solution of sodium
methylate was added to the mixture to finish the reaction.
The acetal product obtained by distillation of the reaction
product at 75-80~ (4 mmHg) contained 98 weight % of the
4 2
effective component.
Into a four-necked flask equipped with a thermometer, a
reflux condenser fitted with a Dienstag trap. a stirrer and
a dropping funnel, 618 weight parts of the purified acetal
product prepared above, 13~ weight parts of
trimethylolpropane and 4 weight parts of p-toluene sulfonic
acid were charged and the mixture was kept at 90~ by
heating under stirring. Methanol was continuously removed
while the reaction proceeded. ~hen 96 weight parts of
melhanol were recovered, the reaction was finished and
compound B-7 was obtained, of which content of non-volatile
matter was 98 weight % and Gardener viscosity was X-Y.
Rxample of preparation of material 14 through 16
Three kinds of compound (D), compounds D-l, D-2 and
D-3, were prepare by the following method.
Into a four-necked flask cquipped with a thermometer, a
roflux condenser, a stirrer and a dropping funnel, an
initial portion of solvent which was n-hutyl acetate 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 Tahle 4 ('composition of
dropped mixture') was added ~y dropping to the solvent at
80~ at a constant rate for 2 hours. When the addition of
43
the dropping composition 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, D-2 and D-3 having the
properties shown in Table ~ were obtained.
Rxample of preparation of material 17
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
2-propanol wer~ charged and the flask was cooled by an ice
bath. Potassium t-butoxide, ~.9 weight parts, was added
to 2-propanol to dissolve in it and a solution of 53.~
weight parts of p-toluene sulfonyl chloride in 300 weight
parts of diethyl ether were added to the solution by
droppin~ 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 ~A1/16 (a
product of Wako Junyaku Co., Ltd.). After removing the
4 4
solvent by using an evaporater, 40 weight parts of
l-methylethyl p-toluene sulfonate were obtained (yield
67%). The thermal latent acid catalyst thus prepared was
dissolved in 238 weight parts of xylene to for~ a solution
of 10 weight % based on p-toluene sulfonic acid.
axample of preparation of 18 and ]9
In Example of preparation of material 18, 2-octanol was
used in place of 2-propanol in Example of preparation of
material 17. In Example of preparation of material 19,
dodecylbenzene sulfonyl chloride was used in place of
p-toluene sulfonyl chloride in Rxample of preparation of
material 17. Other procedures were made in the same way as
Rxample of preparation of material 17. In Example of
preparation of material 18, l mothylheptyl
p-toluene sulfonate was obtained in the yield of 72% and,
in Rxample of preparation of material 19, l-methylethyl
dodecylbenzene sulfonate was obtained in the yield of ~3%.
The thermal latent acid catalysts thus prepared were
dissolved in xylene to form a solution of 10 weight % based
on p-toluene sulfonic acid or dodecylbenzene sulfonic acid
in the same way as in Rxample of preparation of material
17,
~ S
Thermal latent l~yd~oxyl compounds and thermal latent
thiol compounds were prepared by the following methods.
~xample of p~eparation of material 20
Polyol compound A was prepared by the following method.
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~ (a product of
Shinetsu Chemical Industry Co., Ltd., a methoxysilicone
compound, methoxy equivalent 160), 312.0 weight parts of
neopentyl glycol and 0.8 weight parts of p-toluene sulfonic
acid were charged and kept at 160~ u1lder heating and
stirring. When the reaction started, methanol was removed
from the reaction system at temperatures above 140~. After
the reaction was continued until ~6 weight parts of
methanol was r0covered, polyol compound A having ~5 weight
% of non-volatile matter and 242 of hydroxyl value was
prepared.
example of preparation of material 21
Polyol compound B was prepared by the followin~ method.
In a flask equipped with a stopper, 2B8.0 weight parts
of trimethylolpropane, 224 weight parts of
3,4-dihydro-2H-yl-methyl-3,~-dihydro-2H-pyran-2-carboxylate
4 6
2 ~ 2
and 0.4 weight part of dodecylbenzene sulfonic acid were
charged and stirred at the room temperature for 24 hours.
Thus, polyol compound B having 96 % of non-volatile matter
and ~56 of hydroxyl value was prepared.
~xamples 1 through 6
Into a four-necked flask equipped with a thermometer,
reflux condenser. a stirrer and a dropping funnel, a
mixture having the components shown in Table 5 was charged
and a vinyl ether compound shown in Table 5 was dropped
into the mixture at a constant rate in 1.5 hours from the
dropping funnel at a constant temperature of 35~. When the
dropping was finished, the mixture was further stirred at
35~ for 4 hours, Then, 6 weight parts of sodium
bicarbonate aere add~d to the mixture and the reaction was
continued at 35~ for further 5 hours, Sodium bicarbonate
was removed by filtration and the remaining vinyl ether
compounds aere removed by distillation in vacuo. Thermal
latent hydroxyl compounds [1] through [5] and a thermal
latent thiol compound [6] were prepared in the yields shown
in Table 5.
~xamples 7 and 8
(1) Preparation of ~ unsaturated compounds
4 7
2 ~
Into a flask, equipped with a thermometer, a reflux
condenser, a stirrer and a dropping funnel, 911.0 weight
parts of 2-hydroxyethyl methacrylate and 1.8 weight parts
of 35% hydrochloric acid were charged and kept at 35~ under
heating and stirring. In Example 7, 618.2 weight parts of
3,4-dihydro-2H--pyran and, in Example 8, 529.9 weight parts
of ethyl vinyl ether was dropped into the mixture at a
constant rate in 1.5 hours from the dropping funnel. When
the dropping was finished, the mixture was kept at 35
under stirring for further 4 hours. Then, 21 weight parts
of sodium bicarbonate were added to the mixture and the
reaction in the mixture was kept for 5 hours. When the
reaction was finished, sodium bicarbonate was removed by
filtration an~ the remaining vinyl ether compound was
removed by distillation in vacuo. Two kinds of
~ unsaturated compounds were prepared in the following
yields: ~xample 7 (1): 92.3 weight %; example 8 (1): 93.3
weight %.
(2) Preparation of thermal latent hydroxyl compounds
Into a flask, equipped with a thermometer, a reflux
condenser, a stirrer and a dropping funnel, an initial
portion of solvent which was xylene as shown in Table ~ was
charged and kept at 100~ under heatinK and stirring. A
mixture of monomers and a polymeri~ation initiator shown in
4 8
Table 6 ('composition of dropped mixture') was added by
dropping to the solvent 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 30
minutes and, then, an additional amount of initiator
solution shown in Table 6 ('additional catalyst') was added
to the mixture. The mixture was kept at 100~ for 2 hours
before finishing the reaction and finally the thermal
latent hydroxyl compounds [7] and [8] were prepared.
Results of Examples 1 through 8 are summarized in Table
7.
Comparative example of preparation of material 1
One compollnd (A), A-7, was prepared by the following
method.
Into a four-necked flask equipped with a thermometer, a
reflux condenser, a stirrer and a dropping funnel, 200
weight parts of xylene were charged and kept at 80~ under
heating and stirring. A mixture having the following
composition was dropped at a constant rate from the
dropping funnel in 2 hours at 80~, ~hen the dropping was
finished, the 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, After
4 ~
the mixture was kept at 80~ for further 4 hours, the
compound A-7 having 50.3 weight % of non-volatile matter
and Gardener viscosity at 25~ V-~.
2-hydroxyethyl methacrylate 130.0 weight parts
n-butyl methacrylate100.0 weight parts
methyl methacrylate175.1 weight parts
2-ethylhexyl acrylate94.5 ~eight parts
n-butyl acetate 217.5 weight parts
2,2'-azo-bis-isobutyronitrile 22.5 weight parts
~xample 9 through 19
These examples show application of the composition to
ane coat solid color coating.
(1) Pr~paration of coating compositions
Components summarized in Table 8 were utili%ed 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 lO~m. Materials
excluding following components were charged into the sand
mill: the compound A~l in example ~, the compound A-2 in
example 10, the compound A-3 in Rxamples 11 and 12, KR-214~
in example 13, Cymel 303~ in Rxample 14, the compound B-7
in example 15, Coronate RH0 in ~xample 16 and Denacol
eX-421e in ~xample 19. All the raw materials were charged
2 ~ 2
into the sand mill in ~xamples 17 and 18. In Examples 9
through 16 and Example 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 Examples 17 and 18, the materials
treated by the sand mill were utilized for the preparation
of one component coating composition. 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 in Table 9 show that the increase of viscosity
was very 91 ight in all cases and that the coating
composition9 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 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
~ 93 ~ 2
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 millutes 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 ~ord cup No. 4) and applied to the base
test piece prepared before by air spray coating. Test
pieces were prepared by curin~ 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 havin~ good gloss
were prepared. All the coatings showed excellent acid
resi~tance, impact resistanco, weathering resistance and
hardnsss.
Weatherine resistance was evaluated by exposure for
1000 hours.
Comparative examples 1 and 2
Components listed in Table 10 were utili~ed for the
preparation of the coating composit,ions, The components
were dispersed and made into coating compositions by the
same method as in ~xamples 9 through 19. The materials
52
2 ~ 2
excluding pentaerythritol tetrakis(thioglYcolate) in
Comparative example 1 and the materials excluding Coronate
RH0 in Comparative examples 2 were dispersed by using a
sand mill and utilized for preparation of coating
materials.
The coating ~aterials thus prepared were evaluated on
the storage stability in the same method as in Examples 9
through la. In the both examples. viscosity increased
remarkably with the period of storage. In the case of
Comparative example 1, the coating material was gelatinized
after S days because neither thiol group or epoxy group was
blocked to prevent crosslinking reaction of the both
funct;onal groups under the storage condition. In the case
of Co~parativ~ example 2, the coating compositions were
gelatinized after 3 days because neither hydroxyl group or
isocyanate group ~as blocked to prevPnt crosslinking
reaction of the both functional groups under the storage
condition.
~xamples 20 through 23
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
53
2 ~ 2
by mixing raw materials shown in Table 11. The clear
coating compositions prepared were evaluated on storage
stability by the same method as in ~xample 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 12.
(2) Preparation of test pieces
Raw coating compositions thus prepared were di~luted 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,
BFLCOAT No.60000 ~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~ ~or 3 minutes, the
dilutcd clear coating compositions were coated by air spray
coating and the test pieces were cured in the condition
shown in Table 12 to prepare final test pieces.
Results of the evaluation listed in Table 12 show that,
in all cases, uniform coating having good gloss were
prepared and the coating showed excellent acid resistance,
impact resistance, weathering resistance and hardness.
~eathering resistance was evaluated by exposure for
54
2 ~
3000 hours.
Comparative example 3
Clear coating composition was prepared by using
material of the following composition and evaluated on the
storage stability in the same method as in Examples 9
through 19. Viscosity increased remarkably with the period
of storage, leading finally to gellation after 3 days,
because neither hydroxyl group or isocyanate group was
blocked to prevent crosslinking reaction of the both
functional groups under the storage condition.
compound A-7 lO0.0 weight parts
Coronate ~H0 20.0 weigh~ parts
Modaflow~ 0.1 weight parts
xylene 5.0 weight parts
n-butyl acetate1.0 weight parts
examples 24 through 34
These examples show application of the composition to
one coat solid color coating.
(1) Preparation of coating compositiolls
Components summarized in Table 13 were utilized for the
preparation of the coating compositions. A Part of or all
materials were charged into a sand mill and dispersed until
5 5
2 ~ 2
the particle size decreased to not more than 10~m. Materials
excluding following components were charged into the sand
mill: the compound A-l in Example 24, the compound A-2 in
~xample 25, the compound A-3 in Examples 26 and 27, KR-214~
in Example 28, Cymel 303~ in ~xample 29, the compound B-7
in Example 30, Coronate EH~ in Example 31 and Denacol
EX-421~ in Example 34. All the raw materials were charged
into the sand mill in Rxamples 32 and 33. In Examples 24
through 31 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 ~xamples 32 and 33, 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 in Table 1~ 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
5 6
2 ~ 2
Cationic electro coating paint AQUA No.4200~ (a product
of Nippon Oil and Fats Co., Ltd.~ was applied by
electrodeposition to a sof~ 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
Seale.~ (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 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 ~ord cup No. 4) and appli0d 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 14.
Results of the evaluation of coatings are shown in
Table 14. In all cases, uniform coating having good gloss
were prepared. All the coatings showed excellent acid
resistance, impact resistance, weathering resistance and
hardness.
~eathering resistance was evaluated by exposure for
5 7
1000 hours.
Comparative example 4 through 6
Components listed in Table 15 were utilized for the
preparation of the coating compositions. The components
were dispersed and made into coating compositions in the
same method as in Examples 24 through 30. The materials
excluding pentaerythritol tetrakis(thioglycolate) in
Comparative example 4 and the mat0rials excluding Coronate
RHg in Comparative examples 5 and 6 were dispersed by using
a sand mill and utilized for preparation of coating
compositions.
The coating compositions thus prepared were evaluated
on the ~tora8e stability in the same method as in ~xamples
24 tllrough 34. In the both examples, viscosity increased
remarkably with the period of stora~e. In the case of
Comparative example 4, the coating material was gelatinized
after 5 days because neither thiol group or epoxy group was
blocked to prevent crosslinking reaction of the both
i'unctional groups under the storage condition. In the case
of Comparative example 5, the coating Material was
gelatinized after 3 days because neither hydroxyl group or
isocyanate group was blocked to prevent crosslinking
reaction of the both functional groups under the storage
5 8
2~ ~c9~ 2
condition.
Test pieces were prepared and evaluated by utilizing
the coating compositions prepared above by the same method
as in Example 24 through 34. The results are shown in
Table 16. Properties of the coating of Comparative example
6 cured at 120~ was inferior to the coating of Example 23
because thermal latent acid catalyst was not utilized in
Comparative example 6.
~ eathering resistance was evaluated by exposure for
lOOO hours.
~xamples 35 through 41
These exa~ples 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 17. The clear
coating compositions prepared were evaluated on storage
stability by the same method as in Rxample 24 through 34.
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 18.
2) Preparation of test pieces
Raw coating compositions thus prepared were diluted in
5 9
the same method as in Examples 24 through 34. Base test
pieces ~ere also prepared in the same method as in Examples
24 through 3~. A silver metallic base coating composition,
B~LCOAT No.6000~ (a product of Nippon Oil and Fats Co.,
Ltd.) was applied to the base test piece by air spraying
with ;nterval of 1 minute 30 seconds in 2 stages in an
a-ount to form a fiIm having dried thickness of 15~m.
After the test pieces were set at 20~ for 3 minutes, the
diluted clear coating compositions were applied by air
spray coating and the test pieces were cured in the
condition sho~n in Table 18 to prepare final test pieces.
Results of the evaluation listed in Table 18 show that,
in all cases, uniform coating films having good gloss were
preDared and the coating showed excellent acid resistance,
impact resistance, ~eathering resistance and hardness.
~ eathering resistance was evaluated by exposure for
3000 hours.
Comparative examples 7 and 8
Components listed in Table 1~ were utilized for the
preparation of the clear coating compositions and the clear
coating compositions pr0pared were evaluated on the storage
stability in the same way as in ~xamples 24 through 34.
ViscositY increased remarkably with the period of storage,
~ O
leading finally to gellation after 3 days, because neither
hydroxyl group or isocyanate group was blocked to prevent
crosslinking reaction of the both functional groups under
the storage condition in the case of Comparative example 7.
Test pieces were prepared and evaluated by utilizing
the coating materials prepared above by the same method as
in Rxample 35 through 41. The results are shown in Table
20. Properties of the coating of ComParatiVe example 8
cured at 120~ was inferior to the coating of Example 36
because thermal latent acid catalyst was not utilized in
Comparative example 8.
Weathering resistance was evaluated by exposure for
3000 hours.
examples ~2 through 50
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 ra~ materials shown in Table 21, 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 in Table 1~ 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.~200~ (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 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 ~O~m and the plate
was bflked at 140~ for 30 minutes to obtain a base test
piece.
A silver metallic base coating composition, BL~COAT
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 raw clear coating
compositions of (1) which were diluted to spraYing
r
viscosity (25 seconds by Ford cup No. 4 at 20~) were
applied by air spray coating and the test pieces were cured
in the condition shown in Table 22 to prepare final test
pieces.
Results of the evaluation listed in Table 22 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 evalua~ed by exposure for
3000 hours.
Comparative examples 9 and 10
Clear coating compositions were prepared by using
materials of the compositions shown in Table 23 and
evaluated on the storage stability in the same method as in
examples 42 throueh S0. In Comparative example ~, the
coating composition gelatinized after 3 days because the
coating compositions did not utilize a thermal latent
hydroxyl compound unlike Rxample 45, In Comparative
example 10, the coating composition gelatinized after 5
days because the coating composition did not utilize a
thermal latent thiol compound unlike Rxample 47.
Rxamples 51 through 53
6 3
;
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 ra~ materials shown in Table 24. The coating
compositions pr~pared 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 in Table 25 show that the increase of viscosity
was very slight in all cases and that the coating
composition~ had excellent st~rage stability.
(2) Preparation of test pi0ces
Silver metallic base coating composition, BLLCOAT
No.BOOO~ (a product of Nippon Oil and ~ats Co., Ltd.) was
spplied to the base test piece, which was prepared by the
same method as in Lxamples 9 through 19 (2) with
application of intermediate coating, by air spraying with
interval of 1 minute 30 seconds in 2 stages in an amount to
form a film having dried thickness of l5~m. After the test
pieces were set at 20~ for 3 minutes, the raw clear coating
compositions of (1) which were diluted to spraying
6 4
~3~2
viscosity (25 seconds by Ford cup No. 4 at 20~) were
applied by air spray coating and the test pieces were cured
in the condition shown in Table 25 to prepare f inal test
pieces.
Results of the evaluation listed in Table 25 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.
~ eathering resistance was evaluated by exposure for
3000 hours.
~ hile the invention has been particularly shown and
described with reference to preferred embodiments threrof,
it will be understood by those skilled in the art that the
fore~oing and other changes in form and details can be made
therein without departing from the spirit and scope of the
invention.
To summarize the advantages obtained by the invention,
the thermosetting compositions of the invention are
excellent in storage stability and give cured products
having excellent chemical properties, physical properties
and weathering resistance. They are favorably utilized in
coating compositions, ink, adhesive and molded plastics.
6 5
The thermal latent hydroxyl compounds and thermal
latent thiol compounds of the invention are favorably
utilized to provide the thermosetting compositions which
give the above excellent characteristics at relatively low
curing temperature and can be utilized as the one component
thermosetting compositions. The thermal latent hydroxyl
compounds and thermal latent thiol compounds are
efficiently prepared by the method of preparation of the
invention.
T a b l e
~xample of preparation of material 1 2 3
compound (A) A-1 A-2 A-3
OH or SH compound"
composition Praccel 305 1279.4
of the K-flex 188-50 - 1671.4
initial pentaerythritol - - 833.0
material, tetrakis
weight part (thioglycolate)
hydrochloric acid, 1.8 1.7 1.5
35 weight %
vinyl 3,4-dihydro-2H-pyran 618.2 - -
~ther, ethyl vinyl ether - 529.9
~eight part butgl vinyl ether - - 736.5
yield, 91.4 92.3 90.5
~eight X
1) compound comprising polyfunctional hydroxyl groups or e . ' comprising
polyfunctional thiol groups.
67
T a b l e 2
Example of preparation of material 4 5 6
compound A A-4 A-5 A-6
xylene 200.0 200.0 200.0
a,~-unsaturated c n, ~ A-4(a) 231.9
a,~-unsaturated co~pound A-5(a) - 216.5
composition a,~-unsaturated c n, uul-d A-6(a) - - 250.5
of dropped n-butyl methacrylate 100.0 100.0 100.0
mixture, methyl methacrylate 175.1 175.1 175.1
2-ethyl hexyl 94.9 94.9 94.9
weight part acrylate
n-butyl acetate 114.8 130.6 95.9
AIBN 23.3 22.9 24.0
additional n-butyl acetate 57.0 57.0 57.0
catalyst, AIBN 3,0 3.0 3.0
weight part
properties non-volatile 58.3 57.4 60.3
matter,
weight %
Gardener viscosity P-Q S-T T-U
68
T a b 1 e 3
~xample of preparation of 7 8 9 10 11
material
c -. ~ (B) B-l B-2 B-3 B-4 B-5
IAAn 22.40 - - - -
TMSPMA - 16. 60 - - -
MAGME0 - - 19. 22
composition IEM - - - 31.00
of dropped GMA ~ 28.40
mixture, BMA 20. 00 20. 00 2n. 00 20. 00 20.00
weight part MMA 28.87 51.19 33.80 25.10 34.43
EHA 28.73 12. 21 28.90 23.90 17.17
AIBN 2. 00 2.00 2. 00 2. 00 2.00
n-butyl acetate - 54.00 52.08 54.00 54.00
dioxane 54.00
additional n-butyl acetate 3.80 3.80 3.80 3.80 3.80
catalyst, AIBN 0. 20 0. 20 0. 20 0. 20 0. 20
~eight part
properties non-volatile 50.3 51.0 50.2 51.3 50.2
matter,
weight %
Gardoner X-Y S-T V-W R V
viscosity
69
T a b 1 e 4
~xample of preparation of material 14 15 16
compound (D) D-l D-2 D-3
n-butyl acetate, weight parts 40.00 40.00 40.00
compound A-4(a) 23.19
C! .~ld A-5(a) - 2~.65
c . ~ d A-6(a) - - 25.05
2-isocynatoethyl methacrylate 15.50
C.lpO~ t methacryloyloxy trimethoxysilane - 8.30
of dropped itaconic anhydride - - 11.20
mixture, BMA 20.00 20.00 20.00
MMA 32.63 43.11 31.95
weight part EHA 18.87 15.59 23.85
dioxane - - 39.45
xylene 41.31 42.85
AIBN 4.50 4 50 4 50
additional n-butyl acetate 3.80 3.80 3.80
catalyst, AIBN 0.20 0.20 0.20
weight part
properties non-volatile 54.4 53.7 55.5
matter,
weight %
Gardener viscosity R M-N 0-P
~0
T a b l e 5
~xample 1 2 3 4 5 6
thermal latent hYdroxYl or [1] r2] r8] [~] [5] [6]
thiol c~ -. d
Praccel E-488~387.6
K-Flex 188-50~ - 477.5
composition Flexorez UD-32P - - 320.6
of charged polyol compound A - - - 695.6 - -
mixture, polyol compound B - - - - 492.2
pentaerythritol - - - - - 476.0
~eight part tetrakis
(thioglycolate)
hydrochloric acid 0.6 0.5 0.6 0.8 0.8 0.8
35 ~eight %
vinyl ethyl vinyl ether 302.4 151.2 - - - -~
ether, n-propyl vinyl - - - - 361.2
ether
weight part isobutyl vinyl - - 210.0 - - 420.9
ether
3,4-dihydro-2H- - - - 264.6 - -
pyran
yi~ld, ~eight X ~3.4 ~2.3 ~1.8 93.0 92.7 90.6
T a b l e 6
example 7 8
thermal latent hydroxyl compound [7] ~8]
xylene, weight part 191.7 191.7
a,~-unsaturated c~ ~.d 7 (1)231.9
componen~ a,~-unsaturated compound 8 (1) - 216.5
of dropped BNA 100.0 100.0
mixture, MMA 175.1 175.1
EHA 94 9
weight part n-butyl acetate 11~.8 130.6
AIBN 31.6 31.2
additional n-butyl acetate 57.0 57.0
catalyst, AIBN 3.0 3.0
weight part
non-volatile matter, weight % 58.5 57.7
~ 3 ~ ~ ~3 ~J
T a b 1 e 7 (Part 1)
example 1 2 3 4
properties of average number of 4 2 2 3
polyhydroxyl functional group
or polythiol equivalent, g/mole 97 239 160 232
compound number average 388 478 320 696
molecular weight
blocking agent" ~ve EVE IBV~ DHP
solution of thermal latent [l] [2] [3] [4]
hydroxyl or thiol compound
effective c~ pJnen~, 56.573.2 58.3 68.1
weight %
1) ev~: ethyl vinyl ether
IBVe: isobutyl vinyl ether
DHP: 3,4-dihydro-2H-pyran
(Table 7 continued)
73
2 ~
T a b l e 7 (Part 2)
Example 5 6 7 8
properties of average number of 4 4 3.5 3.8
polyhydroxyl functional group
or polythiol equivalent, g/mole 123 119 500 500
compound number average 492 476 1750 1890
molecular weight
blocking agent" PVE IBVE DHP EYE
solution of thermal latent [5] [6] [7] [8]
hydroxyl or thiol compound
effective component, 55.6 49.049.8 50.1
weight X
1) PV~: n-propyl vinyl ether
IBV~: isobutyl vinyl ether
DHP: 3,4-dihydro-2H-pyran
~ve: ethyl vinyl ether
(End of Table 7)
74
T a b I e 8 (Part 1)
Rxample 9 10 11 12 13 14
C~ ding recipe in weight parts
compound A-l 26.7
compound A-2 - 31.1 - - - -
compound A-3 - - 21.9 21.9
compound A-4 - - - - 100
compound A-5 - - - - - 100
compound A-6
compound B-l 100
compound B-2 - 100
c~ B-5 - - 100
c~n,~; J B-6 - -- - 100
c~ B-7
compound D-l
compo1md D-2
cc . ~ D-3
~R-214~ - - - - 49.0
Cymel 303~ - - - - - 21.9
Coronate ~H~ - - - - - -
ex-42l~ - - - - - -
titanium dioxide61.4 64.1 56.6 56.6 74.1 63.1
~odaflowJ 0.2 0.2 0.2 0.2 0.2 0.2
10% PTSA 2.0 2.0 2.0 2.0 2.0 2.0
10% pyridine 1.0 1.0 1.0 1.0 1.0 1.0
xylone 10 10 10 10 10 10
n-butyl acctat~ 2 2 2 2 2 2
(Table 8 continued)
I
T a b l e 8 (Part 2)
Example 15 16 17 18 19
Compounding recipe in weight parts
compound A~
compound A-2
compound A-3 - - - - -
compound A-~ - - -
compound A-5 100
compound A-6 - 100 - - -
compound B-l - - - - -
compound B-2
compound B-5
compound B-6 - - - - -
compound B-7 10.9
compound D-l - - 100
c. ~~.d D-2 - - - 100
compound D-3 - - - - lO0
KR-214~ - -
Cymel 303~ - -
Coronate EH~ - 20.0
eX-~21~ - - - - 7.8
titanium dioxide 54.6 64.2 43.5 43.0 51.4
Modaflo~ 0.2 0.2 0.2 0.2 0.2
10% PTSA 2.0 2.0 2.0 2.0 2.0
10% pyridino 1.0 1.0 1.0 1.0 1.0
xylene 10 10 10 10 10
n-butyl acetate 2 2 2 2 2
(end of Table 8)
76
T a b 1 e 9 (Part 1)
Example 9 10 11
compound ~A) A-l A-2 A-3
compound (B) B-l B-2 B-5
acid anhydride alkoxysilane epoxy group
group group
compound (D)
ratio of mixing (A) 34.8 37.6 29.4
solid c~ ~onen~s (B) 65.2 62.3 70.6
(D)
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity1.1 1.2 1.3
at 50~ after 30
days,
poise
curing condition 120~ 140~ 120~ 140~ 120~ 140~
30 min30 min 30 min 30 min 30 min 30 min
resistancegood good good good good good
properties of to acid 1
coating" resistancegood good ~ood good good good
to acid 2
resistancegood good eood good good good
to acjd 3
impact good good good good good good
resistance
weathering 82X 85% 89% 93% 83% 85%
resistance
Knoop 10.0 10.5 10.3 10.6 11.0 11.2
hardness
1) good: no change ~as observed.
(Table ~ continued)
T a b I e 9 (Part 2)
~xample 12 13 14
compound (A) A-3 A--4 A-5
compound (B) B-6 KR-21~ 6ymel 303
acryloyloxy silanol group alkylated amino-
group methylol group
compound (D)
ratio of mixing (A) 29.4 63.0 72.8
solid c~n,snenls (B) 70.6 37.0 27.2
(D)
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity 1.1 1.1 1.2
at 50~ after 30
days,
poise
c~ring 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
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 84X 86% 90% ~A% 8A% 87%
resistance
Knoop 10.8 11.0 10.2 10.7 9.8 10.3
hardness
1) good: no changs was observed.
(Table 9 continued)
78
T a b l e 9 (Part 3)
Rxample 15 16 17
compound (A) A-5 A-6
compound (B) B-7 Coronate ~H
acetal group isocyanate group
compound (D) - - D-1
isocyanate group
ratio of mixing (A) 8~.0 75.0
solid c~ lents (B) 16.0 25.0
(D) - - 100
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity 1.1 1.3 1.3
at 50~ after 30
days,
poise
curing condition l20~ 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
ueathering 83% 86% 82% 85% 83% 87%
resistance
Knoop 10.4 10.7 10.0 10.4 11.3 11.5
hardness
1) good: no change uas obsel~cd.
(Table ~ continued)
79
3 ~
T a b l e 9 (Part 4)
~xample 18 19
compound (A) - -
compound (B) - EX-421
- epoxy group
compound (D) D--2 D-3
alkoxy silane acid allhydride
group group
ratio of mixing (A) - --
solid components (B) - 12.1
(D) ]00 87.9
initial l.0 1.0
viscosity,
storage poise
stability viscosity 1.1 1.2
at 50~ after 30
days,
poise
curing condition 120~ 140~120~ 1~0~
30 min 30 min 30 min 30 min
resistance good good Kood goo(l
properties of to acid 1
coating " resistance ~ood good good good
to acid 2
resistance good good good good
to acid 3
impact good good good good
resistance
weathering 90% 92% 82% 86%
resistance
oop 1l.0 11,2 10.8 ll.l
hardness
1) good: no change was observed.
(~nd of Table 9)
T a b I e 10
Comparative example 1 2
Compounding recipe in weight parts
compound B-5 100
compound A-7 - 100
pentaerythritol 11.9
tetrakis(thioglycolate)
Coronate EH~ -- 20.0
titanium dioxide JR-602~ 48.7 56.0
Modaflo-~ 0.2 0.2
xylene 10 10
n-butyl acetate 2 2
8 1
T a b I e 11
~xample 20 21 22 23
Compoundin~ recipe in weight parts
compound A-1 26.7 - - -
compound A-6 - lO0
compound B-1 100 - - -
compound D-2 - - 100
compound D-3 - - - 100
Corona~e EH~ - 20
Denaool ~X-421~ - - - 7.8
ModaflowO 0.2 0.2 0.1 0.1
10% PTSA 1.5 1.5 1.5 1.5
10% pyridine 0.7 0.7 0.7 0.7
xylene 5 4 3 4
n-butyl acetate
82
T a b l e 12 (Part 1)
Example 20 21
compolmd (A) A l A-6
compound (B) B-l Coronate EH
acid a~lydride isocyanate group
group
compound (D) - -
ratio of mixing (A) 34.8 75.0
solid components (B) 65.2 25.0
(D)
initial 1.0 1.0
viscosity,
storage poise
stability viscosity 1.2 1.3
at 50~ after 30
days,
poise
curing conditi()ll 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min
resistance good gQad good good
pro~erties of to acid 1
coating" resistance ~ood good good good
~o acid 2
re~istance good good good good
to acid 3
impact good good good good
resistance
weathering good eood good good
resistance
Knoop 10.3 10.7 9.9 10.5
nardness
1) good: no change was ob.served.
(Table 12 continued)
83
T a b 1 e 12 (Part 2)
Example 22 23
compound (A) - -
compound (B) - EX-421
epoxy group
compound (D) D-2 D-3
alkoxysilaneacid anhydride
group group
ratio of mixing (A)
solid comgonents (B) - 12.1
(D) 100 87.9
initial 1.0 1.0
viscosity,
sturage 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~ood good good good
prop~rti0s of to acid 1
coatingl' resistance~ood good good good
to acid 2
resistancegood good good good
to acid 3
impact good good good good
resistance
weatheringgood good good good
resistance
Knoop 10.6 10.9 10.0 10.Z
hardness
1) good: no change was observed.
(~nd of Table 12)
84
T a b l e 13 (Part 1)
Example 24 2526 27 28 29
Compounding recipe in weight parts
compound A-l 26.7
compound A-2 - 31.1 - - - --
compownd A-3 - - 21.9 21.9 - -
compound A-4 - - - - 100
compound A-5 - - - - - 100
compownd A--6
compound B-l 100
compound B-2 - 100 -- - - -
compow~d B--5 - - 100
compound B-6 - - - 100
compound B-7
compound D-1
compownd D-2
c n~c;~nd D-3
KR-214~ - - - - 49.0,
Cymel 303~ - 2109
Coronate ~H~
~X-421~ - -
titanium diox;de61.4 64.1 56.6 56.6 7A.l 63.1
Modaflow~ 0.2 0.2 0.2 0.2 0.2 0.2
10% PTSA 2.3 - - - - -
10% pyridine 1,1
C-1203~ - 1.2 - - - -
acid catalyst A ~ - 2.1 - - --
acid catalyst B - - - 2.1
acid catalyst C - - - - 5.6 4.7
acid catalyst D - - - - -
xy1ene 10 10 10 10 10 ]0
n-butyl acetate 2 2 2 2 2 2
(Table 13 continued)
8 5
2 ~ 2
T a b I e 13 (Part 2)
Example 30 31 32 33 34
Compounding recipe in weight parts
compound A-l - - - - -
compound A--2
compound A-3 - - - - -
compound A-4 - - - - -
compound A-5 100
c~ A-6 - 100
compound B-l
compound B-2 -~
compound B-5
compound B-6 - - - - -
compound B-7 10.9
compound D-l - - 100
compound D-2 - - - 100 -
compound D-3 - - - - 100
KR-214~
Cymel 303~ - - _ _
Coronate EH0 - 20.0
EX-421~ - - - -- 7.8
titanium dioxide 54.6 64.2 43.5 43.0 51.4
ModaflowQ 0.2 0.2 0.2 0.2 0.2
10% PTSA - - -- 1.6
10% pyridine - - - 0 7
c-lao3~ - 1. 0
acid catalyst A2.0 - - -
acid catalyst B - - - - -
acid catalyst C
acid catalyst D - 4.0 2.7
xylene 10 10 10 10 10
n-butyl acetate 2 2 2 2 2
(End of Table 13)
86
T a b 1 e 14 (Part 1)
~xample 2~ 25 26
compound (A) A-l A-2 A-3
compound (B) B-l B-2 B-5
acid anhydridealkoxysilane group epoxy group
group
c 1, ~Il.,d (D)
thermal latent pyridine salt Vesturit l-methylethyl
catalyst (C) of PTSA Catalyst 1203 ester of PrSA
ratio of mixing (A) 34.8 37.6 29.4
solid ~,.nents (B) 65.2 62.3 70.6
(D)
content of (C), weight % 0.44 0.76 0.37
-(C)/{(A)+(B)+(D)}X100
initial 1.0 1.0 1.0
V~ SCOSity,
storags poise
stability viscosity 1.2 1.3 1.3
at 50'C after 30
days,
po is~
curing condition 120~ 140~ 120~ 140~ 120'C 140~
30 min 30 min 30 min 30 min 30 min 30 min
resistance good good good good good good
properti~s of to acid 1
coating~ resistancegood good good good good good
to acid 2
resistancegood good good good good good
to acid 3
impact good good good good good good
resistance
weathering 85% 86% 93% 93% 85% 86%
resistance
Knoop 11.3 11.6 10.2 10.4 11.5 11.5
hardness
1) good: no change was observed.
(Table 14 continued)
87
2 ~
T a b l e 14 (Part 2)
Example 27 28 29
compound (A) A-3 A-4 A-5
compound (B) B-6 KR-214 Cymel 303
acryloyloxy silanol group alkylated amino-
group methylol group
compo1~d (D) - - -
thermal latent l-methylheptyl l-methylethyl l-methylethyl
catalyst (C) ester of PTSA ester of DDBSA ester of DDBSA
ratio of mixing (A) 29.4 63.0 72.8
solid c.l,:nents (B) 70.6 37.0 27.2
(D)
content of (C), weight % 0.50 0.67 0.67
(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~ 140~ 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min 30 min 30 min
rssistance good good good good good good
properties of to acid I
coating" resistance good good good good good good
to acid 2
resistance good good good good good good
to acid 3
impact good ~ood good good good good
resistance
weathering 86% 87% 94% a4% 87% 88%
resistance
Knoop 10.8 lO.g 10.2 10.4 10.8 10.9
hardness
1) good: no change was observed.
(Table 14 continued)
88
~Q~
T a b I e 14 (Part 3~
example 30 31 32
compound (A) A-5 A-6 ~
compound (B) B-7 Coronate EH
acetal group isocyanate group
compound (D) - - D-l
isocyanate group
thermal latent l-methylethyl di-2-ethylhexyl di-2-ethylhexyl
catalyst (C) ester of PTSA phosphate phosphate
ratio of mixing (A) 84.0 75.0
solid components (B) 16.0 25.0
(D) - 100
content of (C), weight X 0.37 0.50 0.50
=(C)/{(A)+(B)+(D)}xlO0
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity 1.2 1.2 1.3
at 50~ after 30
days,
poise
curing condition 120~ 1~0~ 120~ 140~ 120~ l40~
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 86% 87% 85% 88% 87% 87%
resistance
Knoop 10.1 10.4 10.5 10.8 10.9 11.0
hardness
1) good: no change was observed.
(Table 14 continued)
89
3 y ~
T a b l e 14 (Part 4)
Example 33 34
compound (A) -- -
compound (B) - EX-421
epoxy group
compound (D) D-2 D-3
alkoxysilane acid anhydride
group group
thermal latent pyridine Vesturit Catalyst
catalyst (C) salt of PTSA 1203
ratio of mixing (A)
solid c~ r rts (B) - 12.1
(D) 100 87.9
content of (C), weight % 0.44 0.76
=(C)/((A)+(B)+(D)~X100
initial 1.0 1.0
viscosity,
storagc yoise
stabilitY viscosity 1.1 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 good good good good
to acid 2
resistance good good good good
to acid 3
impact good good good good
rosistance
weath~ring ~2% 92X 86% 89%
resistance
Knoop 11.1 11.3 ~0.2 10.5
hardness
1) good: no change was observed (end of Tabl~ 17)
T a b 1 e 15
Comparative example 45 6
C -. 'ing rec;pe in weight parts
c . ~ B-5 100 - -
compound A-6 -- - 100
cln, - ~ A-7 - 100
pentaerythritol 11.9
tetrakis(thioglycolate)
Coronate ~H~ - 20.0 20.0
titanium dioxide JR-6020 48.7 56.0 64.2
Modaflow~ 0.2 0.2 0.2
xylene 10 10 10
n-butyl acetate 2 2 2
acid catalyst D 3.0 3.5
9 1
2 ~ 2
T a b 1 e 16
Comparative example 4 5 6
compound (A) pentaerythritol A-7 A-6
tetrakis
(thioglycolate)
compound (B) B-5 Coronate EH Coronate EH
epoxy group isocyanate group isocyanate group
thermal latent di-2-ethylhexyl di-2-ethylhexyl
catalyst (C) phosphate phosphate
ratio of mixing (A) 19.2 71.4 75.0
solid components (B) 80.8 28.6 25.0
content of (C), ~eight % 0.48 0.50
=(C)/{(A)+(B)}X100
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity gel gel 1.1
at 50~ after 30 after 5 daysafter 3 days
days,
poise
c~ring condition 120~ 140~ 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min 30 min 30 min
resistancegood good goodgood stain good
properties of to acid 1
coating~ resistancegood good good good heavy good
to acid 2 stain
resistancegood ~ood good good cloudy good
to acid 3
impact good good good good crack good
resistance
~eathering 84% 85% 85% 87% 78X 85%
resistance
Knoop 11.6 11.7 10.7 10.~ 7.8 10.5
hardness
1) good: no change ~as observed.
92
T a b 1 e 17
Example 35 36 37 38 39 40 41
Ca~ ing recipe in weight parts
compound A-1 26.7
compound A-6 - 100.0 - - 100.0 100.0100.0
compound B-1 100.0
compound D-2 - - lO0.0
compound D-3 - -- - 100.0
Coronate eH - 20.0 - - 20.0 20.020.0
Denacol ~X-421~ - - - 7.8
Modaflow~ 0.2 0.2 0.1 0.1 0.2 0.2 0.2
10% PTSA 2.3
10% pyridine 1.1 - - - - - -
xylene S 4 3 4 4 4 4
n-butyl acetate
acid catalyst B - - 1.5
acid catalyst C - - - 3.9
acid catalyst D - 4.0
acid catalyst E - - - - 4.0
acid catalyst ~ - - - - - 3.2
acid catalYst G - - - - - - 8.0
g3
T a b l e 18 (Part 1)
Example 35 36 37
compound (A) A-l A-6
compound (B) B-l Coronate EH
acid anhydride isocyanate group
group
compound (D) - D-2
alkoxysilane
group
thermal latent pyridine salt di-2-ethylhexyl l-methylheptyl
catalyst (C) of PTSA phosphate ester of PTSA
ratio of mixing (A) 34.8 75.0
solid cc~,jnen~s (B) 65.2 25.0
(D) - _ 100
content of (C), weight % 0.44 0.50 0.50
=(C)/{(A)+(B)+(D)}xlO0
initial 1.0 1.0 1.0
viscosity,
storags poise
stability viscosity 1.2 1.3 1.3
at 50~ after 30
days,
poise
curine 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 10.7 10.8 11.0 11.3 10.2 11.5
hardness
1) good: no change was observed. 9 4 (Table 18 continued)
~ ~3 ~ 2
T a b 1 e 18 (Part 2)
Example 38 39
compound (A) - A-6
compound (B) EX-421 Coronate EH
epoxy groupisocyanate group
compound (D) D-3
acid anhydride
group
thermal latent l-methylethyl triethylamine
catalyst (C) ester of DDBSAsalt of ZnCl2
ratio of mixing (A) - 75.0
solid components (B) 12.1 25.0
(D) 87.9
content of (C), weight % 0.67 0.50
=(C)/~(A)+(B)+(D)}XlOO
initial 1.0 1.0
viscosity,
storage poise
stability viscosity 1.2 1.2
at 50~ after 30
days,
pol~e
curing condition lZ0~ 140~120~ 140~
30 min 30 min 30 min 30 min
resistancegood good good good
properties of to acid 1
coatingl) resistancegood good good good
to acid 2
resistancegood good good good
to acid 3
impact good good good good
resistance
weatheringgood good good good
resistance
Knoop 10.4 10.7 11.0 11.2
hardness
l) good: no change was observed
(Table 18 continued)
T a b l e 18 (Part 3)
Example 40 ~1
compound (A) A-6 A-6
compound (B) Coronate EH Coronate RH
isocyanate group isocyanate group
c~~ ~ (D)
ther~al latent SB-l2' SB-2a'
catalyst (C)
ratio of mixing (A) 75.0 75.0
solid c ~nents (B) 25.0 25.0
(D)
content of (C), weight ~ 2.00 2.00
=(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 ~ood good good
prop8rties 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
r88istance
Knoop 11.2 11.4 11.3 11.4
hardness
1) good: no change was obse.~d
2) SB-l: 3-methyl-2-butynyltetramethylenesulfonium hexafluoroantimonate;
3) SB-2: 4-methoA~b. ,~ yridinium heAafluoroantimonate
(end of Table 18)
9 6
2,
T a b 1 e 19
Comparative example 7 8
Compounding recipe in weight Parts
compound A-6 - 100.0
compound A-7 100.0
Coronate EH~ 20.0 20.0
Modaflow~ 0.1 0.1
xylene 5.0 S.0
n-butyl acetate 1.0 1.0
acid catalyst D 3.5 -
97
T a b I e 20
Comparative example 7 8
compound (A) A-7 A-6
compound (B)~oronate ~H Coronate EH
isocyanate group isocyanate group
thermal latentdi-2-ethylhexyl
catalyst (C) phosphate
ratio of mixing (A) 75.0 75.0
solid components (B) 25.0 25.0
content of (C), weight X 0.50
-(C)/{(A)+(B)}xlO0
initial 1.0 1.0
viscosity,
storage poise
stability viscosity gel 1.1
at 50~ after 30after 3 days
days,
poise
curing condition 120~ 140~ 120~ 140~
30 min 30 min 30 min 30 min
resistance good good stain eood
prop~rties of to acid 1
coating" resistance good good heavy good
to acid 2 stain
resistance good good cloudy good
~o acid 3
inlpact good good fracture good
resistance
weathering good good crach good
resistance after
2400
hours
Knoop 11.3 11.5 8.2 10.8
hardness
1) good: no change was observed
98
T a b l e 21 (Part 1)
Example 42 43 44 45 46
Compounding recipe of clear coating material in weight parts
compound :1- " 17.2
compound :2-l) - 36.7
c~ .:. 3 - - 27.4
compound 4-l) 34.1
c~n . ~ 5-l) 22.1
compound 6
c . :7
cl :. . :8
c. ~ d B-l 100.0
compound B-2 - 100.0
c~ nd B-3 - - 200.0
c .- ~ B-4 - - - 100.0 100.0
c n~ . ~ B-5
Coronate EH~
Cymel 303~
acid catalyst B 4.0 4.0 6.0 4.0 4.0
acid catalyst E
Modaflo~ 0.2 0.2 0.3 0.2 0.2
xylene 10 10 10 10 10
n-butyl acetate 2 2 2 2 2
1) Thermal latent hydroxyl or thiol l~..n, .Ind
(Table 21 continued)
99
T a b 1 e 21 (Part 2)
example 47 48 49 50
Compounding recipe of clear coating material in weight parts
compound ~
compound :2 ~
compotmd .3 "
compound -4-l)
compound S~ "
compound :6 " 22.9
compound :7 " - 100.0 - 100.0
compound :8-" - - 100.0
c.l,u~)nd B-l - - - -
c~ ~ ~t i 8-2
compound B-3 - - - -
compound B-4 -- - -- -
compound B-5 100.0 - -- -
Coronate EH~ - 20 0 - 20.0
Cy-el 303~ - - 21.9
acid catalyst B 4.0 4.0 4.0
acid catalyst ~ - - - 3.9
Modaflow~ 0.2 0.2 0.2 0.2
xylene 10 10 10 10
n-butyl acetate 2 2 2 2
1) Therltal latcnt hydroxyl or thiol compo~td
(Rnd of Table 21)
1 00
c~
T a b I e 22 (Part 1)
~xample 42 43 44
thermal latent [1] [2] [3]
hydroxyl or thiol compound
compound (B) B-1 B-2 B-3
acid anhydride alkoxysilane alkylated amino-
group group methylol group
mixing ratio, mole/mole 1/1 1/1 1/1
thsrmal latent 1-methylheptyl 1-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 1.3 1.4 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
coating" resistance good 800d 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 10.0 10.4 10.2 10.5 10.1 10.7
hardness
1) ~ood: no r,hange was observed.
(Table 22 continued)
1 0 1
.
T a b l e 22 (Part 2)
Example 45 46 47
thermal latent [4] [5] [6]
hydroxyl or thiol compound
compound (B) B-4 B-4 B-5
isocyanate group isocyanate group epoxy group
mixing ratio, mole/mole 1/1 1/1 1/1
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 1.3 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
resistancegood good good good good good
propsrtie~ Or to acid 1
coating" resistancegood good good good good Kood
to acid 2
resistancegood good good good good good
to acid 3
impact good good good good good good
resistance
weatheringgood good good good good good
resistance
Knoop 11.0 11.4 11.1 11.3 10.8 11.0
hardness
1) good: no change was obssrved,
(Table 22 continued)
~ 02
T a b l e 22 (Part 3)
Example 48 49 50
thermal latent [7] ~8] [7]
hydroxyl or thiol compaund
compound (B) Coronate EHCymel 303 Coronate EH
isocyanate group alkylated amino- isocyanate group
methylol group
mixing ratio, mole/mole 1/1 0.33/1 1/1
thermal latent 1-methylheptyl1-methylheptyltriethylamine
catalyst (C) ester of PTSAester of PTSAsalt of ZnC12
initial 1.0 1.0 1.0
viscosity,
storage poise
stability viscosity 1.3 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
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 11.1 11.4 10.8 11.2 11.0 11.3
hardness
1) good: no change was observed.
(end of Table 22)
1 03
3 2
T a b 1 e 23
Comparative example 9 10
C~ ~. 1ing recipe of clear coating composition in weight parts
polyol compound A~ 24.5
pentaerythritol - 11.9
tetrakis(thioglycolate)
compound B-4 100.0
c. ~ B--5 - 100.0
acid catalyst B 4.0 4.0
Modaflow~ 0.2 0.2
xylene 10.0 10.0
n-b~tyl acetate 2.0 2.0
1) example of preparation of material 20
1 04
T a b 1 e 24
Example 51 52 53
Compounding recipe of clear coating composition in weight parts
thermal latent 100.0 100.0 100.0
hydroxyl c Jud [7]
Cymel 303~ 3.6 3.6 3.6
Coronate EH~ 10.0 - -
compound B-2 - 50.0
compound B-5 - - 50.0
acid catalyst B 3.6 4.4
acid catalyst E - - 4.4
Modaflow~ 0.2 0.3 0.3
xylene 10 11 11
n-butgl acetate 2 3 3
1 O 5
T a b l e 25
Example 51 52 53
thermal latent [7] [7] ~7]
hydroxyl or thiol compound
compound (B) Cymel 303 Cymel 303 Cymel 303
alkylated amino- alkylated amino- alkylated amino-
methylol group methylol group methylol group
Coronate EH B-2 B-5
isocyanate group alkoxysilane epoxy group
group
thermal latent 1-methylheptyl 1-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 1.3 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
prop~rti0s 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 Food good good good
resistance
weathering ~ood good good good good good
resistance
Knoop 11.8 12.0 11.6 11.9 11.4 11.7
hardness
1) good: no change was observed.
106
