JPH0586298A - Fluorine-containing thermosetting composition - Google Patents

Abstract

PURPOSE:To obtain a one-pack composition having high storage stability and giving a cured material having excellent chemical properties, physical properties, stain-resistance and weather resistance at a relatively low temperature by compounding a compound containing specific functional group, a fluorine- containing compound and a thermal latent acid catalyst. CONSTITUTION:The objective composition is produced by compounding (A) a compound having >=2 functional groups of formula (R<1> to R<3> are H or 1-18C organic group; R<4> is 1-18C organic group; R<3> and R<4> may together form a heterocyclic group containing Y<1> as the hetero-atom; Y<1> is O or S), (B) a fluorine- containing compound having >=2 reactive functional groups capable of forming a chemical bond with the above functional group by heating (e.g. epoxy group, alkoxysilane group or hydroxyl group) in one molecule and, as necessary, (C) a thermal latent acid catalyst exhibiting its activity by thermal curing, e.g. a compound produced by neutralizing a protonic acid or a Lewis acid with a Lewis base. The component A is a polymer of an alpha,beta-unsaturated compound or a polyester resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel fluorine-containing thermosetting composition, and more particularly, it has good chemical performance, physical performance, stain resistance and weather resistance, and particularly excellent storage stability. For example, it relates to a fluorine-containing thermosetting composition suitable for paints, inks, adhesives, molded articles and the like.

[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, a vinyl ether group, a vinyl thioether group, an aminomethylol group, an alkylated aminomethylol group, an acetal group, a ketal group or 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 are highly reactive, 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 shorter pot life occur. As a method for solving such a problem, for example, a method of blocking a carboxyl group as t-butyl ester and regenerating it into a free carboxyl group by decomposing and isolating isobutene has been proposed (JP-A-1-104646). Bulletin). 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 sufficiently satisfactory method from the viewpoint of recent resource saving and energy saving.

[0003]

The present invention provides a cured product having excellent chemical performance, physical performance, stain resistance and weather resistance at a relatively low temperature, and has good storage stability.
The purpose of the present invention is to provide a fluorine-containing thermosetting composition that can be used as a one-pack type.

[0004]

The inventors of the present invention have conducted extensive studies to develop a fluorine-containing thermosetting composition having the above-mentioned preferable properties, and as a result, (A) a special vinyl ether group or vinyl thioether. A compound having two or more carboxyl groups in one molecule, which are blocked with a heterocyclic group having a vinyl type double bond having an oxygen atom or a sulfur atom as a hetero atom, (B) the blocked It contains as an essential component a fluorine-containing compound having two or more reactive functional groups capable of forming a chemical bond with a carboxyl group by heating, and optionally (C) a thermal latent acid catalyst showing activity during heat curing. Or (D) special vinyl ether group, vinyl thioether group, or vinyl type double bond having oxygen atom or sulfur atom as a hetero atom A fluorine-containing compound having two or more carboxyl groups blocked with a heterocyclic group in one molecule, (E) a reactive functional group capable of forming a chemical bond with the blocked carboxyl group by heating Having at least one, and optionally (C)
Or a composition containing the thermal latent acid catalyst as an essential component, or the fluorine-containing compound of (D), the fluorine-containing compound of (B), and optionally the heat latent of (C). It has been found that the object can be achieved by a composition containing a carboxylic acid catalyst as an essential component, and the present invention has been completed based on this finding. That is, the present invention provides a compound represented by the general formula (A) in one molecule.

[0005]

[Chemical 4]

(In the formula, 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 1 to 1 carbon atoms.
8 is an organic group, and R ³ and R ⁴ are bonded to each other to form Y ¹
May form a heterocycle having a hetero atom, Y ¹
Is an oxygen atom or a sulfur atom) 2
A compound having two or more groups, (B) a fluorine-containing compound having two or more reactive functional groups capable of forming a chemical bond with the above functional group in one molecule, and (C) heat curing A fluorine-containing thermosetting composition containing a heat-latent acid catalyst which is sometimes active as an essential component,
(D) In one molecule, the general formula

[0007]

[Chemical 5]

(In the formula, 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 1 to 1 carbon atoms.
8 is an organic group, and R ⁷ and R ⁸ are bonded to each other to form Y ²
May form a heterocycle having a hetero atom of Y ²
Is an oxygen atom or a sulfur atom) 2
Or more fluorine-containing compounds, (E) in one molecule,
A fluorine-containing system containing as an essential component a compound having two or more reactive functional groups capable of forming a chemical bond by heating with the functional group, and optionally a thermal latent acid catalyst of the component (C). A thermosetting composition, a fluorine-containing compound as the component (D), a fluorine-containing compound as the component (B), and optionally a heat-latent acid catalyst as the component (C) are contained as essential components. And a fluorine-containing thermosetting composition comprising: Hereinafter, the present invention will be described in detail. The compound used as the component (A) in the composition of the present invention has a general formula

[0009]

[Chemical 6]

Two or more functional groups represented by the formula (wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹ have the same meanings as described above), preferably 2 to 50 functional groups per molecule. A compound having
The functional group represented by the general formula [1] includes a carboxyl group and a general formula

[0011]

[Chemical 7]

(Wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹ have the same meanings as defined above), a vinyl thioether compound, or an oxygen atom or a sulfur atom as a hetero atom. It can be easily formed by a reaction with a heterocyclic compound having a vinyl type double bond. R ¹ in the general formulas [1] and [3],
R ² and R ³ are each a hydrogen atom or an organic group such as an alkyl group having 1 to 18 carbon atoms, an aryl group or an alkaryl group, and R ⁴ is an alkyl group having 1 to 18 carbon atoms or an aryl group;
Organic groups such as alkaryl groups, which may have suitable substituents, and R ³ and R
⁴ may be bonded to each other to form a heterocycle having no substituent or having a substituent in which Y ¹ is a heteroatom. Specific examples of the compound represented by the general formula [3] include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether and n-.
Butyl vinyl ether, isobutyl vinyl ether, 2
-Aliphatic vinyl ether compounds such as ethylhexyl vinyl ether and cyclohexyl vinyl ether, and corresponding aliphatic vinyl thioether compounds, and further 2,3-dihydrofuran, 3,4-dihydrofuran,
2,3-dihydro-2H-pyran, 3,4-dihydro-2
H-pyran, 3,4-dihydro-2-methoxy-2H-
Pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2
Examples thereof include cyclic vinyl ether compounds such as H-pyran, sodium 3,4-dihydro-2H-pyran-2-carboxylate, and 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 a compound represented by the above general formula [3]. be able to. Examples of the compound having two or more carboxyl groups in one molecule include succinic acid, adipic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, and other aliphatic polycarboxylic acids having 2 to 22 carbon atoms, phthalic acid, Aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid,
Alicyclic polycarboxylic acids such as tetrahydrophthalic acid and hexahydrophthalic acid, and 2 carboxyl groups in one molecule
Examples thereof include polyester resins having at least one, acrylic resin, and maleated polybutadiene resin. Further, the compound having two or more carboxyl groups in one molecule is, for example, (1) half-esterified with a polyol having 2 or more, preferably 2 to 50, hydroxyl groups per molecule and an acid anhydride. (2) A carboxyl group-containing α, β-unsaturated monomer for adding a polyisocyanate compound having two or more, preferably 2 to 50, isocyanate groups per molecule to a hydroxycarboxylic acid or an amino acid Is homopolymerized or copolymerized with another α, β-unsaturated monomer, and (4) a carboxyl group-terminated polyester resin is synthesized. Examples of the polyol having two or more hydroxyl groups per molecule include ethylene glycol, 1,
2- and 1,3-propylene glycol, 1,3-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,
Polyhydric alcohols such as 2,4-butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, quinitol, mannitol, trishydroxyethyl isocyanurate and dipentaerythritol; these polyhydric alcohols and γ-butyrolactone and ε -Ring-opening adducts with lactone compounds such as caprolactone; adducts of the polyhydric alcohols with isocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate in the presence of excess alcohol; Alcohols and ethylene glycol divinyl ether, polyethylene glycol divinyl ether,
Butanediol divinyl ether, pentanediol divinyl ether, hexanediol divinyl ether,
Adducts with vinyl ether compounds such as 1,4-cyclohexanedimethanol divinyl ether in the presence of excess alcohol; and the polyhydric alcohols and alkoxy silicone compounds such as KR-213, KR-217, KR-
9218 [all manufactured by Shin-Etsu Chemical Co., Ltd., trade name] and the like can be mentioned as an adduct in the presence of excess alcohol.

On the other hand, examples of acid anhydrides to be reacted with these polyols include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, phthalic acid, maleic acid, trimellitic acid and pyromellitic acid. Mention may be made of acid anhydrides of polyhydric carboxylic acids such as acids, tetrahydrophthalic acid, hexahydrophthalic acid and the like. Further, as the polyisocyanate compound having two or more isocyanate groups per molecule, 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, methylenebis (phenylisocyanate), lysine methyl ester diisocyanate, bis (isocyanatoethyl) fumarate, isophorone diisocyanate, methylcyclohexyl diisocyanate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate and their burettes and isocyanurates And so on. Examples of the hydroxycarboxylic acid include lactic acid, citric acid, hydroxypivalic acid, 12-hydroxystearic acid, malic acid and the like, and examples of the amino acid include DL-alanine, L-glutamic acid, glycine,
Examples thereof include L-theanine, glycylglycine, γ-aminocaproic acid, L-aspartic acid, L-citrulline, L-arginine, L-leucine and L-serine.

Further, the carboxyl group-containing α, β-unsaturated monomer includes, for example, acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, and the like. Examples of the β-unsaturated monomer include 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, α-methylstyrene, p-vinyltoluene,
Acrylonitrile etc. can be mentioned. Further, the carboxyl group-terminated polyester resin can be easily formed according to a usual polyester resin synthesis method in the presence of a polybasic acid excess with respect to the polyhydric alcohol.

The reaction of the compound thus obtained having two or more carboxyl groups in one molecule with the compound represented by the above general formula [3] is usually at room temperature to 100 ° C. in the presence of an acidic catalyst. At a temperature in the range. In the composition of the present invention, the compound of the component (A) may be used alone or in combination of two or more.
As the fluorine-containing compound used as the component (B) in the composition of the present invention, the blocked functional group represented by the general formula [1] in the compound of the component (A) is regenerated to a free carboxyl group by heating. At this time, those having two or more, preferably 2 to 50, reactive functional groups capable of reacting with this to form a chemical bond in one molecule are used. The reactive functional group may be one having the above-mentioned properties and, for example, an epoxy group, an alkoxysilane group, a hydroxyl group, an acetal group and a ketal group are particularly preferable. One of these reactive functional groups may be contained, or two or more thereof may be contained.

The component (B) of the composition of the present invention comprises an α, β-unsaturated monomer having the above-mentioned reactive functional group and a fluorine-containing α, β.
Obtainable by copolymerizing an unsaturated monomer and optionally another α, β-unsaturated monomer. Specific examples of the α, β-unsaturated monomer having a reactive functional group include α, β-unsaturated monomers having an epoxy group such as p-glycidyloxystyrene and p-glycidyloxy-α. -Methylstyrene, p- (3,4-epoxycyclohexylmethyloxy) styrene, p- (3,4-epoxycyclohexylmethyloxy) -α-methylstyrene,
Glycidyl ethylene, 3,4-epoxycyclohexyl methyl ethylene, glycidyl vinyl ether, 3,4-
Epoxy cyclohexyl methyl vinyl ether, glycidyl allyl ether, 3,4-epoxy cyclohexyl methyl allyl ether, and the like, and as the α, β-unsaturated monomer having an alkoxysilane group, for example, vinyltrimethoxysilane, allyltrimethoxysilane, Trimethoxysilyl vinyl ether, trimethoxysilyl allyl ether, p-trimethoxysilylstyrene, p
-Trimethoxysilyl-α-methylstyrene, p-trimethoxysilyloxystyrene, p-trimethoxysilyloxy-α-methylstyrene and the like, and examples of the α, β-unsaturated monomer having a hydroxyl group include Hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxycyclohexyl vinyl ether, hydroxyethyl allyl ether, hydroxypropyl allyl ether, hydroxybutyl allyl ether and the like,
As the α, β-unsaturated monomer having an acetal group, for example, acetalized product of 1 mol of ethylene glycol divinyl ether and 1 mol of monohydric alcohol such as methanol, ethanol, propanol, butanol, 1 mol of propylene glycol divinyl ether and the above An acetalized product of 1 mol of monohydric alcohol, an acetalized product of 1 mol of polyethylene glycol divinyl ether and 1 mol of the monohydric alcohol, an acetalized product of 1 mol of cyclohexanedimethanol divinyl ether and 1 mol of the monohydric alcohol, and the like. You can

Examples of the fluorine-containing α, β-unsaturated monomer include, for example, CF ₂ ═CF ₂ , CHF═CF ₂ , CH ₂
= CF ₂ , CH ₂ = CHF, CClF = CF ₂ , CHCl
= CF ₂ , CCl ₂ = CF ₂ , CClF = CClF, CH
F = CCl ₂ , CH ₂ = CClF, CCl ₂ = CClF,
CF ₃ CF = CF ₂ , CF ₃ CF = CHF, CF ₃ CH = C
F ₂ , CF ₃ CF = CH ₂ , CHF ₂ CF = CHF, CH ₃
CF = CF ₂ , CH ₃ CF = CH ₂ , CF ₂ ClCF = CF
₂ , CF ₃ CCl = CF ₂ , CF ₃ CF = CFCl, CF ₂
ClCCl = CF ₂ , CF ₂ ClCF = CFCl, CFC
l ₂ CF = CF ₂ , CF ₃ CCl = CClF, CF ₃ CCl
= CCl ₂ , CClF ₂ CF = CCl ₂ , CCl ₃ CF = C
F ₂ , CF ₂ ClCCl = CCl ₂ , CFCl ₂ CCl = C
Cl ₂ , CF ₃ CF = CHCl, CClF ₂ CF = CHC
1, CF ₃ CCl = CHCl, CHF ₂ CCl = CC
l ₂ , CF ₂ ClCH = CCl ₂ , CF ₂ ClCCl = CH
Cl, CCl ₃ CF = CHCl, CF ₂ ClCF = C
F ₂ , CF ₂ BrCH = CF ₂ , CF ₃ CBr = CHBr,
_{CF 2 ClCBr = CH 2, CH} 2 BrCF = CCl 2, C
F ₃ CBr = CH ₂ , CF ₃ CH = CHBr, CF ₂ BrC
_{H = CHF, CF 2 BrCF =} CF 2, CF 3 CF 2 CF =
CF ₂ , CF ₃ CF = CFCl ₃ , CF ₃ CH = CFC
F ₃ , CF ₂ = CFCF ₂ CHF ₂ , CF ₃ CF ₂ CF = CH
₂ , CF ₃ CH = CHCF ₃ , CF ₂ = CFCF ₂ CH ₃ , C
F ₂ = CFCH ₂ CH ₃ , CF ₃ CH ₂ CH = CH ₂ , CF ₃
CH = CHCH ₃ , CF ₂ = CHCH ₂ CH ₃ , CH ₃ CF ₂
CH = CH ₂ , CFH ₂ CH = CHCFH ₂ , CH ₃ CF _{2
CH = CH 2, CH 2 =} CFCH 2 CH 3, CF 3 (CF 2) 2
CF = CF ₂ , CF ₃ (CF ₂ ) ₃ CF = CF ₂ , or CH
_{2 = C (CH 3) COOC} 2 H 4 C 4 F 9, CH 2 = C (C
_{H 3) COOC 2 H 4 (} CF 2) 6 CF (CF 3) 3, CH 2 = C
_{(CH 3) COOC 2 H 4} C 8 F 17, CH 2 = C (CH 3) C
OOC like ₂ H ₄ C ₁₀ F ₂₁ and the like.

By using these fluorine-containing α, β-unsaturated monomers, it is possible to form a coating film excellent in acid resistance, stain resistance, weather resistance and water repellency. Further, other α, β-unsaturated monomers include, for example, olefins such as ethylene, propylene, butylene, isoprene and chloroprene, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, t-butyl vinyl ether, pentyl vinyl ether. Vinyl ether such as hexyl vinyl ether, isohexyl vinyl ether, cyclohexyl vinyl ether, octyl vinyl ether, 4-methyl-1-pentyl vinyl ether, cyclopentyl vinyl ether, phenyl vinyl ether, o-, m-, p-tolyl vinyl ether, benzyl vinyl ether and phenethyl vinyl ether, and allyl. Ethers, vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, Vinyl Sokapuron acid, vinyl Pibarikku, vinyl caprate, isopropenyl acetate, vinyl esters and propenyl esters such as isopropenyl propionate, (meth) acrylate, (meth)
Ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate,
(Meth) octyl (meth) acrylate, lauryl (meth) acrylate, methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate, ethoxybutyl (meth) acrylate, etc. Examples thereof include acrylic acid esters, vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and p-chlorostyrene, and acrylonitrile and methacrylonitrile. The compound used as the component (D) in the composition of the present invention has a general formula

[0020]

[Chemical 8]

It has two or more functional groups represented by the formula (R ⁵ , R ⁶ , R ⁷ , R ⁸ and Y ² have the same meanings as described above), preferably 2 to 50 functional groups in one molecule. The functional group represented by the general formula [2] in the compound is a carboxyl group,
General formula

[0022]

[Chemical 9]

A vinyl ether compound represented by the formula (wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ and Y ² have the same meanings as described above),
It can be easily formed by a reaction with 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. R ⁵ , R ⁶ and R ⁷ in the general formulas [2] and [4] are each a hydrogen atom or an organic group such as an alkyl group, an aryl group or an alkaryl group having 1 to 18 carbon atoms, R ⁸
Is an organic group having 1 to 18 carbon atoms such as an alkyl group, an aryl group and an alkaryl group, and these organic groups may have an appropriate substituent, and R ⁷ and R ⁸ are To form a heterocycle having no or no substituent having Y ² as a hetero atom. The general formula [4]
Specific examples of the compound represented by
The compounds exemplified in the description of the compound represented by can be mentioned. The component (D) of the composition of the present invention comprises an α, β-unsaturated monomer having a hydroxyl group and a fluorine-containing α, β.
-Unsaturated monomer and optionally other α, β-unsaturated monomer are copolymerized, and then the acid anhydride is half-esterified with the hydroxyl group of the copolymer, and the produced carboxyl group is converted into the above-mentioned general formula. It is obtained by blocking with the compound represented by [4]. In addition to this method, an α, β-unsaturated monomer having a functional group represented by the general formula [2], a fluorine-containing α, β-unsaturated monomer, and optionally other α, It can also be obtained by directly copolymerizing a β-unsaturated monomer.

Here, α, β-having a hydroxyl group
Specific examples of unsaturated monomers, fluorine-containing α, β-unsaturated monomers and other α, β-unsaturated monomers include (B) above.
The thing illustrated in description of an ingredient can be mentioned. Examples of the acid anhydride used for preparing the component (D) include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, phthalic acid, maleic acid, trimellitic acid. Acid anhydrides of polyvalent carboxylic acids such as pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid and methylated hexahydrophthalic acid. Further, as the α, β-unsaturated monomer having a functional group represented by the general formula [2], for example, acrylic acid, methacrylic acid, crotonic acid, 2-carboxyethyl (meth) acrylate, 2
Of an α, β-unsaturated monomer having a carboxyl group, such as carboxylpropyl (meth) acrylate, 5-carboxylpentyl (meth) acrylate, acrylic acid dimer, and an adduct of (meth) acrylic acid and ε-caprolactone. It can be easily obtained by blocking the carboxyl group with the compound represented by the general formula [4].

As the compound used as the component (E) in the composition of the present invention, the blocked functional group represented by the general formula [2] in the fluorine-containing compound of the component (D) is a free carboxyl group by heating. Those having 2 or more, preferably 2 to 50, reactive functional groups capable of reacting with this to form a chemical bond upon regeneration, are used. The reactive functional group is not particularly limited as long as it has the above-mentioned properties, and for example, 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. , Cyclocarbonate group, vinyl ether group, vinyl thioether group, aminomethylol group, alkylated aminomethylol group, acetal group, ketal group and the like are preferable. One of these reactive functional groups may be contained, or two or more thereof may be contained. Specific examples of the compound as the component (E) include a bisphenol type epoxy resin, an alicyclic epoxy resin, a homopolymer such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate, or a copolymer. An epoxy group-containing compound such as a polyglycidyl compound obtained by reacting a polymer, a polycarboxylic acid or a polyol with epichlorohydrin; a general formula (R ⁹ ) _n Si (OR ¹⁰ ) _4-n ... [5] (R in the formula ⁹ and R ¹⁰ are each an alkyl group or aryl group having 1 to 18 carbon atoms, and n is 0, 1 or 2.

A condensate of a compound represented by the following, a homopolymer of an α, β-unsaturated silane compound such as acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltri-n-butoxysilane, or Silanol group- or alkoxysilane group-containing compounds such as copolymers and hydrolysis products of these compounds; aliphatic polyols, phenols, polyalkyleneoxyglycols, 2-hydroxy (meth) acrylate and 2-hydroxypropyl Homopolymers or copolymers of α, β-unsaturated compounds such as (meth) acrylate, and hydroxyl group-containing compounds such as ε-caprolactone adducts of these polyols; aliphatic and aromatic diamino compounds and polyamino compounds Compound and the polyol Amino group-containing compounds such as polyamino compound obtained by reducing a cyanoethylation reaction product, aliphatic, imino group-containing compounds such as an aromatic polyimino compounds; 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, methylenebis (phenylisocyanate), lysine methyl Ester diisocyanate, bis (isocyanate ethyl) fumarate, isophorone diisocyanate, methylcyclohexyl diisocyanate, 2-isocyanate ethyl-2,
6-diisocyanate hexanoate and burettes and isocyanurates thereof, and further isocyanate group-containing compounds such as adduct compounds of these isocyanates and the above polyols; phenols, lactams and active methylene of the above isocyanate group-containing compounds , Alcohols, acid amides, imides, amines,
Imidazoles, ureas, imines, blocked isocyanate group-containing compounds such as blocks with oximes; 3- (meth) acryloyloxypropylene carbonate homopolymer or copolymer, the epoxy group-containing compound and carbon dioxide A cyclocarbonate group-containing compound such as a polyvalent cyclocarbonate group-containing compound obtained by the reaction of the above; a polyvalent vinyl ether compound, a hydroxyalkyl vinyl ethers and a polyvalent vinyl ether compound obtained by reacting the polyvalent hydroxyl group-containing compound with a halogenated alkyl vinyl ether Polyvinyl ether compound and vinyloxyalkyl (meth) obtained by reaction with a compound containing a valent carboxyl group or the above polyisocyanate compound
Vinyl ether compounds such as copolymers of acrylates and α, β-unsaturated compounds, and vinyl ether groups and vinyl thioether group-containing compounds such as vinyl thioether compounds corresponding thereto; melamine formaldehyde resins, glycoluril formaldehyde resins, urea formaldehyde Resins, aminomethylol groups and alkylated aminomethylol group-containing α, β-unsaturated compounds such as homopolymers or copolymers of aminomethylol groups and alkylated aminomethylol group-containing compounds; polyvalent ketones, polyvalent aldehyde compounds, A polyvalent acetal compound obtained by reacting the polyvalent vinyl ether compound or the like with an alcohol or an ortho acid ester, a condensate of the polyvalent acetal compound and a polyol compound, and further, a vinyloxyalkyl (meth) acrylate and an alkane. Examples thereof include acetal group- and ketal group-containing compounds such as homopolymers or copolymers of adducts with choles and orthoacid esters.

In the composition of the present invention, as the compound of the component (B) or the component (E), a compound having two or more reactive functional groups is used in addition to the compound having one reactive functional group. The component (B) or the component (E) may be used in combination of two or more kinds. However, in this case, a combination in which each functional group is active is unfavorable because the storage stability is impaired. Such unfavorable combinations 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. Examples thereof include a combination of a group and a hydroxyl group. In the fluorine-containing thermosetting composition of the present invention, the components (A) and (E) are α, β-
A polymer of an unsaturated compound and / or a polyester resin is preferable, and the components (B) and (D) are preferably a copolymer of a fluorine-containing α, β-unsaturated monomer. .. In addition, the general formula [1] in the composition,
The functional group represented by [2] and the 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. It is desirable to include each component.

The fluorine-containing thermosetting composition of the present invention is a combination of the above components (A) / (B), (D) / (E) and (D) / (B). In some cases, the components (C) are combined, but in the composition of the present invention, if desired, the components (A) / (B) /
(D) component, (A) component / (B) component / (E) component /
(B) component / (D) component / (E) component, (A) component /
A combination of component (B) / component (D) / component (E) may be used, or in some cases, component (C) may be further combined with each combination. The functional groups represented by the general formulas [1] and [2] of the components (A) and (D) of the present invention regenerate a free carboxyl group under heating,
Component (B), which forms a chemical bond with the reactive functional groups of component (E), in addition to this reaction, as a so-called active ester based on the intramolecular polarization structure, component (B) or component (E) Can react with the reactive functional group of.
In this case, since the elimination reaction is not accompanied during the crosslinking reaction, it is possible to contribute to the reduction of the emission of volatile organic substances.

In the present invention, these compositions may have good storage stability over a long period of time, and when they are cured at a low temperature in a short time, they accelerate the curing reaction to give cured products. For the purpose of imparting good chemical performance and physical performance, a thermal latent acid catalyst which is active during heat curing can be contained as the component (C). The thermal latent acid catalyst is preferably a compound that exhibits acid catalytic activity at a temperature of 60 ° C or higher. When this thermal latent acid catalyst exhibits an acid catalytic activity at a temperature of less than 60 ° C., the composition obtained may have an unfavorable situation such as thickening or gelation during storage. As the thermal latent acid catalyst of the component (C), a compound obtained by neutralizing a protonic acid with a Lewis base, a compound obtained by neutralizing a Lewis acid with a Lewis base, a mixture of a Lewis acid and a trialkyl phosphate, sulfonic acid esters,
Phosphoric acid esters and onium compounds are preferred.

Examples of compounds obtained by neutralizing the protonic acid with a Lewis base include halogenocarboxylic acids, sulfonic acids, sulfuric acid monoesters, phosphoric acid mono- and diesters, polyphosphoric acid esters, boric acid mono- and diesters, and the like. , Various amines such as ammonia, monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethynolamine, diethanolamine, triethanolamine or trialkylphosphines, triarylphosphines, trialkylphosphites , A compound neutralized with triaryl phosphite, and further commercially available as acid-base blocked catalysts, NURECURE 2500X, X-47-110, 3525, 5
225 (trade name, manufactured by King Industry Co., Ltd.) and the like. Examples of compounds obtained by neutralizing a Lewis acid with a Lewis base include BF ₃ , FeCl ₃ , SnCl ₄ , and A.
Examples thereof include compounds obtained by neutralizing a Lewis acid such as 1Cl ₃ , ZnCl ₂ and ZnBr ₂ with the above Lewis base. Alternatively, a mixture of the above-mentioned Lewis acid and trialkyl phosphate may be mentioned. Examples of the sulfonates include those represented by the general formula

[0031]

[Chemical 10]

(Wherein R ¹¹ is phenyl group, substituted phenyl group, naphthyl group, substituted naphthyl group or alkyl group, R ¹²
Is a C3-C18 alkyl group, alkenyl group, aryl group, alkaryl group, alkanol group, saturated or unsaturated cycloalkyl or hydroxycyclo group which is bonded to a sulfonyloxy group through a primary carbon or a secondary carbon. An alkyl group), specifically, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, nonylnaphthalenesulfonic acid and other sulfonic acids, and n-propanol, Primary alcohols such as n-butanol, n-hexanol, and n-octanol or esterification products with secondary alcohols such as isopropanol, 2-butanol, 2-hexanol, 2-octanol, and cyclohexanol, and further the above Sulfonic acids and oxirane groups Such as β- hydroxyalkyl sulfonates obtained by the reaction of organic compounds. Examples of the phosphoric acid esters include those represented by the general formula

[0033]

[Chemical 11]

(R ¹³ in the formula is an alkyl group having 3 to 10 carbon atoms, a cycloalkyl group or an aryl group, 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. The phosphoric acid monoesters or phosphoric acid diesters of Examples of the onium compounds, for example the general formula _{^{[R 14 3 NR 15] +}} X - ... [8] [R 14 3 PR 15] + X - ... [9] [R 14 2 OR 15] + X - ... [ 10] and _{^{[R 14 2 SR 15] +}} X - ... [11] (R 14 in the formula is an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group, alkaryl group, alkanol group or a cycloalkyl group And two R ^{14 s} may combine with each other to form a heterocycle having N, P, O or S as a heteroatom, and R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. , An alkenyl group, an aryl group, an alkaryl group, and X ⁻ is SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ^−, or BF ₄ ⁻ ).

In the composition of the present invention, the thermal latent acid catalyst of the component (C) may be used alone or in combination of two or more, and the compounding amount thereof is the component (A). And (B) component, (D) component and (E) component, or (D)
Per 100 parts by weight of the total solid content of the component and the component (B),
Usually, it is selected in the range of 0.01 to 10 parts by weight. Regarding the temperature and time required for curing the thermosetting composition of the present invention, the temperature at which the free carboxyl group is regenerated from the blocked functional group represented by the general formula [1] or [2], the reactive functional group The curing is completed by heating at a temperature in the range of 50 to 200 ° C. for about 2 minutes to 1 hour, though it depends on the type of the above, the type of thermal latent acid catalyst and the like. The thermosetting composition of the present invention may be used as it is or in a paint, an ink, an adhesive, a molded article, etc., if necessary, by adding a coloring pigment, a filler, a solvent, an ultraviolet absorber, an antioxidant and the like. You can

[0036]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The coating film performance was determined as follows. (1) Acid resistance Place 2 ml of 40 wt% sulfuric acid on the test piece in a spot shape and
After leaving at 30 ° C. for 30 minutes, the abnormality of the coating film was visually determined. (2) Contamination resistance 1 g of JIS type 15 contaminated dust was placed on the coating film, and this was spread evenly by sweeping it 20 times with a brush, and allowed to stand at 20 ° C for 1 day. Next, this was washed in running water using a clean brush, and the degree of contamination was visually evaluated. (3) Impact resistance Impact deformation tester [JIS K-5400 (1990) 8.
3.2 DuPont type], the test piece was inserted into a shooting die having a radius of 6.35 mm, and the damage of the coating film was visually determined when a 500 g weight was dropped from a height of 40 cm. (4) Weather resistance Sunshine weather meter [JIS K-5400
(1990) 9.8.1 Sunshine carbon arc lamp type], and after exposure for 3000 hours, the specular gloss value [JIS K-5400 (1990) 7.6 60 degree specular gloss] of the coating film is measured, Abnormalities in the coating film were visually determined or compared with the gloss value before exposure. (5) Knoop hardness Measured at 20 ° C. with an M type micro hardness meter manufactured by Shimadzu Corporation. The larger the value, the harder it is.

Production Examples 1 and 2(A) Component Compounds A-1, A-2 Solution Production  (1) Production of α, β-unsaturated compound Four-necked flask equipped with thermometer, reflux condenser and stirrer
The mixture having the composition shown in Table 1 was charged to
Stir while maintaining. The acid value of the mixture became 30 or less
By the way, after the reaction was completed, the product was transferred to a separating funnel after cooling.
did. The product obtained is 10 wt% carbonic acid in a separating funnel.
After alkali cleaning with 100 parts by weight of sodium hydrogen solution,
200 parts by weight of deionized water until the pH of the cleaning solution is below 7
Washing with water was repeated. Then the molecular in the organic layer
-Add sheave 4A1 / 16 [Wako Pure Chemical Industries, Ltd.]
By drying for 3 days,
Α, β-Unsaturated Compound A-1 Having Effective Content
(A) and A-2 (a) were obtained.

[0038]

[Table 1]

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

(2) Preparation of solutions of compounds A-1 and A-2 A four-necked flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was used, and the amount of the initially charged solvent ( Xylene) was charged and heated under stirring to maintain 80 ° C. Next, at a temperature of 80 ° C., a mixture of the monomer and the polymerization initiator having the composition shown in Table 2 (dropping component) was added dropwise at a constant rate from a dropping funnel over 2 hours. After completion of the dropping, the temperature of 80 ° C. was maintained for 1 hour, the polymerization initiator solution (additional catalyst) having the composition shown in Table 2 was added, and the reaction was terminated when the temperature of 80 ° C. was further maintained for 4 hours. Compound A-1 and A-2 solutions having the properties shown in Table 2 were obtained.

[0041]

[Table 2]

Note 1) Nonvolatile content measurement conditions 50 ° C., 0.1 mmHg for 3 hours 2) Viscosity; Gardner foam viscosity (25 ° C.) [JIS K-5400 (1990) 4.5.1 Gardner foam viscometer method by]

Production Example 3(A) Preparation of component compound A-3 solution  (1) Production of polycarboxylic acid Four equipped with thermometer, reflux condenser, stirrer, and dropping funnel
Charge the following ingredients into a neck flask and heat with stirring to 120
The temperature was raised to ° C. Pentaerythritol 136.0 parts by weight Methyl isobutyl ketone 538.7 parts by weight Next, while maintaining 120 ° C., methyl hexahydrophthalate
672.0 parts by weight of acid anhydride was added dropwise over 2 hours and mixed.
Acid value of compound (Pyridine / water weight ratio = 9/1 about 5
Solution diluted 0 times by weight and heat-treated at 90 ° C for 30 minutes
Titrated with potassium hydroxide standard solution) to 170 or less
By continuing heating and stirring until
A rubic acid compound solution was obtained.

(2) Production of Compound A-3 Using the polycarboxylic acid compound solution obtained by the above method, a mixture having the following composition was placed in the same flask as above and stirred at 50 ° C. Polycarboxylic acid compound solution of (1) 336.7 parts by weight Isobutyl vinyl ether 120.2 parts by weight 35 wt% hydrochloric acid 0.2 parts by weight Methyl isobutyl ketone 46.3 parts by weight Reaction when the acid value of the mixture is 12 or less Was completed, and after cooling, the product was transferred to a separating funnel. The obtained product is a 10 wt% sodium carbonate aqueous solution 1 in a separating funnel.
After washing with 100 parts by weight of alkali, washing with 300 parts by weight of deionized water was repeated until the pH of the washing solution became 7 or less.
Then, the molecular sieve 4A1 / 16 was added to the organic layer, and the mixture was dried at room temperature for 3 days to give a nonvolatile content of 6
A compound A-3 solution having 0% by weight and a Gardner type foam viscosity EF (25 ° C.) was obtained.

Production Examples 4-8(B) Production of component compounds B-1 to B-5  The stainless steel autoclave with a stirrer has a third
Each monomer of the composition in the table, catalyst solution and sodium borate
After charging, nitrogen substitution, cooling and solidification, and deaeration, the third notation
Introduce the above-mentioned fluorine-containing monomer into the autoclave and
The temperature inside the toclave was gradually raised until it reached 60 ° C.
Then, after continuing the reaction at the same temperature for 20 hours,
Reeve internal pressure is 1kg / cm²When it falls below
I stopped working. The resulting resin solution was added with a large excess of heptane.
Pour into the inside and let the generated resin break out, then wash and dry.
After drying, the fluorine-containing compound was obtained at the yields shown in Table 3, respectively.
Products B-1 to B-5 were obtained. The gel permeation of the obtained resin
Number average by ation chromatography (GPC)
The molecular weight is also shown in Table 3. The obtained resin is
Resin that is completely dissolved in xylene and has a nonvolatile content of 50% by weight
It was a solution.

[0046]

[Table 3]

Production Examples 9 to 11(D) Production of Solution of Component Compounds D-1 to D-3  Using a device similar to Production Examples 4 to 8, a mixture having the following composition was prepared.
By reacting in the same manner as in Production Examples 4 to 8,
A resin solution having a nonvolatile content of 50% by weight was obtained. Hydroxybutyl vinyl ether 33.5 parts by weight Ethyl vinyl ether 4.3 parts by weight Cyclohexyl vinyl ether 4.3 parts by weight Methyl isobutyl ketone 20.0 parts by weight 2,2'-azobisisobutyronitrile 2.0 parts by weight Sodium borate 0 0.5 parts by weight CF₂= CFCl 57.9 parts by weight

Next, the resin solution 2 was placed in a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen gas inlet tube.
00 parts by weight, 44.5 parts by weight of hexahydrophthalic anhydride, and 44.5 parts by weight of methyl isobutyl ketone were charged and heated at a temperature of 120 ° C. under stirring with a nitrogen stream. During the reaction, the acid value (diluted 50 times by weight with a pyridine / water weight ratio = 9/1 mixed solution and heat-treated at 90 ° C. for 30 minutes and titrated with a potassium hydroxide standard solution) was measured over time, The reaction was terminated when the acid value of the mixture became 57 or less.
The obtained resin solution is a polycarboxyl compound solution having a nonvolatile content of 50% by weight. Next, using the polycarboxyl compound solution obtained by the above reaction, a mixture having the composition shown in Table 4 was charged into a four-necked flask similar to the above and stirred at room temperature. After the reaction was terminated when the acid value of the mixture became 1 or less, Kyoward 500 [Kyowa Chemical Industry Co., Ltd.
3 parts by weight of synthetic acid adsorbent] was added, the mixture was stirred at room temperature for 48 hours, filtered, and the filtrate was removed by an evaporator to produce Example 9.
7 parts by weight, in Production Example 10 9 parts by weight, and in Production Example 11 7 parts by weight of the solvent were distilled off to give a fluorine-containing compound D-1 having a nonvolatile content and a number average molecular weight shown in Table 4. ~ D-3 solution was obtained.

[0049]

[Table 4]

Production Examples 12-14(E) Component Compounds E-1 to E-3 Solution Production  4 equipped with thermometer, reflux condenser, stirrer, dropping funnel
Initially charged solvent (xylene) 4 in each neck flask
Charge 0.0 parts by weight and heat under stirring to maintain 100 ° C.
It was. Then, at a temperature of 100 ° C., a unit amount of the composition shown in Table 5 is used.
Body and polymerization initiator mixture (dripping component) over 2 hours
It was added dropwise at a constant speed from the lower funnel. After the dropping, the temperature of 100 ℃
The polymerization initiator solution having the composition shown in Table 5 is maintained for 1 hour.
(Additional catalyst) is added, and the temperature of 100 ° C. is further added for 2 hours.
The reaction was terminated when the temperature was maintained, and
A compound E-1 to E-3 solution having properties was obtained.

[0051]

[Table 5]

Note 1) MZ-11: Chemitite MZ-11, manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., trade name, 2- (1-aziridinyl) ethyl methacrylate MAGME: MAGME100, Mitsui Cyanamide Co., Ltd.
Manufactured, trade name, methyl acrylamide glycolate methyl ether IEM: isocyanate ethyl methacrylate BMA: n-butyl methacrylate MMA: methyl methacrylate EHA: 2-ethylhexyl acrylate AIBN: 2,2'-azobisisobutyronitrile 2) Nonvolatile matter: Dry for 3 hours at 50 ℃ and 0.1mmHg Viscosity (25 ℃): JIS K-5400 (1990) 4.
5.1 According to Gardner-type foam viscometer method.

Production Example 15Production of thermal latent acid catalyst of component (C)  4 ports equipped with stirrer, thermometer, dropping funnel, cooling tube
Add 598.5 parts by weight of 2-octanol to the flask.
And ice-cool it, and potassium-t-butoxide 44.9 wt.
Add parts by weight and dissolve, then add 300 parts of diethyl ether.
53.4 p-toluenesulfonyl chloride dissolved in 1 part
An aliquot was added dropwise over 30 minutes. 1 hour after dropping, use an ice bath
It was removed and allowed to react for another 1 hour. After the reaction is complete,
After washing the mixture 3 times with 400 parts by weight of water, the molecular
-Added Sieve 4A1 / 16 [Wako Pure Chemical Industries, Ltd., trade name]
After dehydration and drying, the solvent is evaporated and dried in a vacuum.
P-toluenesulfonic acid was removed by distillation in a dryer.
(1-Methylheptyl) 49 parts by weight (yield 65%) was obtained.
It was The resulting thermal latent catalyst was 265 parts by weight of xylene.
Dissolve and dilute to 10% by weight in terms of p-toluenesulfonic acid
did.

Comparative Production Example 1Preparation of compound A-4 solution  4 equipped with thermometer, reflux condenser, stirrer, dropping funnel
A neck flask was charged with 200 parts by weight of xylene and stirred.
It heated and kept at 80 degreeC. Next, at the temperature of 80 ℃,
It was added dropwise at a constant rate from the dropping funnel over 2 hours. t-butyl methacrylate 142.0 parts by weight n-butyl methacrylate 100.0 parts by weight methyl methacrylate 178.6 parts by weight 2-ethylhexyl acrylate 105.4 parts by weight n-butyl acetate 192.2 parts by weight 2,2'-azobis Isobutyronitrile 21.8 parts by weight After the completion of dropping, the temperature of 80 ° C. is maintained for 1 hour, and acetic acid n-butyrate is added.
57.0 parts by weight and 2,2'-azobisisobutyronito
3.0 parts by weight of ril is added, and the temperature of 80 ° C. is further added at 4 hours.
Non-volatile content 52.8% by weight, viscosity
(25 ° C.) S-T compound A-4 was obtained.

Examples 1 to 12 (1) Production of clear coating material The raw materials having the compositions shown in Table 6 were mixed to prepare a one-pack type clear coating material. Each of the obtained paints was 1 poise (JIS K-5400) with thinner (xylene / butyl acetate = 8/2 weight ratio).
(1990) 4.5.3 value measured at 20 ° C. by a rotational viscometer method), and then sealed and stored at 50 ° C. 50 ° C
After storage for 30 days at 30 ° C., the viscosity was measured again. As shown in Table 7, almost no increase in viscosity was observed.
It showed excellent storage stability.

(2) Preparation of test piece Cation electrodeposition paint Aqua No. on a zinc phosphate treated mild steel plate
4200 [trade name, manufactured by NOF CORPORATION] dried film thickness 20μ
m by electrodeposition and bake at 175 ° C for 25 minutes,
Further, an intermediate coating material Epico No. 1500 CP sealer [trade name, manufactured by NOF CORPORATION] was air-spray coated to a dry film thickness of 40 μm and baked at 140 ° C. for 30 minutes to prepare a test plate. Next, the raw paint of (1) above was applied with thinner (xylene / butyl acetate = 8/2).
Coating viscosity by weight ratio (Ford Cup No. 4, 20 ° C)
25 seconds) for 25 seconds), and first, Bellcoat No. 6000 silver metallic base coat paint [trade name, manufactured by NOF CORPORATION] on the test plate by air spraying at intervals of 1 minute 30 seconds in 2 stages. Dry film thickness 15μ
m, and set at 20 ° C for 3 minutes, then each of the above-mentioned diluted clear paints is dried by air spray to give a film thickness of 40
A test piece was prepared by coating so as to have a thickness of μm and baking at 140 ° C. for 30 minutes. The coating film performance is shown in Table 7. In all cases, a uniform and glossy coating film was obtained, and excellent acid resistance, stain resistance, impact resistance, weather resistance and hardness were exhibited.

[0057]

[Table 6]

[0058]

[Table 7]

Note 1) Cymel 303: manufactured by Mitsui Cyanamid Co., Ltd., trade name, hexamethoxymethylated melamine resin, nonvolatile content 9
8 wt% 2) Coronate 2513: Nippon Polyurethane Industry Co., Ltd.
Made, trade name, low-temperature dissociation non-yellowing type block polyisocyanate, nonvolatile content 80 wt%, isocyanate content 10.
2 wt% 3) Acid catalyst A: xylene solution of p-toluenesulfonic acid (1-methylheptyl) of Production Example 15 and 10 wt% as p-toluenesulfonic acid 4) Acid catalyst B: tetrahydrofuran solution of pyridine salt of zinc bromide 10% by weight as zinc bromide 5) Acid catalyst C: tetrahydrofuran solution of N-methylmorpholine salt of p-toluenesulfonic acid, 10% by weight as p-toluenesulfonic acid 6) Modaflow: Monsanto leveling agent, trade name

[0060]

[Table 8]

[0061]

[Table 9]

Note 1) PTSA: p-toluenesulfonic acid 2) ○: No abnormality

Comparative Examples 1 and 2 A clear paint was prepared by using the raw materials having the compositions shown in Table 8.
When a storage stability test was conducted in the same manner as in Examples 1 to 12, as shown in Table 9 in Comparative Example 1, both functional groups of the carboxyl group and the epoxy group were not blocked in the crosslinking reaction. Therefore, it gelled after 5 days. A test piece was prepared using the obtained coating material in the same manner as in Examples 1 to 12, and Comparative Example 2 (JP-A-1
-104646 gazette), a sufficient crosslinked coating film cannot be obtained under baking conditions of 140 ° C., and as shown in Table 9, acid resistance, stain resistance, impact resistance, weather resistance, hardness Both were inferior.

[0064]

[Table 10]

Note 1), 2): above

[0066]

[Table 11]

[0067]

The fluorine-containing thermosetting composition of the present invention comprises
It provides a cured product with excellent chemical performance such as acid resistance, impact resistance, hardness, water repellency, etc., stain resistance and weather resistance, as well as excellent storage stability.
It is preferably used for inks, adhesives, molded products and the like.

Claims (9)

[Claims] 1. A compound represented by the general formula: (In the formula, 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. And may form a heterocycle having Y ¹ as a hetero atom, Y ¹ being an oxygen atom or a sulfur atom), a compound having two or more functional groups represented by (B) in one molecule. A fluorine-containing compound having two or more reactive functional groups capable of forming a chemical bond with the above functional group by heating, and optionally (C) a thermal latent acid catalyst showing activity during heat curing as an essential component A fluorine-containing thermosetting composition containing. 2. The fluorine-containing thermosetting composition according to claim 1, wherein the component (A) is a polymer of an α, β-unsaturated compound and / or a polyester resin. 3. The reactive functional group of the component (B) is an epoxy group,
The fluorine-containing thermosetting composition according to claim 1 or 2, which is at least one selected from an alkoxysilane group, a hydroxyl group, an acetal group, and a ketal group. (D) One molecule of the general formula: (In the formula, R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁸ is an organic group having 1 to 18 carbon atoms, and R ⁷ and R ⁸ are bonded to each other. To form a heterocycle having Y ² as a hetero atom, Y ² is an oxygen atom or a sulfur atom), and a fluorine-containing compound having two or more functional groups represented by (E) 1 A compound having two or more reactive functional groups capable of forming a chemical bond with the above-mentioned functional group in a molecule, and optionally (C) a thermal latent acid catalyst showing activity during heat curing as an essential component A fluorine-containing thermosetting composition containing. 5. The fluorine-containing thermosetting composition according to claim 4, wherein the component (E) is a polymer of an α, β-unsaturated compound and / or a polyester resin. 6. The reactive functional group of the component (E) is an epoxy group,
Silanol group, alkoxysilane group, hydroxyl group,
At least one selected from 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. The fluorine-containing thermosetting composition according to claim 4 or 5. (D) One molecule of (D) has the general formula: (In the formula, R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁸ is an organic group having 1 to 18 carbon atoms, and R ⁷ and R ⁸ are bonded to each other. To form a heterocycle having Y ² as a hetero atom, Y ² is an oxygen atom or a sulfur atom), and a fluorine-containing compound having two or more functional groups represented by (B) 1 In the molecule, a fluorine-containing compound having two or more reactive functional groups capable of forming a chemical bond with the above functional group by heating, and (C) a thermal latent acid catalyst which is active during heat curing are used. A fluorine-containing thermosetting composition containing as an essential component. 8. The reactive functional group of the component (B) is an epoxy group,
The fluorine-containing thermosetting composition according to claim 7, which is at least one selected from an alkoxysilane group, a hydroxyl group, an acetal group and a ketal group. 9. A thermal latent acid catalyst of component (C), a compound obtained by neutralizing a protonic acid or a Lewis acid with a Lewis base, a mixture of a Lewis acid and a trialkyl phosphate, a sulfonate ester, a phosphate ester and an onium. The fluorine-containing thermosetting composition according to any one of claims 1 to 8, which is at least one selected from the compounds.