JP2850897B2 - Latent carboxyl compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel latent carboxyl compound and a method for producing the same. More specifically, the present invention provides a thermosetting composition having good chemical performance, physical performance and weather resistance, particularly excellent storage stability, and suitable for paints, inks, adhesives, molded articles, and the like. A latent carboxyl compound that can be provided,
And a method for efficiently producing the latent carboxyl compound.

[0002]

2. Description of the Related Art Conventionally, a compound having a carboxyl group and a reactive functional group capable of forming a chemical bond with the carboxyl group by heating, for example, an epoxy group, a silanol group, an alkoxysilane group, a hydroxyl group, an amino group, an imino group , Isocyanate group, blocked isocyanate group,
Thermosetting compositions comprising a combination with a compound having a cyclocarbonate group, vinyl ether group, vinyl thioether group, aminomethylol group, alkylated aminomethylol group, acetal group, ketal group and the like are known.
These thermosetting compositions, the chemical performance of the resulting cured product,
Because of its excellent physical performance and weather resistance,
For example, it is widely used in the fields of paints, inks, adhesives, and plastic molded products. However, since the carboxyl group and the reactive functional group have high reactivity, in a composition in which a carboxyl group-containing compound and a compound containing the reactive functional group coexist, gelation occurs during storage, Problems such as shortened pot life occur. As a method for solving such a problem, for example, a method has been proposed in which a carboxyl group is blocked as a t-butyl ester, and the carboxyl group is regenerated into a free carboxyl group by elimination and decomposition of isobutene by heating (Japanese Patent Laid-Open No. 1-146646). Gazette). However, this method requires a high temperature of about 170 to 200 ° C. for the thermal decomposition of the t-butyl group, and is not necessarily a satisfactory method from the viewpoint of resource saving and energy saving in recent years.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a one-pack type, which provides a cured product excellent in chemical performance, physical performance, weather resistance and the like at a relatively low temperature, and has good storage stability. The purpose of the present invention is to obtain a latent carboxyl compound useful for providing a thermosetting composition that can be used as a thermosetting composition.

[0004]

The present inventors have conducted intensive studies to develop a latent carboxyl compound capable of providing a thermosetting composition having the above-mentioned preferable properties.
By reacting a specific low molecular weight polycarboxyl compound with a vinyl ether compound to block carboxyl groups in the polycarboxyl compound,
They have found that the object can be achieved, and have completed the present invention based on these findings. That is, the present invention has two or more carboxyl groups per molecule, and has an acid equivalent of 1000 g / mol or less and a number average molecular weight of 400.
In a polycarboxyl compound having a carboxyl group of 0 or less, the carboxyl group can be converted to a vinyl ether compound by a general formula

[0005]

Embedded image

(Wherein R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is a 1 to 1 carbon atom)
In organic group 8, R ³ and R ⁴ may combine with each other to form a heterocyclic ring having Y ¹ as a hetero atom, and Y ¹ is an oxygen atom or a sulfur atom. The present invention provides a latent carboxyl compound characterized by being modified to the functional group represented by the formula (1). Further, the present invention has two or more carboxyl groups per molecule in the presence of an acid catalyst,
And an acid equivalent of 1000 g / mol or less and a number average molecular weight of 4
It is intended to provide a method for producing the latent carboxyl compound, wherein a polycarboxyl compound having a molecular weight of 000 or less is reacted with a vinyl ether compound. Hereinafter, the present invention will be described in detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In a polycarboxyl compound which is a raw material of a latent carboxyl compound of the present invention, when the number of carboxyl groups per molecule is less than 2 or when the acid equivalent exceeds 1000 g / mol, There is a possibility that the final purpose thermosetting composition may be insufficiently cured, and when the number average molecular weight exceeds 4,000, the thermosetting composition tends to have a high viscosity and a decrease in workability.
This polycarboxyl compound is (1) half-esterified a polyol having two or more, preferably 2 to 50 hydroxyl groups per molecule and an acid anhydride,
(2) adding a polyisocyanate compound having two or more isocyanate groups, preferably 2 to 50 isocyanate groups per molecule, to a hydroxycarboxylic acid or an amino acid,
(3) homopolymerization of a carboxyl group-containing α, β-unsaturated monomer or copolymerization with another α, β-unsaturated monomer;
(4) A polyester resin having a carboxyl group terminal is synthesized. Specific examples of each raw material used in these methods include those exemplified as raw materials in the production of a compound having two or more carboxyl groups, which is a raw material of component (A) in the thermosetting composition described below. Can be.

[0008] A preferred method for producing the latent carboxyl compound of the present invention is 2 or more carboxyl groups per molecule, preferably 2 to 50 carboxyl groups, and an acid equivalent of 1000 g / m2.
ol or less and a number average molecular weight of 4000 or less, preferably 2
000 or less polycarboxyl compound and a compound represented by general formula (4)

[0009]

Embedded image

Wherein R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is a carbon atom having 1 to 1 carbon atoms.
In organic group 8, R ³ and R ⁴ may combine with each other to form a heterocyclic ring having Y ¹ as a hetero atom, and Y ¹ is an oxygen atom or a sulfur atom. ) With a cyclic vinyl ether compound such as a vinyl ether compound, a vinyl thioether compound or a heterocyclic compound having a vinyl-type double bond having an oxygen atom or a sulfur atom as a hetero atom, preferably in the presence of an acid catalyst, preferably at room temperature. Or 100
The carboxyl group is added at a temperature of

[0011]

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ and Y ¹ have the same meaning as described above.) It can be easily produced by modifying to a blocked carboxyl group.

R ¹ , R ² and R ³ in the above general formulas (1) and (4) each represent a hydrogen atom or a carbon atom
And R ⁴ is an organic group having 1 to 18 carbon atoms such as an alkyl group, an aryl group or an alkaryl group, and these organic groups are appropriately substituted. And R ³ and R ⁴
May be bonded to each other to form a heterocyclic ring having no or having a substituent having Y ¹ as a hetero atom.

Specific examples of the compound represented by the general formula (4) include, for example, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether Such as aliphatic vinyl ether compounds and the corresponding aliphatic vinyl thioether compounds, furthermore 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
And cyclic vinyl ether compounds such as -dihydro-2-ethoxy-2H-pyran and sodium 3,4-dihydro-2H-pyran-2-carboxylate, and the corresponding cyclic vinyl thioether compounds. The latent carboxyl compound of the present invention is represented by the following general formula (1):

[0014]

Embedded image

(Wherein R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is a 1 to 1 carbon atom)
In organic group 8, R ³ and R ⁴ may combine with each other to form a heterocyclic ring having Y ¹ as a hetero atom, and Y ¹ is an oxygen atom or a sulfur atom. Functional group 2 represented by
And (B) a reactive functional group capable of forming a chemical bond with the functional group by heating in one molecule.
It can be suitably used as a component (A) in a thermosetting composition comprising a compound having at least one compound as an essential component and (C) a heat-latent acid catalyst which is active at the time of heat curing. In addition, the latent carboxyl compound of the present invention contains (D) a molecule represented by the following general formula (2) in one molecule:

[0016]

Embedded image

(Wherein R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁸ is a 1 to 1 carbon atom)
8 an organic group, the R ⁷ and R ^8, taken together Y ² may form a heterocyclic ring with heteroatoms, Y ² is an oxygen atom or a sulfur atom. Functional group 1 represented by
And (b) a self-crosslinking compound having at least one reactive functional group capable of forming a chemical bond with the functional group by heating as an essential component, and (C) active at the time of heat curing And (A) in one molecule, a compound of the general formula (1)

[0018]

Embedded image

(Wherein R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is a group having 1 to 1 carbon atoms)
In organic group 8, R ³ and R ⁴ may combine with each other to form a heterocyclic ring having Y ¹ as a hetero atom, and Y ¹ is an oxygen atom or a sulfur atom. Functional group 2 represented by
And / or (B) in one molecule the functional group represented by the general formula (2) or the general formula (1)
Can be suitably used as the component (A) in a thermosetting composition containing a compound having two or more reactive functional groups capable of forming a chemical bond with the functional group represented by the formula (1) or by heating. In the above thermosetting composition,
The compound used as the component (A) has the general formula (1)

[0020]

Embedded image

(Wherein R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is a 1 to 1 carbon atom)
8, wherein R ³ and R ⁴ may be bonded to each other to form a heterocyclic ring having Y ¹ as a hetero atom, and Y ¹ is an oxygen atom or a sulfur atom. Is a compound having two or more, preferably 2 to 50, functional groups in one molecule, wherein the functional group represented by the general formula (1) is a carboxyl group and a general formula (4)

[0022]

Embedded image

(Wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹ are
It has the same meaning as above. ) Can be easily formed by reaction with a vinyl ether compound, a vinyl thioether compound or a heterocyclic compound having a vinyl double bond having an oxygen atom or a sulfur atom as a hetero atom.

R ¹ , R ² and R ³ in the general formulas (1) and (4) each represent a hydrogen atom or a carbon atom
And R ⁴ is an organic group having 1 to 18 carbon atoms such as an alkyl group, an aryl group or an alkaryl group, and these organic groups are appropriately substituted. And R ³ and R ⁴
May be bonded to each other to form a heterocyclic ring having no or having a substituent having Y ¹ as a hetero atom.

Specific examples of the compound represented by the general formula (4) include, for example, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether. Such as aliphatic vinyl ether compounds and the corresponding aliphatic vinyl thioether compounds, furthermore 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
And cyclic vinyl ether compounds such as -dihydro-2-ethoxy-2H-pyran and sodium 3,4-dihydro-2H-pyran-2-carboxylate, and the corresponding cyclic vinyl thioether compounds.

The compound of the component (A) is obtained by reacting a compound having two or more, preferably 2 to 50 carboxyl groups in one molecule with the compound represented by the general formula (4). be able to. Compounds having two or more carboxyl groups in one molecule include, for example, succinic acid, adipic acid, azelaic acid, sebacic acid, aliphatic polycarboxylic acids having 2 to 22 carbon atoms such as decamethylene dicarboxylic acid, phthalic acid, Aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid;
Alicyclic polycarboxylic acids such as tetrahydrophthalic acid and hexahydrophthalic acid;
Polyester resin, acrylic resin, maleated polybutadiene resin, etc. having at least one resin.

The compound having two or more carboxyl groups in one molecule includes, for example, (1) a half of a polyol having two or more, preferably 2 to 50 hydroxyl groups per molecule and an acid anhydride. Esterify,
(2) adding a polyisocyanate compound having two or more isocyanate groups, preferably 2 to 50 isocyanate groups per molecule, to a hydroxycarboxylic acid or an amino acid,
(3) homopolymerization of a carboxyl group-containing α, β-unsaturated monomer or copolymerization with another α, β-unsaturated monomer;
(4) It can be obtained by a method such as synthesizing a polyester resin having a carboxyl group terminal.

Examples of the polyol having two or more hydroxyl groups per molecule include ethylene glycol, 1,2- and 1,3-propylene glycol,
3-butanediol, 1,4-butanediol, 2,3
-Butanediol, 1,6-hexanediol, diethylene glycol, pentanediol, dimethylbutanediol, hydrogenated bisphenol A, glycerin, 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, trishydroxyethyl isocyanurate, dipenta Polyhydric alcohols such as erythritol; these polyhydric alcohols and γ-
A ring-opening adduct with a lactone compound such as butyrolactone or ε-caprolactone; the polyhydric alcohol and tolylene diisocyanate, diphenylmethane diisocyanate;
Adducts of isocyanate compounds such as hexamethylene diisocyanate and isophorone diisocyanate in excess of alcohol; polyhydric alcohols and ethylene glycol divinyl ether, polyethylene glycol divinyl ether, butanediol divinyl ether, pentanediol divinyl ether, hexanediol divinyl ether Adducts of vinyl ether compounds such as 1,4-cyclohexanedimethanol divinyl ether in excess of alcohol; and polyhydric alcohols and alkoxysilicone compounds such as KR-213 and KR-2
17, KR-9218 (both trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like in the presence of excess alcohol.

On the other hand, acid anhydrides to be reacted with these polyols include, for example, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, phthalic acid, maleic acid, trimellitic acid, and pyromellitic acid. Acid anhydrides of polycarboxylic acids such as acids, tetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid can be mentioned. Examples of the polyisocyanate compound having two or more isocyanate groups per molecule include, for example, p-phenylene diisocyanate, biphenyl diisocyanate, tolylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 1,4- Tetramethylene diisocyanate, hexamethylene diisocyanate, 2,
2,4-trimethylhexane-1,6-diisocyanate, methylene bis (phenyl isocyanate), lysine methyl ester diisocyanate, bis (isocyanate ethyl) fumarate, isophorone diisocyanate,
Examples thereof include methylcyclohexyl diisocyanate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate, and burettes and isocyanurates thereof.

Examples of the hydroxycarboxylic acid include lactic acid, citric acid, hydroxypivalic acid, 12-hydroxystearic acid and malic acid. Examples of the amino acid include DL-alanine, L-glutamic acid and glycine. , L-theanine, glycylglycine, γ-aminocaproic acid, L-aspartic acid, L-
Examples thereof include titrulline, L-arginine, L-leucine, L-serine and the like.

Further, examples of the carboxyl group-containing α, β-unsaturated monomer include acrylic acid, methacrylic acid,
Itaconic acid, mesaconic acid, maleic acid, fumaric acid and the like can be mentioned, and as other α, β-unsaturated monomers, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) A) 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, α-methylstyrene, p-vinyltoluene,
Acrylonitrile and the like can be mentioned.

The carboxyl group-terminated polyester resin can be easily formed in accordance with a general method for synthesizing a polyester resin in a polybasic acid excess with respect to a polyhydric alcohol. The reaction of the thus obtained compound having two or more carboxyl groups in one molecule with the compound represented by the general formula (4) is usually carried out in the presence of an acidic catalyst in the range of room temperature to 100 ° C. Done at temperature.
In the thermosetting composition, one kind of the compound of the component (A) may be used alone, or two or more kinds may be used in combination.

In the above thermosetting composition, as the compound used as the component (B), the blocked functional group represented by the general formula (1) in the compound of the component (A) is converted into a free carboxyl group by heating. When regenerated, two or more reactive functional groups capable of reacting with it to form a chemical bond,
Preferably, those having 2 to 50 in one molecule are used. The reactive functional group may have any of the above properties, and is not particularly limited. Examples thereof include an epoxy group,
Silanol group, alkoxysilane group, hydroxyl group,
Preferred examples include an amino group, an imino group, an isocyanate group, a blocked isocyanate group, a cyclocarbonate group, a vinyl ether group, a vinyl thioether group, an aminomethylol group, an alkylated aminomethylol group, an acetal group, and a ketal group. One of these reactive functional groups may be contained, or two or more thereof may be contained.

Specific examples of the compound of the component (B) include bisphenol-type epoxy resins, alicyclic epoxy resins, glycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate. An epoxy group-containing compound such as a copolymer or a copolymer, a polyglycidyl compound obtained by reacting a polycarboxylic acid or a polyol with epichlorohydrin; general formula (5)

[0035]

Embedded image (R ¹³ ) _m Si (OR ¹⁴ ) _4-m (5)

(Wherein R ¹³ and R ¹⁴ are an alkyl group or an aryl group having 1 to 18 carbon atoms, m is 0, 1 or 2), a condensate of acryloyloxypropyl Homopolymers or copolymers of α, β-unsaturated silane compounds such as trimethoxysilane, methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltri-n-butoxysilane, and hydrolysis products of these compounds. Compounds containing silanol groups or alkoxysilane groups; aliphatic polyols, phenols, polyalkyleneoxy glycols, α, β-unsaturated compounds such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Homopolymer or copolymer, and ε-caprolact of these polyols A hydroxyl group-containing compound such as a ton adduct; an amino group-containing compound such as an aliphatic or aromatic diamino compound or polyamino compound and a polyamino compound obtained by reducing a cyanoethylation reaction product of the polyol; Imino group-containing compounds such as polyimino compounds; p-phenylene diisocyanate, biphenyl diisocyanate, tolylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate, 2,4
-Trimethylhexane-1,6-diisocyanate, methylenebis (phenylisocyanate), lysine methylester diisocyanate, bis (isocyanateethyl) fumarate, isophorone diisocyanate, methylcyclohexyl diisocyanate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate and the like Burettes and isocyanurates, and isocyanate-containing compounds such as adducts of these isocyanates with the polyol; phenols and lactams of the isocyanate-containing compounds;
Blocked isocyanate group-containing compounds such as blocks with active methylenes, alcohols, acid amides, imides, amines, imidazoles, ureas, imines, oximes; 3- (meth) acryloyloxypropylene carbonate Homopolymers or copolymers, cyclocarbonate group-containing compounds such as polyvalent cyclocarbonate group-containing compounds obtained by reacting the epoxy group-containing compound with carbon dioxide; the polyvalent hydroxyl group-containing compound and halogenated alkyl vinyl ethers A vinyl ether compound obtained by reacting a hydroxyalkyl vinyl ether with a compound containing a polyvalent carboxyl group or the above-mentioned polyisocyanate compound; Vinyl ether compounds such as copolymers of acrylates and α, β-unsaturated compounds, and corresponding compounds containing vinyl ether groups and vinyl thioether groups such as vinyl thioether compounds; melamine formaldehyde resin, glycolyl formaldehyde resin, urea formaldehyde Resin, aminomethylol group or alkylated aminomethylol group-containing compound such as homopolymer or copolymer of aminomethylol group or alkylated aminomethylol group-containing α, β-unsaturated compound; polyhydric ketone, polyhydric aldehyde compound, A polyacetal compound obtained by reacting the polyvalent vinyl ether compound or the like with an alcohol or an orthoacid ester, a condensate of the polyacetal compound with a polyol compound, and a vinyloxyalkyl (meth) acrylate and an alcohol; Acetal group- and ketal-group-containing compounds such as homopolymers or copolymers of adducts with carboxylic acids and orthoacid esters.

In the thermosetting composition, as the compound of the component (B), in addition to the compound having one kind of reactive functional group, a compound having two or more kinds of reactive functional groups may be used. The component (B) may be used in combination of two or more. However, at this time, a combination in which the respective functional groups are active with each other is not preferred because storage stability is impaired. Examples of such an undesired combination include, 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 And a combination of a group with a hydroxyl group.

The thermosetting composition may contain the compound of the above-mentioned component (A) and the compound of the above-mentioned component (B). (2)

[0039]

Embedded image

(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ and Y ² have the same meaning as described above), and at least one, preferably 2 to 50, functional groups; It may contain a self-crosslinking compound having one or more, preferably 2 to 50 reactive functional groups capable of forming a chemical bond with the functional group. Further, the thermosetting composition may contain the compound of the component (D) and the compound of the component (A) and / or the compound of the component (B). in this case,
The reactive functional group of the component (B) forms a chemical bond with the functional group represented by the general formula (2) and / or the functional group represented by the general formula (1) by heating.

In the compound of the component (D), (a) the functional group represented by the general formula (2) includes the functional group of the component (A), that is, the functional group represented by the general formula (1). The same ones as exemplified in the description can be mentioned. The (b) reactive functional group may be the same as those exemplified as the reactive functional group in the compound of the component (B).

The compound (D) is a compound having one or more, preferably 2 to 50, carboxyl groups and one or more, preferably 2 to 50, reactive functional groups in one molecule. As a raw material, it can be produced by the same method as described in the method for producing the compound of the component (A), or the above-described reaction with the unsaturated compound having a functional group represented by the general formula (2) It can also be produced by copolymerizing with an unsaturated compound having a functional functional group.
The compound of the component (D) may contain two or more reactive functional groups together with the functional group represented by the general formula (2). In this case, the component (B) Similarly to the compound of the above, a combination in which the respective functional groups are active with each other is not preferred because storage stability is impaired.

In the thermosetting composition, the component (A) and / or the component (B), or the component (D) and the optional component (A) and / or (B)
It is preferable that at least one selected from the components is a polymer of an α, β-unsaturated compound or a polyester resin, and is represented by the general formula (1) or (2) in the composition. Each component may be contained such that a functional group and a reactive functional group capable of forming a chemical bond by heating with the functional group have an equivalent ratio of 0.2: 1.0 to 1.0: 0.2. desirable. (A) in the thermosetting composition
General formulas (1), (2) and (3) of the component and the component (D)
The functional group represented by the formula (1) regenerates a free carboxyl group under heating and forms a chemical bond with the reactive functional groups of the components (B) and (D). As a so-called active ester based on the internal polarization structure, an addition reaction can be caused to the reactive functional group of the component (B) or the component (D). In this case, since no elimination reaction is involved during the cross-linking reaction, it can contribute to a reduction in the emission of volatile organic substances.

In the above-mentioned thermosetting compositions, these compositions may optionally have good long-term storage stability and accelerate the curing reaction when cured at low temperatures in a short time. For the purpose of imparting good chemical performance and physical performance to the cured product, a heat-latent acid catalyst having activity at the time of heat curing can be contained as the component (C). The thermal latent acid catalyst is preferably a compound exhibiting an acid catalytic activity at a temperature of 60 ° C. or higher. This latent heat acid catalyst is 6
When the acid catalyst activity is exhibited at a temperature lower than 0 ° C., the resulting composition may cause undesirable situations such as thickening or gelling during storage. Examples of the heat latent acid catalyst of the component (C) include a compound obtained by neutralizing a protic acid with a Lewis acid, a compound obtained by neutralizing a Lewis acid with a Lewis base, a mixture of a Lewis acid and a trialkyl phosphate, and sulfonic acid esters. , Phosphate esters, and onium compounds.

Examples of the compound obtained by neutralizing the protonic acid with a Lewis base include halogenocarboxylic acids, sulfonic acids, sulfuric acid monoesters, phosphoric acid mono- and diesters, polyphosphate esters, boric acid mono- and diesters and the like. Ammonia, monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, various amines such as triethanolamine or trialkylphosphine, triarylphosphine, trialkylphosphite, Compounds neutralized with triaryl phosphites, as well as Nailure 2500X, X-47-110, 3525, 52, which are commercially available as acid-base blocking catalysts
25 (trade name, manufactured by King Industry Co., Ltd.). Compounds obtained by neutralizing a Lewis acid with a Lewis base include, for example, BF ₃ , FeCl ₃ , SnCl ₄ , Al
Examples include compounds obtained by neutralizing a Lewis acid such as Cl ₃ or ZnCl ₂ with the above-mentioned Lewis base. Alternatively, a mixture of the above Lewis acid and a trialkyl phosphate may also be used. The sulfonic acid esters include, for example, those represented by the general formula (6)

[0046]

Embedded image

[0047] (R ¹⁵ is a phenyl group in the formula, a substituted phenyl group, a naphthyl group, substituted naphthyl group or alkyl group, R ¹⁶
Is an alkyl group having 3 to 18 carbon atoms, an alkenyl group, an aryl group, an alkaryl group, an alkanol group, a saturated or unsaturated cycloalkyl or hydroxycyclo which is bonded to a sulfonyloxy group via a primary carbon or a secondary carbon. An alkyl group), specifically, sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and nonylnaphthalenesulfonic acid, and n-propanol; esterified products with primary alcohols such as n-butanol, n-hexanol and n-octanol or secondary alcohols such as isopropanol, 2-butanol, 2-hexanol, 2-octanol and cyclohexanol; Sulfonic acids and oxirane groups Such as β- hydroxyalkyl sulfonates obtained by the reaction of organic compounds. Examples of the phosphoric esters include those represented by the general formula (7)

[0048]

Embedded image

(Wherein R ¹⁷ is an alkyl group, cycloalkyl group or aryl group having 3 to 10 carbon atoms, and m is 1 or 2), and more specifically,
Primary alcohols such as n-propanol, n-butanol, n-hexanol, n-octanol and 2-ethylhexanol, and secondary alcohols such as isopropanol, 2-butanol, 2-hexanol, 2-octanol and cyclohexanol Phosphoric acid monoesters or phosphoric acid diesters. Examples of the onium compound include, for example, general formulas (8) to (11)

[0050]

Embedded image _{^{(R 18 3 NR 19) +}} X - (8) (R 18 3 PR 19) + X - (9) (R 18 2 OR 19) + X - (10) (R 18 2 SR 19) ⁺ X ^- (11)

[0051] (R ¹⁸ is an alkyl group having 1 to 12 carbon atoms in the formula, alkenyl group, aryl group, alkaryl group, an alkanol group or a cycloalkyl group, two R ¹⁸
R ¹⁹ may be bonded to each other to form a heterocyclic ring having N, P, O or S as a hetero atom, and R ¹⁹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group,
Alkaryl group, X ^- is _{^{SbF - 6, AsF - 6,}} PF - 6
Or BF ^- ₄ ). In the thermosetting composition, one kind or two or more kinds of the heat-latent acid catalyst of the component (C) may be used, and the mixing ratio of the component (A) to the component (B) )component,
Alternatively, the amount is usually selected in the range of 0.01 to 10 parts by weight per 100 parts by weight of the total solid content of the component (D) and the component (A) and / or the component (B) optionally used.

The temperature and time required for curing the thermosetting composition are as follows: the temperature at which free carboxyl groups are regenerated from the blocked functional groups represented by the general formula (1) or (2); The curing is usually completed by heating at a temperature in the range of 50 to 200 ° C. for about 2 minutes to 1 hour, depending on the type of the group, the type of the thermal latent acid catalyst, and the like.

The above-mentioned thermosetting composition may be used as it is or, if necessary, by blending a coloring pigment, a filler, a solvent, an ultraviolet absorber, an antioxidant, etc., into paints, inks, adhesives, molded articles and the like. Can be used.

[0054]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the coating film performance was determined as follows. (1) Acid resistance-1 2 ml of 40 wt% sulfuric acid was spotted on the test piece,
After being left at 20 ° C. for 48 hours, abnormality of the coating film was visually determined. (2) Acid resistance-2 ml of 40 wt% sulfuric acid was spotted on the test piece,
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 kept at 60 ° C for 24 hours, and then the abnormality of the coating film was visually judged. (4) Impact resistance Impact deformation tester [JIS K-5400 (1979)
6.13.3 B method], the test piece was sandwiched in a shooting die having a radius of 6.35 mm, and damage to the coating film when a 500 g weight was dropped from a height of 40 cm was visually determined. (5) Weather resistance: Sunshine weather meter (JIS
B-7753), and after exposure for 1000 hours or 3000 hours, the coating film has a 60-degree specular gloss value (JIS K-54).
00 (1979) 6.7 60-degree specular gloss) was measured, and the abnormality of the coating film was visually judged or compared with the gloss value before exposure. (6) Knoop hardness Measured at 20 ° C. with an M-type micro hardness tester manufactured by Shimadzu Corporation. The higher the value, the harder it is.

Production Examples 1 to 6 Production of (B) Component Compounds B-1 to B-6 Initially charged solvent (xylene) was placed in a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel. 4
0.0 parts by weight were charged, and the mixture was heated under stirring and kept at 100 ° C. Next, at a temperature of 100 ° C., a mixture of the monomer and the polymerization initiator (dropping component) having the composition shown in Table 1 was dropped at a constant speed from the dropping funnel over 2 hours. After completion of the dropwise addition, the temperature was kept at 100 ° C. for 1 hour, a polymerization initiator solution (additional catalyst) having the composition shown in Table 1 was added, and the reaction was terminated when the temperature was further kept at 100 ° C. for 2 hours. Compounds B-1 to B-6 having the properties shown in Table 1 were obtained.

[0056]

[Table 1]

[0057]

Note 1) GMA: Glycidyl methacrylate TMSPMA: Methacryloyloxypropyltrimethoxysilane MZ-11: Chemitite MZ-11, manufactured by Nippon Shokubai Chemical Co., Ltd. 2- (1-aziridinyl) ethyl methacrylate MAGME: MAGME100, Mitsui Cyanamid Co., Ltd., methyl acrylamide glycolate methyl ether IEM: isocyanate ethyl methacrylate PMA: vinyl ether group-containing methacrylate obtained by the following method 130 parts by weight of 2-hydroxyethyl methacrylate, 3,4-dihydro-2H in a flask with a stopper Stirring 224 parts by weight of -yl-methyl-3,4-dihydro-2H-pyran-2-carboxylate and 0.3 part by weight of dodecylbenzenesulfonic acid at room temperature for 24 hours. Is obtained. BMA: n-butyl methacrylate MMA: methyl methacrylate EHA: 2-ethylhexyl acrylate AIBN: 2,2′-azobisisobutyronitrile 2) Nonvolatile matter: dried at 50 ° C., 0.1 mmHg for 3 hours Gardner viscosity (25) ° C): JIS K-5400 (1
979) 4.2.2 With a foam viscometer.

Production Example 7 Production of Component (C) The Heat Latent Acid Catalyst 315 parts by weight of 2-propanol was placed in a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser, and cooled with ice. Then, 44.9 parts by weight of potassium-t-butoxide was added and dissolved, and 53.4 parts by weight of p-toluenesulfonyl chloride dissolved in 300 parts by weight of diethyl ether was added dropwise over 30 minutes. One hour after the addition, the ice bath was removed, and the reaction was further performed for one hour. After completion of the reaction, the reaction mixture was washed three times with 300 parts by weight of water, and then molecular sieve 4A1 / 16 (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, followed by dehydration and drying treatment, and the solvent was distilled off with an evaporator.
-Toluenesulfonic acid (1-methylethyl) 40 parts by weight (yield 67%) was obtained. The obtained heat-latent acid catalyst was dissolved in 238 parts by weight of xylene and diluted to 10% by weight in terms of p-toluenesulfonic acid.

Production Examples 8 and 9 In Production Example 8, 2-octanol was used in place of 2-propanol in Production Example 7, and in Production Example 9, dodecylbenzene chloride was used in place of p-toluenesulfonyl chloride in Production Example 7. Except that sulfonyl was used, by performing the same operation as in Production Example 7, in Production Example 8, p-toluenesulfonic acid (1-methylheptyl)
Was obtained at a yield of 72%, and in Production Example 9, dodecylbenzenesulfonic acid (1-methylethyl) was obtained at a yield of 83%. Each of the obtained latent heat acid catalysts was p
-Diluted with xylene so as to be 10% by weight in terms of toluenesulfonic acid and dodecylbenzenesulfonic acid.

Production of Latent Polycarboxyl Compound Example 1 (1) Production of polycarboxyl compound In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 134.0 parts by weight of trimethylolpropane and hexahydroanhydride were placed. 462.0 parts by weight of phthalic acid and 149.0 parts by weight of methyl isobutyl ketone were charged and heated with stirring to maintain the reflux temperature for 6 hours. Thereafter, the acid value of the mixture (diluted approximately 50-fold with a mixture of pyridine / water (weight ratio) = 9/1 and heat-treated at 90 ° C. for 30 minutes, titrated with a potassium hydroxide standard solution) to 226 or less The heating and stirring were continued until the solution was obtained, whereby a polycarboxyl compound solution was obtained. (2) Production of latent carboxyl compound Using the polycarboxyl compound solution obtained by the above method, a mixture having the following composition was charged into a flask similar to the above and stirred at room temperature. The above polycarboxyl compound solution 248.3 parts by weight Ethyl vinyl ether 108.0 parts by weight Monooctyl phosphate 0.6 parts by weight Xylene 76.4 parts by weight The reaction was terminated when the acid value of the mixture became 3 or less. 10 parts by weight of KYOWARD 500 (manufactured by Kyowa Chemical Industry Co., Ltd., synthetic acid adsorbent) were added, and the mixture was stirred at room temperature for 48 hours. By removing, the effective content is 50 wt% and the Gardner viscosity (JIS K-5400 (1979) 4.
A latent carboxyl compound solution (1) of FG was obtained using a 2.2 foam viscometer.

Examples 2 to 4 (1) Production of polycarboxyl compound A mixture having the composition shown in Table 2 was charged into the same flask as in Example 1 (1), and the same operation as in Example 1 (1) was performed. By heating and stirring until the acid value of the mixture reached 170 in Example 2, 117 in Example 3, and 145 in Example 4, polycarboxylic acid compound solutions were obtained. (2) Production of a latent carboxyl compound A latent carboxyl compound solution having the properties shown in Table 3 by performing the same operation as in Example 1 (2) using a mixture having the composition shown in Table 3. (2)-
(4) was obtained.

[0063]

[Table 2] Note 1) Caprolactone polyol, manufactured by Daicel Chemical Industries, Ltd., hydroxyl value 579, trade name 2) King Company, polyester diol, nonvolatile content 96
wt%, hydroxyl value 235, trade name 3) King Company, urethane diol, nonvolatile content 97.5
wt%, hydroxyl value 350, trade name

[0064]

[Table 3]

Example 5 (1) Production of polycarboxyl compound A silicone KR was placed in a four-necked flask equipped with a thermometer, a reflux condenser equipped with a Dean-Stark trap, and a stirrer.
-213 (manufactured by Shin-Etsu Chemical Co., Ltd., methoxy silicone compound, methoxy equivalent: 160) 480.0 parts by weight,
312.0 parts by weight of neopentyl glycol and 0.8 parts by weight of p-toluenesulfonic acid were charged and heated with stirring to maintain a temperature of 160 ° C. After the start of the reaction, the methanol removal reaction proceeded at a temperature of 140 ° C. or higher, and the reaction was continued until 96 parts by weight of methanol was obtained. Next, the Dean-Stark trap was removed, 462.0 parts by weight of hexahydrophthalic anhydride and 288.7 parts by weight of methyl isobutyl ketone were added to the flask, and the same operation as in Example 1 (1) was performed. By heating and stirring until the temperature became 117 or less, a polycarboxyl compound solution was obtained. (2) Production of latent carboxyl compound A mixture having the following composition was subjected to the same operation as in Example 1 (2), and then 43 parts by weight of a solvent were distilled off by an evaporator to obtain an effective component of 50 wt% and Gardner. Viscosity J
-K latent latent carboxyl compound solution (5) was obtained. Polycarboxyl compound solution of Example 5 (1) 479.6 parts by weight n-propyl vinyl ether 129.0 parts by weight Monooctyl phosphate 1.2 parts by weight Xylene 200.6 parts by weight

Example 6 (1) Production of polycarboxyl compound Coronate EH (manufactured by Nippon Polyurethane Industry Co., Ltd., trimer of hexamethylene diisocyanate, isocyanate content: 21% by weight) was placed in the same flask as in Example 1 (1).
200.0 parts by weight of trade name), 300.0 parts by weight of 12-hydroxystearic acid, and 125.0 parts by weight of butyl acetate were charged and heated with stirring to keep the temperature at 100 ° C.
When the isocyanate content in the mixture became 0.1 wt% or less, the reaction was terminated to obtain a polycarboxyl compound solution. (2) Production of latent carboxyl compound A mixture having the following composition was subjected to the same operation as in Example 1 (2), and then 43 parts by weight of a solvent were distilled off by an evaporator to obtain an effective component of 50 wt% and Gardner. Viscosity L
-M latent carboxyl compound solution (6) was obtained. Polycarboxyl compound solution of Example 6 (1) 625.0 parts by weight n-propyl vinyl ether 129.0 parts by weight Monooctyl phosphate 1.5 parts by weight Xylene 287.5 parts by weight

Example 7 (1) Production of polycarboxyl compound In a flask similar to that of Example 1 (1), 200.0 parts by weight of coronate EH (supra), 75.1 parts by weight of glycine, N-
Example 6 was prepared by charging 68.8 parts by weight of methylpyrrolidone.
By performing the same operation as in (1), a polycarboxyl compound solution was obtained. (2) Production of latent carboxyl compound A mixture having the following composition was subjected to the same operation as in Example 1 (2), and then 42 parts by weight of a solvent were distilled off by an evaporator to obtain an effective component of 50 wt% and Gardner. Viscosity S
A latent carboxyl compound solution (7) of -T was obtained. Polycarboxylic acid compound solution of Example 7 (1) 343.9 parts by weight 3,4-dihydro-2H-pyran 126.0 parts by weight Monooctyl phosphate 0.8 parts by weight Methyl isobutyl ketone 121.5 parts by weight

Example 8 (1) Production of α, β-unsaturated compound 86.0 parts by weight of methacrylic acid and 100.9 parts by weight of 3,4-dihydro-2H-pyran were added to the flask of Example 1 (1). , Hydroquinone monomethyl ether 0.2 parts by weight, 3
0.1 parts by weight of 5 wt% hydrochloric acid was charged and stirred while keeping at 50 ° C. When the acid value of the mixture became 30 or less, the reaction was terminated. After cooling, the product was transferred to a separating funnel. The obtained product was washed with 100 parts by weight of a 10 wt% aqueous sodium hydrogen carbonate solution in a separating funnel with alkali, and then repeatedly washed with 200 parts by weight of deionized water until the pH of the washing solution became 7 or less. Thereafter, Molecular Sieve 4A1 / 16 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the organic layer, and the mixture was added at room temperature for 3 hours.
By drying for days, an α, β-unsaturated compound was obtained with an effective content of 95.1 wt%. (2) Production of latent carboxyl compound 200.0 parts by weight of xylene was charged into a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, and heated to 100 ° C. by stirring. Next, a mixture having the following composition was dropped at a constant speed over 2 hours at a temperature of 100 ° C. After completion of the dropwise addition, a temperature of 100 ° C. was maintained for 30 minutes, and a solution of 3.0 parts by weight of 2,2′-azobisisobutyronitrile dissolved in 57.0 parts by weight of n-butyl acetate was added.
When the temperature of 0 ° C. was maintained for 2 hours, the reaction was terminated, and a latent carboxyl compound solution (8) having an effective content of 50 wt% and Gardner viscosity OP was obtained. Α, β-unsaturated compound of Example 8 (1) 178.8 parts by weight n-butyl methacrylate 100.0 parts by weight methyl methacrylate 178.6 parts by weight 2-ethylhexyl acrylate 135.4 parts by weight n-butyl acetate 115.0 parts by weight 2,2'-azobisisobutyronitrile 32.2 parts by weight Examples 1 to 8 are summarized in Table 4.

[0069]

[Table 4]

[0070]

[Table 5]

Response to 2-coat 1-bake metallic color
Use Application Examples 1-9 (1) mixing raw materials of the composition of Table 5 the production of clear paint was Ichieki coating material. Each of the obtained paints was diluted with a thinner (xylene / butyl acetate = 8/2 weight ratio) to 1 poise (measured at 20 ° C. using a Brookfield viscometer) and stored tightly at 50 ° C. After storage at 50 ° C. for 30 days, the viscosity was measured again. As shown in Table 6, almost no increase in viscosity was observed, indicating excellent storage stability. (2) Preparation of test piece A cationic electrodeposition paint Aqua No. was applied to a zinc phosphate-treated mild steel sheet.
4200 (trade name, manufactured by NOF Corporation) with a dry film thickness of 20
μm, and baked at 175 ° C. for 25 minutes. 1500 sealer (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) was applied by air spray so as to have a dry film thickness of 40 μm, and baked at 140 ° C. for 30 minutes to prepare a test plate. Then, Bellcoat No. 6000 silver metallic base coat paint (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) by air spray at intervals of 1 minute and 30 seconds, dry film thickness of 2 stages at 15 μm
m, and set at 20 ° C. for 3 minutes. Then, the clear paint of the above (1) was applied with a coating viscosity (Ford Cup N
o. (4, 25 seconds at 20 ° C.) were applied by air spraying and baked under the conditions shown in Table 6 to prepare test specimens. The coating film performance is shown in Table 6. In each case, a uniform and glossy coating film was obtained, showing excellent acid resistance, impact resistance, weather resistance and hardness.

[0072]

[Table 6] Note 1) Latent carboxyl compound solutions (1) to in Table 4
Same as (8). 2) Same as compounds (B-1 to B-6) in Table 1. 3) Acid catalyst B: p-toluenesulfonic acid of Production Example 8 (1
-Methylheptyl) in xylene. 4) Acid catalyst E: a solution obtained by diluting triethylamine salt of zinc chloride to 10% by weight with dimethyl sulfoxide.

[0073]

[Table 7]

[0074]

[Table 8]

[0075]

[Table 9] Note 1) Latent carboxyl compound solutions (1) to in Table 4
Same as (8). 2) Same as compounds (B-1 to B-6) in Table 1. 3) PTSA: p-toluenesulfonic acid 4) Sunshine weather meter (JIS B-77)
After exposure for 3000 hours using (53), the state of the coating film was visually judged.

Comparative Example 1 The polycarboxyl compound solution 33.1 of Example 2 (1)
Parts by weight, 100 parts by weight of compound B-2, 2.0 parts by weight of acid catalyst-B, 0.3 parts by weight of modaflow, xylene 1
A clear paint comprising 0.0 parts by weight and 2.0 parts by weight of n-butyl acetate was prepared, and subjected to a storage stability test in the same manner as in Application Examples 1 to 9. Since no compound was used, the gel was formed after 3 days.

Response to 2-coat 1-bake metallic color
Use applications 10-12 (1) mixing the raw material in the composition of Table 7 prepared clear coating was a one-pack clear paint. Each of the obtained paints was diluted to 1 poise (measured at 20 ° C. with a Brookfield viscometer) using thinner (xylene / n-butyl acetate = 8/2 weight ratio), and then diluted with 5 wt.
Stored sealed at 0 ° C. After storage at 50 ° C. for 30 days, the viscosity was measured again. As shown in Table 8, almost no increase in viscosity was observed, and excellent storage stability was exhibited. (2) Preparation of test piece A cationic electrodeposition paint Aqua No. was applied to a zinc phosphate-treated mild steel sheet.
4200 (trade name, manufactured by NOF Corporation) with a dry film thickness of 20
μm and baked at 175 ° C. for 25 minutes. A 1500 CP sealer (trade name, manufactured by NOF CORPORATION) was applied by air spray coating so as to have a dry film thickness of 40 μm, and baked at 140 ° C. for 30 minutes to prepare a test plate. Then, Bellcoat No. 6000 silver metallic base coat paint (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) by air spray at intervals of 1 minute and 30 seconds, dry film thickness of 2 stages at 15 μm
m, and set at 20 ° C. for 3 minutes. Then, the clear paint of the above (1) was applied with a coating viscosity (Ford Cup N
o. (4, 25 seconds at 20 ° C.) was applied by air spray coating and baked under the conditions shown in Table 8 to prepare test specimens. The coating film performance is shown in Table 8. In each case, a uniform and glossy coating film was obtained, showing excellent acid resistance, impact resistance, weather resistance and hardness.

[0078]

[Table 10]

Note 1) Same as the latent carboxyl compound solution (1) in Table 4. 2) Compound B-8 28.4% by weight of glycidyl methacrylate, 13.0% by weight of hydroxyethyl methacrylate, 10.0% by weight of butyl methacrylate, 24.7% of methyl methacrylate
A monomer mixture consisting of 23.9% by weight of 2-ethylhexyl acrylate and 23.9% by weight was synthesized in the same manner as in Compound B-1 (Preparation Example 1). Non-volatile content 50 wt%, Gardner viscosity W. 3) Compound B-9 glycidyl methacrylate 28.4% by weight, methacryloyloxypropyltrimethoxysilane 8.3% by weight,
A monomer mixture consisting of 20.0% by weight of butyl methacrylate, 27.7% by weight of methyl methacrylate, and 15.6% by weight of 2-ethylhexyl acrylate was prepared using Compound B-1.
It was synthesized in the same manner as in (Production Example 1). Non-volatile content 50wt
%, Gardner viscosity U 4) Cymel 303: Methylated melamine resin manufactured by Mitsui Cyanamid Co., Ltd., nonvolatile content 98 wt% 5) Coronate 2513 (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.) Non-volatile content 80wt%, isocyanate content 1
0.2 wt% 6) Acid catalyst B: p-toluenesulfonic acid (1
-Methylheptyl) in xylene.

[0080]

[Table 11] Note 1) PTSA: p-toluenesulfonic acid 2) Sunshine weather meter (JIS B-77)
After exposure for 3000 hours using (53), the state of the coating film was visually judged.

[0081]

The latent carboxyl compound of the present invention not only gives a cured product having excellent chemical performance, physical performance and weather resistance, but also has excellent storage stability. For example, paints, inks, adhesives, molded articles, etc. It can be suitably used to provide a thermosetting composition that is suitably used, and can be efficiently produced by the method of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08J 3/24 C08J 3/24 C08L 101: 00 (72) Inventor Osamu Oe 7-17-3 Ebara Shinagawa-ku, Tokyo (56) References JP-A-1-104646 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) B05D 7/24 302 C08F 20/04-20/40 C08G 63/91 C08J 3/24

Claims (10)

(57) [Claims] 1. A polycarboxyl compound having two or more carboxyl groups per molecule and having an acid equivalent of 1,000 g / mol or less and a number average molecular weight of 4000 or less,
The carboxyl group is converted to a vinyl ether compound by a general formula (1). (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 18 carbon atoms, and R ³ and R ⁴ are bonded to each other. May form a heterocyclic ring having Y ¹ as a hetero atom, and Y ¹ is an oxygen atom or a sulfur atom.) . 2. The latent carboxyl compound according to claim 1, wherein the polycarboxyl compound is a half esterified product of a polyol having two or more hydroxyl groups per molecule and an acid anhydride. 3. The latent carboxyl compound according to claim 2, wherein the polyol is a polyhydric alcohol. 4. The latent carboxyl compound according to claim 2, wherein the polyol is a lactone-modified polyol. 5. The latent carboxyl compound according to claim 2, wherein the polyol is a urethane-modified polyol. 6. The latent carboxyl compound according to claim 2, wherein the polyol is a silicone-modified polyol. 7. The latent carboxyl compound according to claim 1, wherein the polycarboxyl compound is an adduct of a polyisocyanate compound having two or more isocyanate groups per molecule with a hydroxycarboxylic acid or an amino acid. 8. The latent carboxyl compound according to claim 1, wherein the polycarboxyl compound is a polyester resin. 9. The latent carboxyl compound according to claim 1, wherein the polycarboxyl compound is an acrylic resin. 10. An acid catalyst having two or more carboxyl groups per molecule and an acid equivalent of 1000 g / mo in the presence of an acid catalyst.
The method for producing a latent carboxyl compound according to any one of claims 1 to 9, wherein a polycarboxyl compound having a number of 1 or less and a number average molecular weight of 4000 or less is reacted with a vinyl ether compound.