KR950010118B1 - Thermosetting compositions - Google Patents

Abstract

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Description

Thermosetting composition

The present invention relates to a novel thermosetting composition. More specifically, the present invention relates to a thermosetting composition having good chemical performance, physical performance and weather resistance, and particularly excellent in storage stability and suitable for, for example, paints, inks, adhesives, molded articles and the like.

Conventionally, a compound having a carboxyl group and a reactive functional group capable of forming a chemical bond by heating the carboxyl group, for example, an epoxy group, a silinol group, an alkoxysilane group, a hydroxyl group, an amino group, an imino group, an isocyanate group, a blocked isocyanate group The thermosetting composition which consists of a compound with the compound which has a cyclocarbonate group, a vinyl ether group, a bithyl thioether group, an aminomethylol group, an alkylated aminomethylol group, an acetal group, a ketal group, etc. is known. Since these thermosetting compositions are excellent in the chemical performance, physical performance, weather resistance, etc. of the hardened | cured material obtained, they are used widely in the field of paints, an ink, an adhesive agent, or a plastic molded article, for example.

However, since a carboxyl group and the said reactive functional group have high reactivity, the composition which a carboxyl group-containing compound and the compound containing this reactive functional group coexist, a problem arises, such as gelatinizing during storage and shortening a usable time.

As a method of solving such a problem, for example, a method of blocking a carboxyl group as t-butyl ester and regenerating a carboxyl group liberated by isobutenali decomposition by heating has been proposed (Japanese Patent Laid-Open No. 1). -104646). However, this method requires a high temperature of about 170 to 200 ° C for pyrolysis of t-butyl group, and cannot be said to be sufficiently satisfactory from the viewpoint of resource saving and energy saving.

This invention is made | formed in order to obtain the thermosetting composition which gives hardened | cured material excellent in chemical performance, physical performance, or weather resistance, etc. at comparatively low temperature, and has favorable storage stability, and can be used as a one-part type.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to develop the thermosetting composition which has the above-mentioned desirable property, (A) vinyl type double bond which makes a special vinyl ether group, a vinyl thioether group, or an oxygen atom or a sulfur atom a hetero atom A compound having at least two carboxyl groups blocked with a cyclic group having a single molecule in one molecule, (B) a compound having at least two reactive functional groups capable of forming a chemical bond by heating with the blocked carboxyl group, and optionally It was found that the object can be attained by a composition comprising, as an essential component, a thermal latent acid catalyst exhibiting activity at the time of heat curing (C) used, and thus, the present invention has been completed based on these findings.

That is, this invention is a general formula in (A) 1 molecule.

(Wherein R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1-18 carbon atoms, R ⁴ is an organic group having 1-18 carbon atoms, and R ³ and R ⁴ are bonded to each other and Y ¹ is a hetero atom) Or a heterocyclic ring, and Y ¹ is an oxygen atom or a sulfur atom.) A compound having two or more functional groups represented by (), (B) in one molecule, capable of forming a chemical bond by heating with the functional group. The present invention provides a thermosetting composition comprising, as an essential component, a compound having two or more reactive functional groups and a heat-promoting acid catalyst which exhibits activity at the time of heat curing.

Hereinafter, the present invention will be described in detail.

In the present invention, the compound used as the component (A) is a general formula

(Wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹ have the same meaning as above)

It is a compound which has 2 or more, preferably 2-50, functional groups represented by 1 molecule, and the functional group represented by the said General formula (1) is a carboxyl group, and a general formula

(Wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹ have the same meaning as above)

It can form easily by reaction with the vinyl ether compound, vinylthioether compound, or the heterocyclic compound which has a vinyl double bond which has an oxygen atom or a sulfur atom as a hetero atom.

R ¹ , R ² and R ³ in the general formulas [1] and [2] are each a hydrogen atom or an organic group such as an alkyl group having 1 to 18 carbon atoms, an allyl group, or an alkylyl group, and R ⁴ is 1 to As an organic group, such as an alkyl group, an allyl group, or an alkylyl group of 18, these organic groups may have a suitable substituent, and R <^3> and R <^4> combine with each other and do not have or have a substituent which makes Y <^1> a hetero atom You may form a ring.

As a specific example of the compound represented by the said General formula [2], methylvinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether Aliphatic vinyl ether compounds such as cyclohexyl vinyl ether and aliphatic vinylthioether compounds corresponding thereto, or 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, Cyclic vinyl ether compounds such as 4-dihydro-2-ethoxy-2H-pyran and sodium 3,4-dihydro-2H-pyran-2-carboxylate, and cyclic vinylthioether compounds corresponding thereto Can be.

The compound of the above-mentioned (A) component can be obtained by reaction with the compound which has two or more, preferably 2-50 carboxyl groups in 1 molecule, and the compound represented by the said General formula [2]. Examples of the compound having two or more carboxyl groups in one molecule include, for example, aliphatic polycarboxylic acids having 2 to 22 carbon atoms such as succinic acid, adipic acid, azaline acid, sebacic acid, decamethylene dicarboxylic acid, phthalic acid, isophthalic acid, telephthalic acid and tri Substituted polycarboxylic acids such as aromatic polycarboxylic acids such as methalic acid and pyromellitic acid, tetrahydrophthalic acid and hexahydrophthalic acid, and polyester resins having two or more carboxyl groups in one molecule, acrylic resins and maleated polybutadiene resins; Can be mentioned.

Further, the compound having two or more carboxyl groups in one molecule, for example, (1) semi-esterified polyol and acid anhydride having two or more hydroxyl groups, preferably 2 to 50 hydroxyl groups per molecule. (2) A polyisocyanate compound having two or more isocyanate groups, preferably 2-50, per molecule, and hydroxycarboxylic acid or amino acid are added. (3) The carboxyl group-containing α, β-unsaturated monomer is homopolymerized or copolymerized with other α, β-unsaturated monomers. (4) A polyester resin at the end of the carboxyl group is synthesized. It is obtained by such a method.

Examples of the polyol having two or more hydroxyl groups per molecule include ethylene glycol, 1,2- and 1,3-propylene glycol, 1,3-butadiol, 1,4-butanediol, and 2,3. Butanediol, 1,6-hexanediol, diethylene glycol, pentanediol, dimethylbutanediol, water addition bisphenol A, glycerin, sorbitol, neopentylglycol, 1,8-octanediol, 1,4-cyclohexanedimethanol, 2 -Methyl-1,3-propanediol, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, kitol, mannitol, trihydroxy Polyhydric alcohols such as ethyl isocyanurate and dipentaerythritol; An open-ring adduct with these polyhydric alcohols and lactone compounds, such as (gamma) -butyrolactone and (epsilon) -caprolactone; Adduct under excessive alcohol with these polyhydric alcohols and isocyanate compounds, such as a trylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate; Vinyl ether compounds such as polyhydric alcohols, ethylene glycol divinyl ether, polyethylene glycol divinyl ether, butanediol divinyl ether, pentanediol divinyl ether, hexanediol divinyl ether, 1,4-cyclohexanedimethinol divinyl ether Adducts under excess alcohol; And condensates under excessive alcohol with these polyhydric alcohols and alkoxysilicone compounds, for example, KR-213, KR-217, KR-9218 (both manufactured by Japanese Sietsu Chemical Co., Ltd.) and the like. Can be.

On the other hand, examples of the acid anhydride to be reacted with these polyols include succinic acid, glutaric acid, adipic acid, azaline acid, sebacic acid, decamethylenedicarboxylic acid, phthalic acid, maleic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, Acid anhydrides of polyhydric carboxylic acids, such as hexahydrophthalic acid, are mentioned.

Moreover, as a polyisocyanate compound which has two or more 1 molecular weight isocyanate groups, it is P-phenylene diisocyanate, biphenyl diisocyanate, trienedi isocyanate, 3,3'- dimethyl- 4,4'- biphenylenedi, for example. Isocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, methylene bis (phenyl isocyanate), ridine methyl ester diisocyanate, bis (ethyl isocyanate) Fmaleate, isophorone diisocyanate, methylcyclohexyl diisocyanate, 2-isocyanate ethyl-2,6- diisocyanate hexanoate, these biuret, isocyanurate, etc. are mentioned.

Moreover, as hydroxycarboxylic acid, lactic acid, citric acid, hydroxy pivaric acid, 12-hydroxystearic acid, malic acid, etc. are mentioned, As an amino acid, for example, DL-alanine, L-glutamic acid, glycine, L-theanine, glycylglycine, r-amino caproic acid, L-aspartic acid, L-cytorurine, L-arginine, L-leucine, L-serine, etc. are mentioned.

As the carboxyl group-containing α, β-unsaturated monomer, for example, acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, etc. may be mentioned. As other α, β-unsaturated monomers, for example, methyl (Meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (Meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, styrene, (alpha) -methylstyrene, P-vinyl toluene, acrylonitrile, etc. are mentioned Can be.

Moreover, the polyester resin of a carboxyl terminal terminal can be easily formed with respect to polyhydric alcohol by the synthesis method of the conventional polyester resin under polybasic acid excess.

Moreover, the compound of this (A) component is a reaction product of (alpha), (beta)-unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, maleic acid, and fumaric acid, and the compound represented by the said General formula [2]. It can also be obtained by homopolymerization, and this reaction product can also be obtained by copolymerizing with an α, β-unsaturated compound having no other reactive functional group. As an alpha, beta- unsaturated compound which does not have this reactive functional group, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-, for example Butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, Styrene, α-methylstyrene, P-vinyltoluene, acrylonitrile and the like.

The reaction between the compound having two or more carboxyl groups in one molecule thus obtained and the compound represented by the above general formula [2] is usually carried out at a temperature in the range of room temperature to 100 ° C in the presence of a neat catalyst.

In this composition, 1 type of compounds of this (A) component may be used, and may be used in combination of 2 or more type.

In the composition of the present invention, as the compound used as the component (B), when the blocking functional group represented by the general formula [1] in the compound of the component (A) is regenerated by a free carboxyl group by heating, it reacts with this. Thus, those having two or more reactive functional groups capable of forming chemical bonds, preferably 2-50 in one molecule, are used. The reactive functional group may be any of those having the above properties, and is not particularly limited. Examples thereof include epoxy groups, silanol groups, alkoxysilane groups, hydroxyl groups, amino groups, imino groups, isocyanate groups, blocked isocyanate groups, cyclocarbonate groups, and vinyl ethers. Preferable examples of the group include a butylthioether group, an aminomethylol group, an alkylated aminomethylol group, an acetal group and a ketal group. 1 type may be contained in these reactive functional groups, and 2 or more types may be contained.

As a specific example of such a compound of (B) component, homopolymers or copolymers, such as a bisphenol-type epoxy resin, an alicyclic epoxy resin, a glycidyl (meth) acrylate, and 3, 4- epoxycyclohexylmethyl (meth) acrylate And epoxy group-containing compounds such as polyglycidyl compounds obtained by the reaction of polycarboxylic acids or polyols with epichlorohydrin; General formula

(R ⁵ ) _n Si (OR ⁶ ) _4-n ......... [5]

(In formula, R <^5> and R <^6> is a C1-C18 alkyl or allyl group, respectively, n is 0.1 or 2.)

(Alpha), (beta)-unsaturated silanes, such as a condensate of the compound shown, acryloyloxypropyl trimethoxysilane, methacryloyloxypropyl trimethoxysilane, and methacryloyloxypropyl tri-n-butoxysilane Silanol groups and alkoxysilane-containing compounds such as homopolymers or copolymers of compounds and hydrolysis products of these compounds; Homopolymers or copolymers of α, β-unsaturated compounds such as aliphatic polyols, phenols, polyalkyreneoxyglycols, 2-hydroxy (meth) acrylates and 2-hydroxypropyl (meth) acrylates, and these Hydroxyl group-containing compounds such as ε-caprolactone adducts of polyols; Amino group-containing compounds such as aliphatic and aromatic diamino compounds and polyamino compounds, and polyamino compounds obtained by reducing the cyano ethylation reaction product of the polyol; Imino group-containing compounds such as aliphatic and aromatic polyimino compounds; P-phenylene diisocyanate, biphenyl diisocyanate, triene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2, 4-trimethylhexane-1,6-diisocyanate, methylenebis (phenylisocyanate), ridinemethylester diisocyanate, bis (isocyanate ethyl) formalate, isophorone diisocyanate, methylcyclohexyl diisocyanate, 2-isocyanate ethyl-2 Isocyanate group-containing compounds such as 6-diisocyanate hexanoate, biuret and isocyanurate thereof, or an adduct compound of these isocyanates and the polyol; Blocked isocyanate group-containing compounds such as phenols, lactams, active methylenes, alcohols, acid amides, imides, amines, imidazoles, ureas, amines, and oximes of the above-mentioned isocyanate group-containing compounds; Cyclocarbonate group-containing compounds such as homopolymers or copolymers of 3- (meta_acryloyloxypropylene carbonate) and polyvalent cyclocarbonate groups-containing compounds obtained by the reaction of the epoxy group-containing compound with carbon dioxide; Polyvinyl ether compound obtained by reaction of the said polyhydroxyl group-containing compound and halogenated alkylvinyl ethers, Polyvinyl ether compound obtained by reaction of hydroxyalkyl vinyl ether, a polyvalent carboxyl group-containing compound, or the said polyisocyanate compound Vinyl ether compounds such as vinyl ether compounds such as copolymers of vinyloxyalkyl (meth) acrylates and α, β-unsaturated compounds, and vinylthioether compounds such as vinylthioether compounds corresponding thereto; Aldehyde Resin, Glycolyl Formaldehyde Resin, Urea Form Aminomethylol groups and alkylated aminomethylol group-containing compounds, such as homopolymers or copolymers of dehydration resins, aminomethylroll groups and alkylated aminomethylroll groups, and α-β-unsaturated compounds, such as polyvalent ketones, polyvalent aldehyde compounds, and polyvalent vinyl ether compounds. Homopolymer or air of the polyvalent acetal compound obtained by reaction with alcohols or ortho-acid esters, and a condensate of these and a polyol compound, or the adduct of the said vinyloxyalkyl (meth) acrylate and an alcohol or an ortho-acid ester Acetal groups, such as coalescence, a ketal group containing compound, etc. are mentioned.

In the composition of the present invention, as the compound of the component (B), a compound having two or more reactive functional groups may be used in addition to the compound having one reactive functional group, and the component (B) may be a combination of two or more thereof. You may use it. However, at this time, the combination in which each functional group is active is not preferable because the storage stability is impaired. As such an undesirable combination, for example, a combination of a functional group selected from an epoxy group, an isocyanate group, a vinyl ether group, a vinyl thioether group, a cyclocarbonate group and a silanol group with an amino group or an imino group, an isocyanate group or a vinyl ether group and a hydroxide And combinations with siloxane groups.

In the thermosetting composition of this invention, it is preferable that at least 1 chosen from the said (A) component and / or (B) component is a polymer of a (alpha), (beta)-unsaturated compound, or polyester resin, and the said general in this composition It is preferable to contain each component so that the functional group represented by Formula [1] and this and the reactive functional group which can form a chemical bond by heating in an equivalence ratio of 0.2: 1.0-1.0: 0.2 will be included.

The functional group represented by the general formula [1] of the component (A) of the present invention regenerates a free carboxyl group under heating, and forms a compound bond with the reactive functional group of the component (B). Based on what is called active ester, addition reaction can be made to the reactive functional group of (B) component. At this time, since it does not involve desorption reaction at the time of crosslinking reaction, it can contribute also to emission reduction of volatile organic substance.

In the present invention, these compositions, if desired, maintain good long-term storage stability of the composition, and also accelerate the curing reaction when cured at a low temperature for a short time, and have good chemical and physical properties for the cured product. For the purpose of imparting, the thermal latent acid catalyst exhibiting activity at the time of heat curing can be contained as the component (C). It is preferable that this heat latent acid catalyst exhibits an acid catalyst activity at a temperature of 60 ° C or higher. When this thermal latent acid catalyst exhibits an acid catalyst activity at a temperature of less than 60 ° C, the resulting composition may cause an undesirable condition such as an increase in viscosity or gelation during storage.

As the heat latent acid catalyst of the above-mentioned (C) component, the compound which neutralized protonic acid by the Lewis base, the compound which neutralized Lewis acid by the Lewis base, the compound of Lewis acid and a trialkyl phosphate, sulfonic acid ester, phosphate ester, and onium Onium compounds are preferable.

As a compound which neutralized the said protonic acid with a Lewis base, halogeno carboxylic acid, sulfonic acid, the monosulfate sulfate, monophosphate and diester, polyphosphate ester, monoborate, diester, etc. are mentioned, for example. , Various amines such as monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, or trialkylphosphine, tri Compounds neutralized with allylphosphine, trialkyl phosphite, triallyl phosphite, or Nacure 2500X, X-47-110, 3525, 5255 (trade name, manufactured by Kings Industries Co., Ltd.) commercially available as an acid-base blocking catalyst Etc. can be mentioned.

In addition, as the compound neutralizing the Lewis acid with a Lewis base, for example, _{BF 3, FeCl 3, SnCl 4} , AlCl 3, ZnCl there may be mentioned the compound neutralizing the Lewis acid with the above-mentioned base _2, and so on. Or the mixture of said Lewis acid and trialkyl phosphate is also mentioned.

As said sulfonic acid ester, it is a general formula, for example.

(Wherein R ⁷ is a phenyl group, a substituted phenyl group, a naphthyl group, a substituted naphthyl group or an alkyl group, R ⁸ is an alkyl group having 3 to 18 carbon atoms bonded to a sulfonyloxy group via primary carbon or secondary carbon, alkenyl group, Aryl group, alkali group, alkanol group, saturated or unsaturated cycloalkyl or hydroxycycloalkyl group.)

Compounds represented by these, specifically, sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecyl benzenesulfonic acid, naphthalenesulfonic acid, nonylnaphthalenesulfonic acid, n-propanol, n-butanol, n-hexanol, n-octane Esterified compounds with primary alcohols such as ol or secondary alcohols such as isopropanol, 2-butanol, 2-hexanol, 2-octanol, cyclohexanol, or the above-mentioned sulfonic acids and oxirane-containing compounds; (Beta) -hydroxyalkyl sulfonic acid ester obtained by reaction of the above, etc. are mentioned.

As said phosphate ester, it is a general formula, for example.

(In formula, R <^9> is a C3-C10 alkyl group, a cycloalkyl group, or an aryl group, m is 1 or 2.)

Compounds represented by the above, and more specifically, primary alcohols such as n-propanol, n-butanol, n-hexanol, n-octanol, 2-ethylhexanol and isopropanol, 2-butanol, Phosphate monoesters or phosphate diesters of secondary alcohols such as 2-hexanol, 2-octanol and cyclohexanol. As said onium compound, it is a general formula, for example

[R ¹⁰ ₃ NR ¹¹ ] + X-... … … … … … … … … … … … … … … … … … [5]

[R ¹⁰ ₃ PR ¹¹ ] + X-... … … … … … … … … … … … … … … … … … [6]

[R ¹⁰ ₃ OR ¹¹ ] + X-... … … … … … … … … … … … … … … … … … [7]

And [R ¹⁰ ₃ SR ¹¹ ] + X-... … … … … … … … … … … … … … … … … … [8]

Wherein R ¹⁰ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group, an alkali group, an alkanol group or a cycloalkyl group, and two R ¹⁰ groups are bonded to each other to form a heterocyclic ring having N, P, O or S as a hetero atom. Or R ¹¹ may be a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group, an alkali group, and X ⁻ is SbF _6- , PF _6- , or BF _4- .

The compound etc. which are represented by are mentioned.

In the composition of the present invention, one type of salt latent acid catalyst of the above-mentioned (C) component may be used, or may be used in combination of 2 or more type, and the compounding quantity is a total solid of (A) component and (B) component Per 100 weight part of quantity, it is normally selected in the range of 0.01-10 weight part.

The temperature and time required for the curing of the thermosetting composition of the present invention vary depending on the temperature of regenerating the free carboxyl group from the blocked functional group represented by the general formula [1], the type of the reactive functional group, the type of the thermal latent acid catalyst, and the like. Hardening is completed, heating at the temperature of 50-200 degreeC normally for 2 minutes-about 1 hour.

The thermosetting composition of the present invention may be used as it is or in combination with coloring pigments, fillers, solvents, ultraviolet absorbers, antioxidants, and the like, for use in paints, inks, adhesives, molded articles, and the like.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited at all by these Examples.

In addition, coating-film performance was calculated | required as follows.

(1) acid resistance-1

2 ml of 40 wt% sulfuric acid was placed on the test piece in a spot shape, and after standing at 20 ° C. for 48 hours, the abnormality of the coating film was visually determined.

(2) acid resistance-2

2 ml of 40 wt% sulfuric acid was placed on the test piece in a spot shape, and after heating at 60 ° C. for 30 minutes, the abnormality of the coating film was visually determined.

(3) acid resistance-3

The test piece was immersed in 0.1 N sulfuric acid and maintained at 60 ° C. for 24 hours, and then visually examined for abnormalities in the coating film.

(4) impact resistance

Using the impact deformation tester [JISK-5400 (1979) 6.13.3B method], the test piece was inserted into an impact frame having a radius of 6.35 mm and visually inspected for damage to the coating film when the weight of 500 g was dropped from the height of 40 cm. Determined.

(5) weather resistance

After 1000 hours or 3000 hours of exposure using the Sunshine Weather Mirror [JISB-7753], the 60-degree specular gloss value [JISK-5400 (1979) 6.7 60-degree specular gloss] of the coating film was measured. It was compared with the glossiness value at the time of examination or unexposure.

(6) Kunouf hardness

It measured at 20 degreeC with the M-type microhardness meter of Shimadzu Corporation (Japan). Larger values indicate harder ones.

[Production Examples 1-3]

(A) Preparation of Component Compounds A-1 to 1-3

(1) Preparation of α, β-unsaturated compound

The composition mixture of Table 1 was respectively inserted into the four-piece Frasco equipped with the thermometer, the reflux cooler, and the stirrer, and stirred while maintaining 50 degreeC. The reaction was terminated when the acid value of the mixture became 30 or less, and the product was transferred to a separatory funnel after cooling. The obtained product was washed with 100 parts by weight of an aqueous 10 wt% sodium hydrogen carbonate solution in a separatory funnel and washed with 200 parts by weight of deionized water until the pH of the washing solution became 7 or less. Thereafter, moreover 4A1 / 16 (manufactured by Wako Junyaku Co., Ltd. (Japan)) was added to the organic layer and dried for 3 days at room temperature, respectively, to form α, β-unsaturated compounds having the active ingredient contents as described in Table 1 below. Compound A-2 (a)-A-3 (a) were obtained.

TABLE 1

Note 1) The effective component content was determined by gas chromatography.

2) Preparation of Compounds A-1 to A-3

An initial injection solvent (xylene) of the amounts shown in Table 2 was respectively added to a four-part Frasco equipped with a thermometer, a reflux cooler, a stirrer, and a dropping funnel, and heated under stirring to maintain 8 hours. Next, at a temperature of 80 ° C., the mixture of the monomers and polymerization initiators (dropping components) of the composition described in Table 2 was added dropwise from the dropping funnel over 2 hours. After completion of the dropwise addition, the temperature at 80 ° C was maintained for 1 hour, the polymerization initiator solution (addition catalyst) of Table 2 was added, and the reaction was terminated when the temperature at 80 ° C was maintained for 4 hours. Compounds A-1 to A-3 having the characteristics of the substrate were obtained.

TABLE 2

Note 1) Non-volatile content measurement conditions

3 hours at 50 ° C and 0.1mmHg

2) viscosity; Gardner viscosity (25 ℃)

[By JISK-5400 (1979) 4.2.2 bubble viscometer]

[Production Example 4]

(A) Preparation of Component Compound A-4

(1) Preparation of Polycarboxylic Acid

The following component was inserted into the four-piece Frasco equipped with the thermometer, the reflux cooler, the stirrer, and the dropping funnel, and heated under stirring to raise the temperature to 120 ° C.

Pentaerythritol 136.0 parts by weight

Methyl isobutyl ketone 538.7 parts by weight

Subsequently, 672.0 parts by weight of methylhexahydrophthalic anhydride was added dropwise while maintaining the temperature at 120 ° C., diluted with an acid value (pyridine / water weight ratio = 9/1 mixture of about 50% by weight, and heated at 90 ° C. for 30 minutes. The tetrafunctional polycarboxylic acid compound A-4 (a) solution was obtained by continuing heating stirring until the solution was titrated with potassium hydroxide standard solution to 170 or less.

(2) Preparation of Compound A-4

Using the polycarboxylic-acid compound solution obtained by the said method, the mixture of the following composition was inserted in the same frasco, and it stirred, maintaining 50 degreeC.

336.7 parts by weight for the polycarboxylic acid compound of the above (1)

120.2 parts by weight of isobutyl vinyl ether

35 wt% 0.2 parts by weight

Methyl isobutyl ketone 46.3 parts by weight

The reaction was terminated when the acid value of the mixture became 12 or less, and the product was transferred to a separatory funnel after cooling. The obtained product was washed with 100 parts by weight of an aqueous 10 wt% sodium carbonate solution in a separatory funnel, followed by water washing with 300 parts by weight of deionized water until the pH of the cleaning solution became 7 or less. Thereafter, moreover 4A1 / 16 was added to the organic layer and dried at room temperature for 3 days to obtain a compound A-4 solution having a nonvolatile content of 60 wt% and a guidener viscosity E-F (25 ° C).

Production Example 5-10

(B) Preparation of Component Compounds B-1 to B-6

40.0 parts by weight of an initial injection solvent (xylene) was respectively added to a four-piece Frasco equipped with a thermometer, a reflux cooler, a stirrer, and a dropping funnel, and heated under stirring to maintain 100 ° C. Next, at a temperature of 100 ° C., the monomer and polymerization initiator mixture (dropping component) of the composition described in Table 3 was added dropwise from the dropping funnel over 2 hours. After completion of the dropwise addition, the temperature at 100 ° C was maintained for 1 hour, the polymerization initiator solution (addition catalyst) of the composition described in Table 3 was added, and the reaction was terminated when the temperature at 100 ° C was maintained for 2 hours. Compounds B-1 to B-6 having the characteristics of the substrate were obtained.

TABLE 3

Note 1) GMA; Glycidyl methacrylate

TMSPMA; Methacryloyloxypropyltrimethoxysilane

MZ-11; Chemityr MZ-11, Nippon Shokubai Chemical Co., Ltd., 2- (1-aziridinyl) ethyl methacrylate

MAGME; MAGME 100, Japan, Matsui cyanamide Co., Ltd. product, methyl acrylamide glycolate methyl ether

IEM; Isocyanate Ethyl Methacrylate

PMA; 130 parts by weight of 2-hydroxyethyl methacrylate, 3,4-dihydro-2H-yl-methyl-3,4-di in a PASCO with a vinyl ether group-containing methacrylate stopper obtained by the following method It is obtained by stirring 224 parts by weight of hydro-2H-pyran-2-carboxylate and 0.3 part by weight of dodecylbenzenesulfonic acid at room temperature for 24 hours.

BMA; n-butyl methacrylate

MMA; Methyl methacrylate

EHA; 2-ethylhexyl acrylate

AIBN; 2,2'-azobisisobutylonitrile

2) non volatile matter: Gardner viscosity (25 degreeC) dried at 50 degreeC and 0.1 mmHg for 3 hours; JISK-5400 (1979) 4.2.2 Based on foam accuracy meter.

[Production Example 11]

(B) Preparation of Component Compound B-7

20 parts by weight of methyl ortho methane and 0.3 parts by weight of diethyl ether boron trifluoride were added to a four-part prasco equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, and the mixture was cooled to 0-5 ° C. under stirring. Maintained. Next, 87.7 parts by weight of butyl vinyl ether was added at a constant velocity dropwise from the dropping funnel at a temperature of 5 ° C or lower. After completion of the dropwise addition, the temperature below 5 ° C. was maintained for 1 hour, and 0.4 parts by weight of a 30 wt% methanol solution of sodium methylate was added to terminate the reaction. The obtained product was distilled at 75-80 ° C. (4 mmHg) to obtain an acetalide having an effective content of 98 wt%.

Next, 618 parts by weight of the resulting purified acetalate, 134 parts by weight of trimethylolpropane and 4 parts by weight of P-toluenesulfonic acid were inserted into a four-piece Frasco equipped with a thermometer, a reflux cooler with a die-in-strap trap, a stirrer and a dropping funnel. The mixture was heated under stirring to maintain 90 ° C. As the reaction proceeded, a demethanol reaction occurred, and the reaction was terminated when 96 parts by weight of methanol was recovered, thereby obtaining Compound B-7.

[Manufacture example 12]

Preparation of heat latent acid catalyst of component (C)

315 parts by weight of 2-propanol was added to a four-part fresco equipped with a stirrer thermometer, a dropping funnel and a cooling tube, and the mixture was cooled by ice. 44.9 parts by weight of potassium-t-butoxide was added thereto, dissolved, and then dissolved in 300 parts by weight of diethyl ether. 53.4 parts by weight of P-toluenesulfonyl chloride was added dropwise over 30 minutes. After dropping, the freezing bath was removed for 1 hour, and the reaction was further performed for 1 hour. After completion of the reaction, the reaction mixture was washed three times with 300 parts by weight of water, followed by addition and dehydration drying treatment of Moreexclusive 4A1 / 16 (manufactured by Wako Junyaku Co., Ltd.), and the solvent was distilled off by an evaporator. 40 weight part (yield 67%) of sulfonic acid (1-methylethyl) was obtained. The resulting latent acid catalyst was dissolved by 238 parts by weight of xylene and diluted to 10% by weight in terms of P-toluenesulfonic acid.

[Production Example 13,14]

For Production Example 13, 2-octanol was used instead of 2-propane in Production Example 12, and for Production Example 14, dodecylbenzenesulfonyl chloride instead of P-toluenesulfonyl chloride in Production Example 12. In the same manner as in Production Example 12, except that was used, in Preparation Example 13, P-toluenesulfonic acid (1-methylhexyl) was yielded at 72%, and in Production Example 14, dodecylbenzenesulfonic acid (1-methylethyl) ) Was obtained in a yield of 83%.

The resulting latent acid catalyst was diluted with xylene in the same manner as in Production Example 12 to be 10% by weight in terms of P-toluenesulfonic acid and dodecyl benzenesulfonic acid, respectively.

[Comparative Production Example 1]

Preparation of Compound A-5

200 parts by weight of xylene was inserted into a four-piece Frasco equipped with a thermometer, a reflux cooler, a stirrer, and a dropping funnel, and heated to a stirrer to maintain 80 ° C. Next, the following components were dripped uniformly from the dropping funnel over 2 hours at the temperature of 80 degreeC.

t-butyl methacrylate 142.0 parts by weight

10-part by weight of n-butyl methacrylate

178.6 parts by weight of methyl methacrylate

105.4 parts by weight of 2-ethylhexyl acrylate

192.2 parts by weight of n-butyl acetate

21.8 parts by weight of 2,2'-azobisisobutylonitrile

After completion of dropping, the temperature at 80 ° C was maintained for 1 hour, 57.0 parts by weight of n-butyl acetate and 3.0 parts by weight of 2,2'-azobisisobutylolnitrile were added, and the temperature was maintained at 80 ° C for 4 hours. 52.5 wt% of non volatile matters and the compound A-5 of Gardner viscosity (25 degreeC) ST were obtained.

Application to 1 color solid color

[Example 1-9]

(1) Manufacture of paint

In the composition of Table 4, in Example 1, Denacol EX-421, Example 2, Compound B-2, Example 3, Cheminite PZ-33, Example 4 Compound A-4, Example 5 Coronate EH, Cymel 303 in Example 6, Compound B-1 in Example 7, KR-214 in Example 8, Compound B-7 except Example B-7 in Example 9 were injected into a sand mill, and the particle size was 10. The dispersion was carried out until it became 탆. Then, the raw material except at the time of pigment dispersion was added and mixed, and it was set as one-component coating material. Each coating material obtained was diluted with one poise (measured at 20 degreeC by a Brookfeed viscometer) with the tinner (xylene / butyl acetate = 8/2 weight ratio), and was stored sealed at 50 degreeC. After storage at 50 ° C. for 30 days, the viscosity was measured again. As shown in Table 5, almost no increase in viscosity was observed and excellent stability was shown.

TABLE 4

Note 1) Denacol EX-421; Polyepoxy compound, epoxy equivalent 155 of product of Japan, Nagase Chemical Co., Ltd.

2) chematite PZ-33; 6.2 mol / kg of polyadiridine adirin content of Nippon Shokubai Chemical Co., Ltd.

3) coronate EH; Hexamethylene diisocyanate trimer of Nippon Urethane Co., Ltd., isocyanate content 21wt%

4) Cymel 303; Methylated melamine resin, non-volatile content 98wt% of Mitsui Cyanamid Co., Ltd. in Japan

5) KR-214; Silicon varnish, 490 equivalent, non-volatile content 70wt% of product made in Japan, Xingetsu Chemical Co., Ltd.

6) titanium dioxide JR-602; Rutile type titanium dioxide of Japan, Teikoku Chemical Co., Ltd.

7) Modaflow; Monsanto product leveling agent

8) 10% PTSA; 10wt% isopropyl alcohol solution of P-toluenesulfonic acid

9) 10% pyridine; 10 wt% xylene solution of pyridine

(2) Preparation of test piece

Cationic electrodeposition paint on zinc phosphated mild steel Arc No. 4200 (trade name, manufactured by Nippon Yushi Co., Ltd.) was electrodeposited to a dry film thickness of 20 µm and baked at 175 ° C. for 25 minutes. A test plate was prepared by applying an air spray coating to a 1500CP sealer (trade name, manufactured by Nippon Yushi Co., Ltd.) so as to have a dry film thickness of 40 μm, and baking at 140 ° C. for 30 minutes.

Subsequently, after diluting the raw material of the above (1) with a coating viscosity (Pod Cup No. 4. 25 seconds at 20 DEG C) using a turner (xylene / butyl acetate = 8/2 weight ratio), the test piece prepared by the above-described method. It coated by air spraying, baked on conditions of Table 5, and created the test piece.

Although the coating film performance is shown in Table 5, in either case, a uniform and glossy coating film is obtained, and it shows the outstanding acid resistance, impact resistance, weather resistance, and hardness under the baking conditions of 140 degreeC.

TABLE 5a

TABLE 5b

TABLE 5c

[Comparative Examples 1,2]

In the composition of Table 6, coating was carried out after pigment dispersion in the same manner as in Examples 1 to 9 except for the polycarboxylic acid of Preparation Example A-4 (a) in Comparative Example 1 in Denacol EX-421 and Comparative Example 2 .

TABLE 6

The storage stability test was carried out in the same manner as in Examples 1 to 9, and in Comparative Example 2, as shown in Table 7, in the crosslinking reaction between the carboxyl group and the epoxy group, they were not lower-blocked like the functional groups of both. As a result, the viscosity increased remarkably with time, and finally gelled for 5 days.

Moreover, when the test piece was produced similarly to Examples 1-9 using the obtained coating material, in Comparative Example 1 (the technique of Unexamined-Japanese-Patent No. 1-104646), a crosslinked coating film sufficient even by baking at 140 degreeC is produced. It was not able to be obtained, and as shown in Table 7, it was inferior in acid resistance, impact resistance, weather resistance, and hardness.

TABLE 7

Application of 2 coats 1 make metallic color

[Examples 10-11]

(1) Manufacture of transparent paint

The composition raw materials of Table 8 were mixed to obtain a one-component transparent paint. When the obtained paints were subjected to the storage stability test in the same manner as in Examples 1 to 9, as shown in Table 9, almost no increase in viscosity was observed in any case, and the excellent storage stability was shown.

(2) Preparation of test piece

Each raw paint obtained was diluted similarly to Examples 1-9. Subsequently, to the test piece created by the method similar to Examples 1-9, Belcoat No. After coating 6000 silver metallic base coating (trade name, Nippon Yushi Co., Ltd. product) by air spray to dry film thickness of 15 占 퐉 with intervals of 1 minute 30 seconds and 2 stages, set at 20 ° C for 3 minutes, and then Each diluted transparent paint was coated with air spray and baked under the conditions described in Table 9 to prepare test pieces.

Although the coating film performance is shown in Table 9, in all cases, a uniform and glossy coating film was obtained, and it showed the outstanding acid resistance, impact resistance, weather resistance, and hardness under the baking conditions of 140 degreeC.

TABLE 8

TABLE 9

[Comparative Example 3, 4]

A transparent raw material was prepared using the composition raw materials shown in Table 10, and the storage stability test was conducted in the same manner as in Examples 1 to 9. In Comparative Example 4, as shown in Table 11, the crosslinking reaction between the carboxyl group and the epoxy group was performed. Since both functional groups were not lower-blocked, they gelled after 5 days.

In addition, using the obtained paint, test specimens were prepared in the same manner as in Examples 10 to 11, and in Comparative Example 3 (Technology of Japanese Patent Laid-Open No. 1-104646), a sufficient crosslinked coating film was obtained under baking conditions at 140 ° C. As shown in Table 11, acid resistance, impact resistance, weather resistance, and hardness were all inferior.

TABLE 10

TABLE 11

Application to 1 color solid color

[Examples 12-20]

(1) Manufacture of paint

In the composition of Table 12, Denacol EX-421 in Example 12, Compound B-2 in Example 13, Chemitite PZ-33 in Example 14, Compound A-4 in Example 15, and Coro in Example 16 Nate EH, cymel 303 in Example 17, compound B-1 in Example 18, KR-214 in Example 19, compound B-7 in Example 20, and the mixture was injected into a sand mill, and the particle size was 10 탆. It disperse | distributed until it became below. Then, the raw materials except at the time of pigment dispersion were added and mixed, and it was set as one-component coating material. Each paint obtained was diluted with a teaser (xylene / butyl acetate = 8/2 weight ratio) to 1 poise (measured at 20 degreeC by a Brookfeed viscometer), and was sealed-stored at 50 degreeC. After storage at 50 ° C. for 30 days, the viscosity was measured again. As shown in Table 13, almost no increase in viscosity was observed and excellent storage stability was shown.

TABLE 12

Note 1) Denacol EX-421; Polyepoxy compound, epoxy equivalent 155 of product of Japan, Nagase Chemical Co., Ltd.

2) Chemitite PX-33; 6.2 mol / kg of polyadiridine adiridine content of Nippon Shokubai Chemical Co., Ltd.

3) coronate EH; Nippon Urethane Co., Ltd. product hexamethylene diisocyanate trimer, isocyanate content 21wt%

4) Cymel 303; Japan, Mitsui Cyanamid Co., Ltd. methylated melamine resin, non-volatile content 98wt%

5) KR-214; Silicon varnish, 490 equivalent, non-volatile content 70wt% of product made in Japan, Xingetsu Chemical Co., Ltd.

6) titanium dioxide JR-602; Rutile type titanium dioxide of Japan, Teikoku Chemical Co., Ltd.

7) Modaflow; Monsant Leveling Agent

8) 10% PTSA; 10wt% isopropyl alcohol solution of P-toluenesulfonic acid

9) 10% pyridine; 10 wt% xylene solution of pyridine

10) C-1203; Abbreviation for Vesturit Catalyst1203, Imp Chemicals Co., Ltd., Biogenic heat latent acid catalyst, 50% by weight of non-volatile matter

11) acid catalyst A; Xylene solution of P-toluenesulfonic acid (1-methylethyl) of Preparation Example 12

12) acid catalyst B; Xylene solution of P-toluenesulfonic acid (1-methylheptyl) of Preparation Example 13

13) acid catalyst C; Xylene solution of dodecylbenzenesulfonic acid (1-methylethyl) of Preparation Example 14

14) acid catalyst D; 10 wt% isobutanol solution of 2-ethylhexyl phosphate [manufactured by Wako Pure Chemical Industries, Ltd.]

(2) Preparation of test piece

Cationic electrodeposition paint on zinc phosphated mild steel Arc No. 4200 (trade name, manufactured by Nippon Yushi Co., Ltd.) was electrodeposited to a dry film thickness of 20 µm and baked at 175 ° C. for 25 minutes. A test plate was prepared by applying an air spray coating to a 1500CP sealer (trade name, manufactured by Nippon Yushi Co., Ltd.) so as to have a dry film thickness of 40 μm, and baking at 140 ° C. for 30 minutes.

Subsequently, the raw paint of the above (1) was diluted with a coating viscosity (podod No. 4. 25 seconds at 20 DEG C) with a tinner (xylene / butyl acetate = 8/2 weight ratio), respectively, and the test plate prepared by the method described above. It coated by air spraying, baked in the conditions of Table 13, and created the test piece.

Although the coating film performance is shown in Table 13, even in all cases, a uniform and glossy coating film was obtained, and the outstanding acid resistance, impact resistance, weather resistance, and hardness were shown.

Table 13a

Table 13b

TABLE 13c

[Comparative Example 5]

In the composition of Table 14, except for the polycarboxylic acid of Production Example A-4 (a), coating was carried out after pigment dispersion in the same manner as in Examples 12 to 20.

When the obtained coating material was subjected to the storage stability test in the same manner as in Example 12-20, as shown in Table 15, in the crosslinking reaction of the carboxyl groups, both functional groups were not at all listed. Increased viscosity and finally gelled at 5 days.

TABLE 14

Note 1) Acid catalyst A; Xylene solution of P-toluenesulfonic acid (1-methylethyl) of Preparation Example 12

TABLE 15

Note 1) PTSA: P-toluenesulfonic acid

2) 1000 hours of exposure time [as in Table 5 Note 1)]

Application of 2-coat 1-baked metallic color

[Examples 21-25]

(1) Manufacture of transparent paint

The composition raw materials of Table 16 were mixed to obtain a one-component transparent paint. Each of the obtained paints was tested for storage stability in the same manner as in Examples 12 to 20. As shown in Table 17, almost no increase in viscosity was observed in any case, and the storage stability was excellent.

(2) Preparation of test piece

Each raw paint obtained was diluted similarly to Examples 12-20. Subsequently, to the test plate created by the method similar to Examples 12-20, Belcoat No. After coating 6000 silver metallic base coating (trade name, Nippon Yushi Co., Ltd. product) by air spray to dry film thickness of 15㎛ in 2 stages 1 minute 30 seconds, set at 20 ° C for 3 minutes, and then Each diluted transparent paint was coated with air spray and baked under the conditions described in Table 17 to prepare a test piece.

Although the coating film performance is shown in Table 17, in either case, a uniform and glossy coating film was obtained, and the outstanding acid resistance, impact resistance, weather resistance, and hardness were shown.

TABLE 16

Note 1) Acid catalyst A; Xylene solution of P-toluenesulfonic acid (1-methylethyl) of Preparation Example 12

2) acid catalyst B; Xylene solution of P-toluenesulfonic acid (1-methylheptyl) of Preparation Example 13

3) acid catalyst C; Xylene solution of dodecylbenzenesulfonic acid (1-methylethyl) of Preparation Example 14

4) acid catalyst E; A solution of diethylamine salt of zinc chloride diluted to 10% by weight with dimethyl sulfoxide

5) acid catalyst F; 50% by weight dithichloroethane solution of 3-methyl-2-butynyltetramethylenesulfonium hexafluoroantimonate

6) acid catalyst G; 20 wt% acetone solution of 4-methoxybenzylpyridinium hexafluoroantimonate

Table 17a

Table 17b

Note 1) PTSA: P-toluenesulfonic acid

2) DDBSA: dodecylbenzenesulfonic acid

3) 3000 hours of exposure time [as in Table 9 Note 1)]

Comparative Example 6

A transparent paint was prepared using the composition raw materials shown in Table 18, and the storage stability test was conducted in the same manner as in Examples 12 to 20. In Comparative Example 6, as shown in Table 19, the crosslinking reaction between the carboxyl group and the epoxy group was performed. Since both functional groups were not lower-blocked, they gelled after 5 days.

TABLE 18

Note 1) Catalytic A: Xylene solution of P-toluenesulfonic acid (1-methylethyl) of Preparation Example 12

TABLE 19

1) PTSA: P-toluenesulfonic acid

2) 1000 hours of exposure time [as in Table 5 Note 1)]

As described above, the thermosetting composition of the present invention gives a cured product excellent in chemical performance, physical performance and weather resistance, and is excellent in storage stability, and can be suitably used, for example, in paints, inks, adhesives, molded articles, and the like.

Claims (17)

(D) In the general flux, (A) general formula

Wherein R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴ is an organic group having 1 to 8 carbon atoms, and R ³ and R ⁴ are bonded to each other and Y ¹ is a hetero atom The heterocyclic ring may be formed, and Y ¹ is an oxygen atom or a sulfur atom.) A compound having two or more functional groups represented by the above, (B) A thermosetting composition comprising a compound having two or more reactive functional groups capable of forming a chemical bond by heating with the functional group in one molecule. The reactive functional group of the component (B) is an epoxy group, a silanol group, an alkoxysilane group, a hydroxyl group, an amino group, an imino group, an isocyanate group, a blocked isocyanate group, a cyclocarbonate group, a vinyl ether group, or a vinylthioether. The thermosetting composition which is at least 1 sort (s) chosen from group, an aminomethylol group, an alkylated aminomethylol group, an acetal group, and a ketal group. The thermosetting composition of Claim 1 or 2 whose (A) component and / or (B) component are polymers of (alpha), (beta)-unsaturated compounds. The thermosetting composition of Claim 1 or 2 whose (A) component and / or (B) component are polyester resin. The finishing composition containing the thermosetting composition of Claim 1 or this and a pigment is apply | coated to a to-be-coated body, The coating finishing method characterized by the above-mentioned. A method of applying a composite film to a coating body consisting of applying a colored film-forming composition on a substrate to form a base coat, and then applying a clear film-forming composition to the base coat to form a transparent dope coat. WHEREIN: Any of these dope coat clear film forming compositions or all of these dope coat clear film forming compositions and colored film forming compositions are finish coatings containing the thermosetting composition of Claim 1; The painting finish method characterized by the above. The article coated by the coating finishing method of Claim 5. The article coated by the coating finishing method of Claim 6. The thermosetting composition according to claim 1, comprising (C) a thermal latent acid catalyst that exhibits activity upon thermal curing. The reactive functional group of the component (B) is an epoxy group, a silanol group, an alkoxysilane group, a hydroxyl group, an amino group, an imino group, an isocyanate group, a blocked isocyanate group, a cyclocarbonate group, a vinyl ether group, or a vinylthioether. The thermosetting composition which is at least 1 sort (s) chosen from group, an aminomethylol group, an alkylated aminomethylol group, an acetal group, and a ketal group. The compound of claim 9 or 10, wherein the thermal latent acid catalyst of component (C) neutralizes protonic acid or Lewis acid with a Lewis base, a mixture of Lewis acid and trialkyl phosphate, sulfonic acid esters, phosphate esters, and onium. Thermosetting composition which is at least 1 sort (s) chosen from a compound. The thermosetting composition of Claim 9 or 10 which is a polymer of the (alpha), (beta)-unsaturated compound of (A) component and / or (B) component. The thermosetting composition of Claim 9 or 10 whose (A) component and / or (C) component are polyester resins. The finishing composition containing the thermosetting composition of Claim 9, or this and a pigment is apply | coated to a to-be-coated body, The coating finishing method characterized by the above-mentioned. A method of applying a composite film to a coating body consisting of applying a colored film-forming composition on a substrate to form a base coat, and then applying a clear film-forming composition to the base coat to form a transparent dope coat. In the dope coating clear film forming composition only, or all of the dope coating clear film forming composition and the colored film forming composition is a finish coating containing the thermosetting composition according to claim 9 The painting finish method characterized by the above. An article coated by the coating method according to claim 14. An article coated by the painting finishing method according to claim 15.