CA2040592C - Thermosetting compositions, thermal latent hydroxyl compounds, thermal latent thiol compounds and methods of preparation thereof - Google Patents

Abstract

Thermosetting compositions are excellent in storage stability, useful as one component thermosetting compositions, give cured products having excellent chemical properties, physical properties and weathering resistance and favorably utilized in coating compositions, ink, adhesive and molded plastics.
The thermosetting compositions comprise a compound having in the molecule two or more hydroxyl groups and/or thiol groups blocked by a vinyl ether compound, a vinyl thioether compound or a heterocyclic compound having a vinyl type double bond and oxygen or sulfur as the hetero atom, a compound having two or more reactive functional groups which can form a chemical bond with the blocked hydroxyl and/or thiol compound by heating and a thermal latent acid catalyst, The blocked hydroxyl and/or thiol group of the first compound and the reactive functional group of the second compound may be comprised in the same molecule.

Description

- 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 ~

-R'-Y'-C-Y2-R5 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 -R6-Z' -C-z2-Rl o 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 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]:

-R'l-y3-c y4-Rls 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 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 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 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.

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 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 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, ~ 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;

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]:

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 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 ~ 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 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.

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 ~ 2 The esters of phosphoric acid are, for example, compounds of the formula [8]:

(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, 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 ,, 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.

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 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.

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.

~ 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 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 ~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.

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 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 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 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 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 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 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 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 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 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 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 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 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 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 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 ;

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 ~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.

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.

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

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 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 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) 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) 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) 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) 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) 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 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 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) 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) 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) 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) 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) 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) ~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) 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 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.

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) 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 -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 hours Knoop 11.3 11.5 8.2 10.8 hardness 1) good: no change was observed 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) 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) 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) .

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) 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 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 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.

Claims (14)

1. 1. A thermosetting composition which comprises, as the essential components:
(A) a compound having in the molecule two or more functional groups of the general formula [1]

[1]
wherein R1 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, R5 is an organic group of 1 to 18 carbon atoms, Y1 and Y2 are respectively selected from the group consisting of an oxygen atom and a sulfur atom and R3 and R5 or R4 and R5 may 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.

2. A thermosetting composition as claimed in Claim 1, wherein the reactive functional groups of the compound (B) are at least one kind selected from the group consisting of 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, alkylated aminomethylol group, acetal group and ketal group.

3. A thermosetting composition as claimed in Claim 1 or Claim 2, wherein the thermal latent acid catalyst (C) is at least one kind selected from the group consisting of a compound prepared by neutralizing a protonic acid or a Lewis acid with a Lewis base, a compound of ester of a sulfonic acid, a compound of ester of phosphoric acid, an onium compound and a compound prepared by mixing a Lewis acid with trialkyl phosphate.

4. A thermosetting composition as claimed in Claim 1, Claim 2 or Claim 3, wherein the compound (A) and/or the compound (B) are polymers of .alpha.,.beta.-unsaturated compounds.

5. A thermosetting composition as claimed in Claim 1, Claim 2 or Claim 3, wherein the compound (A) and/or the compound (B) are polyester resins.

6. A thermosetting composition which comprises:
(D) a self-crosslinking compound having in the molecule (a) one or more functional groups of the general formula [2]:

[2]
wherein R6 is a bivalent organic group of 1 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, R10 is an organic group of 1 to 18 carbon atoms, Z1 and Z2 are respectively selected from the group consisting of an oxygen atom and a sulfur atom and R8 and R10 or R9 and R10 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 [1]:

[1]
wherein R1 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, R5 is an organic group of 1 to 18 carbon atoms, Y1 and Y2 are respectively selected from the group consisting of an oxygen atom and a sulfur atom and R3 and R5 or R4 and R5 may be bonded with each other to form a heterocyclic 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 heating with either one or both of the functional group of the general formula [1] and the functional group of the general formula [2].

7. A thermosetting composition as claimed in Claim 6, wherein the reactive functional groups (b) of the compound (D) and the reactive functional groups of the optionally utilized compound (B) are selected from the group consisting of epoxy group, 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, alkylated aminomethylol group, acetal group and ketal group.

8. A thermosetting composition as claimed in Claim 6 or Claim 7, wherein the thermal latent acid catalyst of (C) is at least one kind selected from the group consisting of a compound prepared by neutralizing a protonic acid or a Lewis acid with a Lewis base, a compound of ester of a sulfonic acid, a compound of ester of phosphoric acid, an onium compound and a compound prepared by mixing a Lewis acid with trialkyl phosphate.

9. A thermosetting composition as claimed in Claim 6, Claim 7 or Claim 8, wherein at least one of the compound (D) and the compound (A) and/or the compound (B) is polymer of an .alpha.,.beta.-unsaturated compound.

10. A thermosetting composition as claimed in Claim 6, Claim 7 or Claim 8, wherein at least one of the compound (D) and the compound (A) and/or the compound (B) is polyester resin.

11. A thermal latent compound selected from the group consisting of a thermal latent hydroxyl compound and a thermal latent thiol compound which is 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 1000g/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]:

[3]
wherein R11 is a bivalent organic group of 1 to 18 carbon atoms, R12, R13 and R14 are respectively selected from the group consisting of a hydrogen atom and an organic group of 1 to 18 carbon atoms, R15 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 R13 and R15 or R14 and R15 may be bonded with each other to form a heterocyclic structure which comprises Y4 as the hetero atom component

12. A thermal latent compound as claimed in Claim 11, wherein the polyol compound or the polythiol compound is a polyester resin.

13. A thermal latent compound as claimed in Claim 11, wherein the polyol compound or the polythiol compound is an acrylic resin.

14. A method of preparation of the thermal latent compound claimed in Claim 11, Claim 12 or Claim 13 which 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 1000g/mole and number average molecular weight of not more than 4000 is made to react with a vinyl ether compound.