JP2746005B2 - Thermosetting composition, heat latent acid catalyst, coating finishing method and coated article - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel thermosetting composition,
The present invention relates to a heat latent acid catalyst, a paint finishing method, and a painted article. More specifically, the present invention provides good chemical performance,
The present invention relates to a thermosetting composition which gives physical performance and weather resistance and has excellent storage stability, and a coating finishing method which uses these as a top coat and has excellent coating properties and finish appearance.

[0002]

BACKGROUND 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, an oxazoline group,
Silanol group, alkoxysilane group, amino group, 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 alkylaminomethylol group, an acetal group, a ketal group and the like are known.
As such a known technique, for example, a composition comprising a combination of a carboxyl group and an epoxy group is disclosed in Japanese Patent Laid-Open Publication No. 51-114429, European Patent Publication No. 29,595, U.S. Pat. 371,667
No., the 4,650,718 Patent, the 4,6 81, 811
Nos. 4,703,101 and 4,764,430. Further, as a composition comprising a combination of a carboxyl group and an oxazoline group, US Pat. No. 3,505,297, Japanese Patent Publication No.
0-88038 and JP-A-2-115238. These thermosetting compositions are widely used in the fields of, for example, paints, inks, adhesives, and plastic molded articles because the obtained cured products have excellent chemical performance, physical performance, and even weather resistance. ing. 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. In addition, the carboxyl group-containing compound used in the conventional thermosetting composition is a compound having a low solubility in general-purpose organic solvents due to the strong hydrogen bonding property of the carboxyl group, or a compound having a functional group that reacts with the carboxyl group. However, when this thermosetting composition is used as an overcoat, there is a problem that it is difficult to make a high solid, or the finished appearance is inferior. 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 thermal decomposition of the t-butyl group, and foams isobutene gas which is a decomposition reaction product,
There is a problem that defoaming marks remain on the surface of the cured product, and this method cannot always be said to be a satisfactory method.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a cured product excellent in chemical performance, physical performance and weather resistance at a relatively low temperature, and has good storage stability and high solid It is an object of the present invention to provide a thermosetting composition that can be used as a liquid type. Another object of the present invention is to provide a heat-latent acid having both good storage stability and excellent curability. The purpose is to provide a catalyst. Still another object of the present invention is to provide a paint finishing method capable of giving an excellent finish appearance with a small amount of organic solvent discharged and an article obtained by the method.

[0004]

The present inventors have conducted intensive studies to develop a thermosetting composition having the above-mentioned preferable properties. As a result, (A) a specific vinyl ether group, vinyl thioether group, or A compound having, in one molecule, two or more carboxyl groups blocked by a heterocyclic group having a vinyl-type double bond having an oxygen atom or a sulfur atom as a hetero atom, (B) a compound having the blocked carboxyl group; A compound having two or more reactive functional groups capable of forming a chemical bond by heating, (E) specific vinyl ethers or vinyl thioethers, and (C) a heat-latent acid catalyst which is active when cured by heating. Or a composition containing (D)
(E) a self-crosslinking compound having at least one blocked carboxyl group in one molecule and at least one reactive functional group capable of forming a chemical bond with the blocked carboxyl group by heating; A specific vinyl ether or vinyl thioether, and optionally a component (C) as an essential component, and optionally a composition containing the component (A) and / or component (B), or Component (A), component (B), and (F) a composition containing, as an essential component, a special heat-latent acid catalyst having activity during heat curing, or the component (D), (F) The composition comprising the component and optionally the component (A) and / or the component (B) further comprises the component (A) and (G) two oxazoline groups per molecule. It has been found that the above-mentioned compound and, optionally, (C) a composition comprising, as an essential component, a heat-latent acid catalyst exhibiting activity at the time of heat curing can achieve the object, and furthermore, the above-mentioned preferred compounds can be achieved. It has been found that a coating finishing method using a thermosetting composition having properties as an overcoat paint has a small amount of organic solvent and can provide excellent finished appearance, and based on these findings, completes the present invention. Reached. That is, the present invention provides (A) a compound represented by the general formula [1]

[0005]

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(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)
R ³ and R ⁴ are bonded to each other to form Y ¹
May form a heterocyclic ring having a hetero atom of Y ¹
Is an oxygen atom or a sulfur atom).
(E) a compound having two or more reactive functional groups capable of forming a chemical bond with the above functional group by heating in one molecule, and (E) a general formula [2]

[0007]

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(Wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹ have the same meanings as described above), and (C) a thermal latent material having activity upon heat curing. An object of the present invention is to provide a thermosetting composition containing a neutral acid catalyst as an essential component. Further, the present invention provides (D) one molecule,
(B) General formula [3]

[0009]

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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 carbon atom having 1 to 1 carbon atoms.
And R ⁷ and R ⁸ are bonded to each other to form Y ²
May form a heterocyclic ring having a hetero atom of Y ²
Is an oxygen atom or a sulfur atom).
(E) a self-crosslinking compound having at least one reactive functional group capable of forming a chemical bond with the functional group by heating, and (E) a general formula [2]

[0011]

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(Wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹ have the same meanings as described above) and optionally (C) a thermal latent material having activity upon heat curing. And a functional group represented by the general formula [3] or the general formula [1] in one molecule of the component (A) and / or (B). It is intended to provide a thermosetting composition comprising a compound having two or more reactive functional groups capable of forming a chemical bond by heating with a functional group or both.

[0013]

[0014]

[0015]

The present invention also relates to (A) a compound represented by the general formula:

[0017]

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(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)
R ³ and R ⁴ are bonded to each other to form Y ¹
May form a heterocyclic ring having a hetero atom of Y ¹
Is an oxygen atom or a sulfur atom).
And (G) a compound having two or more oxazoline groups in one molecule and (C) a heat-latent acid catalyst which is active when heated and cured as an essential component. A curable composition is provided. Further, the present invention provides a heat-latent acid catalyst comprising a Lewis acid and a Bronsted acid or a complex of a Lewis acid and a Bronsted salt. The present invention also provides a paint finishing method using the thermosetting composition as a top coat and an article coated by the paint finishing method. Hereinafter, the present invention will be described in detail. In the composition of the present invention, the compound used as the component (A) is represented by the general formula [1]:

[0019]

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(In the formula, R ¹ , R ² , R ³ , R ⁴ and Y ¹ have the same meanings as described above). A compound having
The functional group represented by the general formula [1] includes a carboxyl group and a general formula [2]

[0021]

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(Wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹ have the same meanings as described above), a vinyl thioether compound, or an oxygen atom or a sulfur atom as a hetero atom. 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 [2],
R ² and R ³ each represent 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; R ⁴ represents an alkyl group having 1 to 18 carbon atoms, an aryl group;
An organic group such as an alkaryl group, these organic groups may have a suitable substituent, also, R ³ and R
⁴ may be bonded to each other to form a heterocyclic ring having no or a substituent having Y ¹ as a hetero atom. Specific examples of the compound represented by the general formula [2] include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, and n-propyl vinyl ether.
Butyl vinyl ether, isobutyl vinyl ether, 2
Aliphatic vinyl ether compounds such as -ethylhexyl vinyl ether and cyclohexyl vinyl ether and the corresponding aliphatic vinyl thioether compounds, furthermore 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
Cyclic vinyl ether compounds such as H-pyran and sodium 3,4-dihydro-2H-pyran-2-carboxylate; and cyclic vinyl thioether compounds corresponding thereto.

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 [2]. 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 decamethylenedicarboxylic acid, phthalic acid, Aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid;
Examples include alicyclic polycarboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid, polyester resins having two or more carboxyl groups in one molecule, acrylic resins, and maleated polybutadiene resins. The compound having two or more carboxyl groups in one molecule is, for example, (1) half-esterifying a polyol having two or more, preferably 2 to 50 hydroxyl groups per molecule with an acid anhydride. , (2) two or more isocyanate groups per molecule,
(3) Carboxyl group-containing α, β-unsaturated monomer is homopolymerized or other α, β-unsaturated monomer is added, preferably a polyisocyanate compound having 2 to 50 amino acids and a hydroxycarboxylic acid or an amino acid. And (4) synthesizing a carboxyl group-terminated polyester resin.

The polyol having two or more hydroxyl groups per molecule includes, for example, 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, 1,2,4-butanetriol, trimethylolethane, trimethylolpropane, pentane Polyhydric alcohols such as erythritol, quinitol, mannitol, trishydroxyethyl isocyanurate and dipentaerythritol; ring-opened adducts of these polyhydric alcohols with lactone compounds such as γ-butyrolactone and ε-caprolactone; Arco Adducts of alcohols with isocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate in excess of alcohol; the polyhydric alcohols and ethylene glycol divinyl ether, polyethylene glycol divinyl ether, butanediol diisocyanate Adducts of vinyl ether compounds such as vinyl ether, pentanediol divinyl ether, hexanediol divinyl ether, and 1,4-cyclohexanedimethanol divinyl ether in excess of alcohol; and polyhydric alcohols and alkoxysilicone compounds such as KR-213 , KR-21
7, KR-9218 [Both trade names, Shin-Etsu Chemical Co., Ltd.
And condensates thereof in the presence of an excess of 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, decamethylenedicarboxylic acid, phthalic acid, maleic acid, trimellitic acid, pyromellitic acid, tetrahydroacid Acid anhydrides of polycarboxylic acids such as phthalic acid, hexahydrophthalic acid and methylhexahydrophthalic acid can be mentioned.

The polyisocyanate compound having two or more isocyanate groups per molecule includes, for example, p-phenylene diisocyanate, biphenyl diisocyanate, tolylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, One,
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, methylcyclohexyl diisocyanate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate and burettes thereof.
An isocyanurate form and the like can be mentioned. Also,
Examples of the hydroxycarboxylic acid include lactic acid, citric acid, hydroxypivalic acid, 12-hydroxystearic acid, malic acid, and the like. Examples of the amino acid include DL-alanine, L-glutamic acid, glycine, and L-theanine. Glycylglycine, γ-aminocaproic acid, L-aspartic acid, L-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, and other α, β-unsaturated monomers. Examples of the saturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 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 according to a general method for synthesizing a polyester resin in a polybasic acid excess with respect to a polyhydric alcohol. The reaction between the thus obtained compound having two or more carboxyl groups in one molecule and the compound represented by the general formula [2] 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 composition of the present invention, the compound of the component (A) may be used alone or in combination of two or more. In the composition of the present invention, as the compound used as the component (B), when the blocked functional group represented by the general formula [1] in the compound of the component (A) is regenerated into a free carboxyl group by heating, Having two or more, preferably 2 to 50, reactive functional groups in one molecule capable of forming a chemical bond by reacting with the same. The reactive functional group is not particularly limited as long as it has the above properties, and examples thereof include an epoxy group, an oxazoline group, a silanol group, an alkoxysilane group, a hydroxyl group, an amino group, an imino group, an isocyanate group, and a block. Preferred examples include an 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, and single polymers such as 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;
1,2-bis (2-oxazolinyl-2) ethane, 1.4
-Bis (2-oxazolinyl-2) butane, 1,6-bis (2-oxazolinyl-2) hexane, 1,8-bis (2-oxazolinyl-2) octane, 1,4-bis (2-oxazolinyl-2) ) Oxazoline compounds having an oxazoline ring bonded to an alkyl chain such as cyclohexane, 1,2-bis (2-oxazolinyl-2) benzene, 1,3-bis (2-oxazolinyl-2) benzene, 1,4-bis (2 -Oxazolinyl-2) benzene, 5,5'-dimethyl-2,2'-bis (2-oxazolinyl-2) benzene, 4,4,4 ', 4'-tetramethyl-
2,2′-bis (2-oxazolinyl-2) benzene,
1,2-bis (5-methyl-2-oxazonyl-2) benzene, 1,3-bis (5-methyl-2-oxazonyl-2) benzene, 1,4-bis (5-methyl-2-oxazonyl-) 2) an oxazoline compound in which two oxazoline rings are bonded to an aromatic nucleus such as benzene, and 2,2′-bis (2-oxazone), 2,2′-bis (4-methyl-2
-Oxazoline), bis- (2-oxazoline) compounds such as 2,2'-bis (5-methyl-2-oxazoline), and polyvalent oxazolines obtained by reacting hydroxyalkyl-2-oxazoline with the above polyisocyanate compound Compound, furthermore, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline,
-Vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4
-Methyl-2-oxazoline, 2-isopropenyl-5
-Oxazoline group-containing compounds such as homopolymers or copolymers such as -ethyl-2-oxazone, and further, commercially available oxazoline group-containing compounds such as C
X-RS-1200, CX-RS-3200 (all manufactured by Nippon Shokubai Co., Ltd.), general formula (R ¹⁰ ) _n Si (OR ¹¹ ) _4-n ... [4] (R ¹⁰ and R in the formula ¹¹ is an alkyl group or an aryl group having 1 to 18 carbon atoms, and n is 0, 1 or 2), a condensate of acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, methacryloyl Homopolymers or copolymers of α, β-unsaturated silane compounds such as oxypropyltri-n-butoxysilane, and compounds containing silanol groups or alkoxysilane groups such as hydrolysis products of these compounds; aliphatic polyols , Phenols, polyalkyleneoxy glycols, 2-hydroxy (meth) acrylate and 2-hydroxypropyl (meth) acrylate Any α, β-unsaturated homopolymer or copolymer of a unsaturated compound, and hydroxyl group-containing compounds such as ε-caprolactone adducts of these polyols; aliphatic, aromatic diamino compounds and polyamino compounds and the polyols Amino group-containing compounds such as polyamino compounds obtained by reducing a cyanoethylation reaction product; imino group-containing compounds such as aliphatic and aromatic polyimino compounds; p-phenylenediisocyanate, biphenyldiisocyanate, tolylenediisocyanate, 3,3 ′ -Dimethyl-4,4'-biphenylenediisocyanate, 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, methylcyclohexyl diisocyanate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate and burettes thereof. Isocyanurate compounds, further isocyanate group-containing compounds such as adduct compounds of these isocyanates with the polyols; phenols, lactams, active methylenes, alcohols, acid amides, imides of the isocyanate group-containing compounds; Blocked isocyanate group-containing compounds such as amines, imidazoles, ureas, imines, oximes and the like; 3-
A cyclocarbonate group-containing compound such as a homopolymer or copolymer of (meth) acryloyloxypropylene carbonate, a polyvalent cyclocarbonate group-containing compound obtained by reacting the epoxy group-containing compound with carbon dioxide; A polyvalent vinyl ether compound obtained by reacting a compound containing a compound with a halogenated alkyl vinyl ether; a polyvinyl ether compound obtained by reacting a hydroxyalkyl vinyl ether with a compound containing a polyvalent carboxyl group or the polyisocyanate compound; ) Vinyl ether compounds such as copolymers of acrylates and α, β-unsaturated compounds, and vinyl ether group or vinyl thioether group-containing compounds such as vinyl thioether compounds corresponding thereto; Contains aminomethylol groups and alkylated aminomethylol groups such as homoforms or copolymers of minformaldehyde resin, glycolyl formaldehyde resin, urea formaldehyde resin, aminomethylol group and alkylated aminomethylol group-containing α, β-unsaturated compound Compounds: polyhydric ketones, polyhydric aldehyde compounds, polyhydric acetal compounds obtained by reacting the above polyhydric vinyl ether compounds and the like with alcohols and orthoacid esters, condensates of these with polyol compounds, and the above vinyl Acetal group- and ketal-group-containing compounds such as homopolymers or copolymers of adducts of oxyalkyl (meth) acrylates with alcohols or orthoacid esters are included.

In the composition of the present invention, as the compound of the component (B), a compound having two or more reactive functional groups may be used in addition to the compound having one reactive functional group. The component (B) may be used in combination of two or more kinds. However, in this case, a combination in which each functional group is active is not preferable because storage stability is impaired. Examples of such unfavorable combinations include, for example, combinations 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 composition of the present invention may contain the compound of the component (A) and the compound of the component (B), or (D) in one molecule, (a) the general formula [3]

[0029]

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(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ and Y ² have the same meaning as described above), and at least one, preferably 1 to 50, functional groups; One or more reactive functional groups, preferably one, capable of forming a chemical bond with the functional group by heating
It may contain a self-crosslinking compound having up to 50 compounds. Further, it 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 [3] and / or the functional group represented by the general formula [1] by heating. The (A) functional group represented by the general formula [3] in the compound of the component (D) is exemplified in the description of the functional group represented by the component (A), that is, the functional group represented by the general formula [1]. The same 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 of component (D) is a compound having one or more, preferably 1 to 50, carboxyl groups and one or more, preferably 1 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-mentioned reaction with the unsaturated compound having a functional group represented by the general formula [3] 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 [3]. In this case, the compound of the component (B) Similarly to the above compound, a combination in which the respective functional groups are active with each other is not preferred because storage stability is impaired. Examples of the compound containing two or more oxazoline groups per molecule (G) used in the thermosetting composition of the present invention include the aforementioned oxazoline group-containing compounds. The compound of component (G) is excellent in performance such as low-temperature curability and coating hardness. In the thermosetting composition of the present invention, the component (A) and / or the component (B), or the component (D) and the component (A) and / or
Alternatively, at least one selected from the component (B), the component (A) and / or the component (G) is preferably a polymer of an α, β-unsaturated compound or a polyester resin, and the composition In which the functional group represented by the general formula [1] or [3] and a reactive functional group capable of forming a chemical bond with the functional group by heating have an equivalent ratio of 0.2: 1.0 to 1.0:
It is desirable that each component be contained so as to have a ratio of 0.2.

The functional groups represented by the general formulas [1] and [3] of the components (A) and (D) of the present invention regenerate free carboxyl groups under heating, and the components (B) and (B) D)
It forms a chemical bond with the reactive functional group of the component and the component (G). In addition to this reaction, the component (B) or the component (D) or the component (G) is a so-called active ester based on an intramolecular polarization structure. )) An addition reaction may be caused to the reactive functional group of the component. 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. The component (E) represented by the general formula [2] used in the thermosetting composition of the present invention is used for the hydrolysis reaction of a blocked carboxyl group when moisture is present in the thermosetting composition. Has the role of blocking again the free carboxyl group generated by the above and increasing storage stability.
When water is contained in the thermosetting composition in an amount of 0.1% by weight or more, the hydrolysis reaction is particularly likely to occur, and it is extremely effective to include the component (E).

As the compound represented by the general formula [2] used as the component (E), the same vinyl ethers or vinyl thioethers as those used in the above-mentioned carboxyl group blocking can be used. The aliphatic vinyl ether compounds such as 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 and the like, and the corresponding aliphatic vinyl thioether compounds, Is 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- Hydro-4,4-dimethyl -
Cyclic vinyl ether compounds such as sodium 2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran, and 3,4-dihydro-2H-pyran-2-carboxylate, and corresponding cyclic vinyl thioethers And the like, preferably ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether. The amount of the component (E) used in the present invention is 0.1 to 20 with respect to the thermosetting composition.
% By weight, and particularly preferably from 1 to 10% by weight. When the amount of the component (E) is less than 0.1% by weight, the effect of improving storage stability may not be sufficient,
On the other hand, if it exceeds 20% by weight, the solid content of the thermosetting composition may be reduced, which is not preferable.

In the present invention, these compositions may be used, if necessary, to maintain good long-term storage stability of the composition and to accelerate the curing reaction when cured at a low temperature for a short period of time. For the purpose of imparting good chemical performance and physical performance, a heat-latent acid catalyst having activity at the time of heat curing can be contained as the component (C). As the thermal latent acid catalyst, a compound exhibiting an acid catalytic activity at a temperature of 60 ° C. or more is desirable. If the heat-latent acid catalyst exhibits an acid catalyst activity at a temperature lower than 60 ° C., the resulting composition may cause undesirable situations such as thickening or gelling during storage. As the heat-latent acid catalyst of the component (C), a compound obtained by neutralizing a Bronsted acid or a Lewis acid with a Lewis base, a complex compound comprising a Lewis acid and a Bronsted acid or a Lewis acid and a Bronsted salt;
Sulfonates, phosphates, and onium compounds. The Bronsted acid constituting the above-mentioned heat latent acid catalyst is a substance that dissociates protons and exhibits acidity, and is preferably sulfuric acid, sulfonic acid, phosphoric acid, boric acid, carboxylic acid, or a derivative thereof. Specific examples thereof include, for example, sulfuric acid, sulfuric acid monoester, phosphoric acid, phosphoric acid mono- and diesters, polyphosphate esters, boric acid mono- and diesters, sulfonic acid, carboxylic acid, halogenocarboxylic acid, and the like, preferably dodecylbenzene. C1-C50 mono- or di-halogenocarboxylic acid such as C1-C50 alkylbenzenesulfonic acid such as sulfonic acid, chloroacetic acid, dichloroacetic acid, C1-C50 phosphorus such as monomethyl phosphate, dimethyl phosphate, etc. Acid alkyl monoesters and diesters. One of these Bronsted acids may be used, or two or more thereof may be used in combination.

The Lewis acid constituting the above-mentioned heat-latent acid catalyst is a compound having an electron accepting property, and is preferably a metal halide or an organic metal compound represented by the following general formula. (R ⁹ ) _n -M (wherein R ⁹ is one selected from a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group, an acyloxy group, or a carbonyl group adjacent to an active methylene group or Two or more organic groups, M is B, Mg, Al, C
a, Sn, Pb or the fourth to sixth periods in the long-period table
Transition metal atoms belonging to groups 3A to 7A, 8 groups, 1B and 2B in the period, and n is an integer of 1 to 6.)
The classification of the metal atoms constituting the Lewis acid in the Long Periodic Table is based on the IUPAC inorganic chemical nomenclature in 1988.
Specific examples thereof include, for example, boron trifluoride, aluminum trichloride, ferrous titanium chloride, ferric chloride, ferrous chloride, ferric chloride, zinc chloride, zinc bromide, stannous chloride, and chloride. Stannic, stannous bromide, metal halides such as stannic bromide, trialkyl boron, trialkyl aluminum, dialkyl aluminum halide,
Monoalkyl aluminum halide, tetraalkyl tin, aluminum acetylacetonate, iron acetylacetonate, zirconium acetylacetonate, dibutyltin acetylacetonate, dibutyltin dilaurate, dioctyltin ester malate, magnesium naphthenate, calcium naphthenate, manganese naphthenate , Iron naphthenate, cobalt naphthenate, copper naphthenate, zinc naphthenate, zirconium naphthenate, lead naphthenate, calcium octylate, manganese octylate,
Iron octylate, cobalt octylate, zinc octylate,
Organic metal compounds such as zirconium octylate, tin octylate, lead octylate, zinc laurate, magnesium stearate, aluminum stearate, calcium stearate, cobalt stearate, zinc stearate, and lead stearate are exemplified. These organometallic compounds may be used alone or in combination of two or more.

The Lewis base used to neutralize the above Bronsted acid and Lewis acid is a compound having an electron donor property, and more specifically, ammonia, triethylamine, pyridine, aniline, morpholine, N-methylmorpholine, pyrrolidine, N-methylpyrrolidine,
Piperidine, N-methylpiperidine, cyclohexylamine, n-butylamine, dimethyloxazoline, imidazole, N-methylimidazole, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N , N-dibutylethanolamine, N, N-dimethylisopropanolamine, N, N-diethylisopropanolamine, N, N-dipropylisopropanolamine, N, N
-Dibutylisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine, N-propyldiisopropanolamine, N-butyldiethanol Amines such as isopropanolamine, triethanolamine, triisopropanolamine, tri-s-butanolamine, N,
Amide compounds such as N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide, sulfoxide compounds such as dimethyl sulfoxide, ether compounds such as diethyl ether and tetrahydrofuran, dimethyl Thioether compounds such as sulfide, phosphate compounds such as trimethylphosphoric acid, triethylphosphoric acid and tributylphosphoric acid, boric acid ester compounds such as trimethylboric acid, carboxylic acids such as ethyl acetate and butyl acetate An ester compound, a carbonate compound such as ethylene carbonate, or a trialkylphosphine compound such as tributylphosphine may be used. The heat latent acid catalyst obtained by neutralizing the aforementioned Bronsted acid or Lewis acid with the above Lewis base has a ratio of the base activity of the Lewis base to the acid activity of each acid in the range of 0.1 to 10. When the molar ratio is less than 0.1, the catalytic activity of the acid compound may not be sufficiently suppressed during storage. When the molar ratio is more than 10, the catalytic activity may not be sufficiently exhibited during heating. This is not preferred. Examples of the sulfonic acid esters used as the heat-latent acid catalyst of the component (C) include, for example, those represented by the general formula [4]:

[0037]

Embedded image

[0038] (R ¹² is a phenyl group in the formula, a substituted phenyl group, a naphthyl group, substituted naphthyl group or alkyl group, R ¹³
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 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 [5]

[0039]

Embedded image

(Wherein R ¹⁴ 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. In addition, β-hydroxyester compounds obtained by reacting phosphoric acid with an oxirane compound may also be used. Examples of the onium compounds, for example the general formula _{^{[R 15 3 NR 16] +}} X - ... [6] [R 15 3 PR 16] + X - ... [7] [R 15 2 OR 16] + X - ... [ 8] and _{^{[R 15 2 SR 16] +}} X - ... [9] (R 15 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 ^{15 s} may be bonded to each other to form a heterocyclic ring having N, P, O or S as a hetero atom, and R ¹⁶ may be a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Alkenyl group, aryl group, alkaryl group, and X ⁻ is SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ or BF ₄ ⁻ ).

The complex compound (F) composed of a Lewis acid and a Bronsted acid or a Lewis acid and a Bronsted salt among the components of the heat-latent acid catalyst (C) used in the composition of the present invention is the present invention. A novel heat-latent acid catalyst particularly useful for thermosetting compositions, and a complex compound comprising a Lewis acid and a Bronsted acid is the most excellent heat-latent acid catalyst. This complex compound (F) component is superior in storage stability, thermosetting reactivity, and other low-temperature curability as compared with other heat-latent acid catalysts. The Bronsted salt constituting the component (F) is a compound obtained by neutralizing the above-mentioned Bronsted acid with a base substance, and includes, for example, sulfuric acid, sulfuric acid monoester, phosphoric acid, mono- and diesters of phosphoric acid, polyphosphate, boric acid. Mono- and diesters, sulfonic acids,
Carboxylic acids, Brønsted acids such as halogenocarboxylic acids, ammonia, triethylamine, pyridine, aniline, morpholine, N-methylmorpholine, pyrrolidine, N-methylpyrrolidine, piperidine, N-methylpiperidine, cyclohexylamine, n-butylamine,
Compounds blocked with various amines such as diethanolamine, triethanolamine, imidazole and N-methylimidazole, or trialkylphosphines such as tributylphosphine, and triarylphosphines such as triphenylphosphine, and further, an acid-base blocking catalyst NACURE 2500 commercially available as
X, 3525, 5225 (trade name, manufactured by King Industry Co., Ltd.) and the like. The novel heat-latent acid catalyst (F) component is a compound exhibiting the catalytic activity of a Lewis acid, in which a conjugate base of a Bronsted acid or a Bronsted salt is coordinated to an empty electron orbital and complexed, as described above. A Lewis acid and the above-mentioned Bronsted acid or the above-mentioned Bronsted salt are mixed with each other in a mole ratio of the Bronsted acid or the Bronsted salt in a molar ratio of 0.1 to 4 with respect to the empty electron orbital of the Lewis acid. Can be easily obtained.
If the molar ratio is less than 0.1, utilization of the Lewis acid may not be sufficiently suppressed during storage, and if it exceeds 4, the catalyst activity tends to be hardly exhibited during heating.

In the present invention, one kind of the heat-latent acid catalyst of the component (C) or the component (F) may be used,
Two or more of them may be used in combination, and the compounding amounts thereof are as follows: component (A) and component (B), or component (D) and component (A) and / or component (B) optionally used or component (A). The amount is usually selected from the range of 0.01 to 10 parts by weight, preferably the range of 0.02 to 5 parts by weight, per 100 parts by weight of the total solid content of the component () and the component (G). Regarding the temperature and time required for curing the thermosetting composition of the present invention, the temperature at which a free carboxyl group is regenerated from the blocked functional group represented by the general formula [1] or [3], the reactive functional group Depends on the type of heat-latent acid catalyst, etc.
The curing is completed by heating at a temperature usually in the range of 50 to 200 ° C. for about 2 minutes to 10 hours. In addition, the thermosetting of the thermosetting composition of the present invention can be sufficiently caused even at a temperature of 160 ° C. or less, and has a feature that does not require a high temperature.

The thermosetting composition of the present invention as it is,
Or, if necessary, a coloring pigment, a filler, a solvent, an ultraviolet absorber, an antioxidant, etc.
It can be used for adhesives, molded products and the like. Further, when the thermosetting composition of the present invention is used as a topcoat,
A coating finishing method having a small amount of organic solvent emission and excellent finish appearance can be realized, and is extremely useful in the field of industrial coating such as automobile coating. In the case of this top coat, the pigment is used in an amount of 0 to 1 per 100 parts by weight of the thermosetting composition.
It is preferable to mix 00 parts by weight, particularly preferably 0 to 5 parts by weight. Further, the thermosetting composition of the present invention, when applied to a method of adjusting the painted article in a plurality of layers consisting of a pigmented basecoat and the clearcoat,
An extremely excellent finish appearance can be obtained. The film-forming composition of the base coat contains a resin binder and a pigment. Examples of the resin binder include, in addition to the thermosetting composition of the present invention, conventional acrylic polymers, polyesters (including alkyd resins), polyurethanes, and the like. In addition, pigments contained in the film-forming composition of the base coat include aluminum, copper, brass, bronze, stainless steel, or mica-like iron oxide, flaky metallic powder, titanium oxide and oxide Metal pigments such as mica fragments coated with iron are used. In addition, other inorganic pigments such as titanium dioxide, iron oxide, yellow iron oxide, and carbon black; organic pigments such as phthalocyanine blue, phthalocyanine green, and quinacridone red pigment; and extender pigments such as precipitated barium sulfate, clay, silica, and talc. And the like.

The film-forming composition of the base coat may contain various commonly used additives such as a surfactant, a leveling agent, a thixotropic agent, a filler, an antifoaming agent, an organic solvent, and a catalyst. it can. The substrate on which the film-forming composition of the base coat is applied is not particularly limited, and various substrates can be used, such as wood, glass, metal, cloth, plastic, foam, and elastic body. Is mentioned. The thickness of the base coat is not particularly limited, but is usually about 5 to 4
0 μm, preferably 10 to 30 μm. After applying the base coat film forming composition to the substrate, a base coat film is formed. This can be obtained by heating or simply air-drying an organic solvent or water as a solvent from the base coat film. After the base coat film is formed, the clear coat film forming composition is applied thereon. The clear coat film-forming composition,
It is a thermosetting composition of the present invention. The above-mentioned pigments, various additives, dyes having good weather resistance, and the like can be added to the clear coat film-forming composition, if necessary, to the extent that transparency is not impaired. The thickness of the clear coat is not particularly limited, but is usually about 20 to 100 μm.
m, preferably 20 to 50 μm. Examples of the method of applying the base coat and the clear coat include commonly used methods such as brush coating, spray coating, immersion coating, and flow coating. Spray coating is preferred.
Next, after coating the base coat and clear coat,
After leaving at room temperature for 0 minutes, at 50-200 ° C for 2 minutes- 10
After baking for a time, the coated article of the present invention is obtained.

[0045]

Next, the present invention will be described in more detail by way of 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 [JISK-5400 (1990) 8.
Using a “3.2 Dupont method”, the test piece was sandwiched in a shooting mold 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 [JISK-5400
(1990) 9.8.1] for 1000 hours or 3
After exposure for 2,000 hours, the 60 ° specular gloss value of the coating film [JIS
K-5400 (1990) 7.6 Specular gloss]], and the abnormality of the coating film was visually judged or compared with the gloss value at the time of no 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 3 (A) Production of Component Compound A-1 to A-3 Solutions (1) Production of α, β-Unsaturated Compounds Four ports equipped with a thermometer, a reflux condenser and a stirrer Each mixture having the composition shown in Table 1 was charged into a flask, and the mixture was stirred while maintaining the temperature 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 alkali-washed with 100 parts by weight of a 10 wt% aqueous sodium hydrogen carbonate solution in a separating funnel,
Washing with 200 parts by weight of deionized water was repeated 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 dried at room temperature for 3 days, thereby obtaining an α, β-unsaturation having an effective content shown in Table 1 respectively. Compound A-1
(A) to A-3 (a) were obtained.

(2) Preparation of Solutions of Compounds A-1 to A-3 Into a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, the amount of the initially charged solvent shown in Table 2 was added. (Xylene) and heated under stirring to maintain 80 ° C. Next, at a temperature of 80 ° C., a mixture of the monomer and the polymerization initiator (dropping component) having the composition shown in Table 2 was dropped at a constant speed from the dropping funnel over 2 hours. After completion of the dropwise addition, the temperature was kept at 80 ° C. for 1 hour, a polymerization initiator solution (additional catalyst) having the composition shown in Table 2 was added, and the reaction was terminated when the temperature was kept at 80 ° C. for 4 hours. Compound A-1 to A-3 solutions each having the properties shown in Table 2 were obtained.

[0049]

[Table 1]

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

[0051]

[Table 2]

Note 1) Non-volatile content measurement conditions, 50 ° C, 0.1 mmHg for 3 hours 2) Viscosity: Gardner viscosity (25 ° C) [JIS K-5400 (1990) 4.5.1 Gardner-type foam viscosity method]

Production Example 4 (A) Production of Component Compound A-4 Solution (1) Production of Polycarboxylic Acid Compound A-4-a Four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel The following components were charged into a
The temperature was raised to ° C. Pentaerythritol 136.0 parts by weight Methyl isobutyl ketone 538.7 parts by weight Next, while maintaining the temperature at 120 ° C., 672.0 parts by weight of methyl hexahydrophthalic anhydride was added dropwise over 2 hours, and the acid value of the mixture (pyridine / water Weight ratio = about 5 with 9/1 mixture
The solution was diluted to 0 weight times and heat-treated at 90 ° C. for 30 minutes, and titrated with a potassium hydroxide standard solution) to 170 or less to continue heating and stirring, whereby the tetrafunctional polycarboxylic acid compound A-4- a solution was obtained.

(2) Preparation of Compound A-4 Solution Using the polycarboxylic acid compound solution obtained by the above method, a mixture having the following composition was charged into the same flask as above, and the mixture was stirred at 50 ° C. . 336.7 the polycarboxylic acid compound solution of the above (1)
Parts by weight isobutyl vinyl ether 120.2
Weight part 35wt% hydrochloric acid 0.2
Parts by weight methyl isobutyl ketone 46.3
The reaction was terminated when the acid value of the mixture by weight became 12 or less, and after standing to cool, the product was transferred to a separating funnel. The obtained product was mixed with a 10 wt% aqueous sodium carbonate solution 1 in a separating funnel.
After washing with 00 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.
Thereafter, the molecular sieve 4A1 / 16 was added to the organic layer, and the mixture was dried at room temperature for 3 days.
A compound A-4 solution having 0.0 wt% and Gardner viscosity EF (25 ° C.) was obtained.

(3) Production of Compound A-5 Solution Using the polycarboxylic acid compound solution obtained by the above method, a mixture having the following composition was charged into the same flask as above, and the mixture was stirred while maintaining the temperature at 60 ° C. . The polycarboxylic acid compound solution of the above (1) 1277.
5 parts by weight n-propyl vinyl ether 447.
9 parts by weight 2-ethylhexyl phosphate
8 parts by weight When the reaction rate obtained from the acid value of the mixture became 98% or more, the heating was stopped, and excess vinyl ether and 348.2 parts by weight of methyl isobutyl ketone were distilled off under reduced pressure. , Gardner viscosity (25 ° C) [JIS K-
5400 (1990) 4.5.1 Gardner Viscometer Method] to give a solution of compound A-5. Production Examples 5 and 6 (B) Production of Component Compound B-1 and B-2 Solutions Initially charged solvent (xylene) 4 in a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel.
0.0 parts by weight were charged and heated under stirring to keep 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 3 was dropped at a constant speed from the dropping funnel over 2 hours. After completion of the dropwise addition, the temperature was maintained at 100 ° C. for 1 hour, a polymerization initiator solution (additional catalyst) having the composition shown in Table 3 was added, and the reaction was terminated when the temperature was further maintained at 100 ° C. for 2 hours. Compound B-1 and B-2 solutions having the properties shown in Table 3 were obtained.

[0056]

[Table 3]

Note 1) GMA: glycidyl methacrylate TMSPMA: methacryloyloxypropyltrimethoxysilane MZ-11: Chemitite MZ-11, Nippon Shokubai Chemical Industry
2- (1-aziridinyl) ethyl methacrylate BMA: n-butyl methacrylate MMA: methyl methacrylate EHA: 2-ethylhexyl acrylate AIBN: 2,2′-azobisisobutyronitrile 2) Nonvolatile content: 50 ° C. , Dried at 0.1 mmHg for 3 hours Gardner viscosity (25 ° C): JIS K-5400 (19
90) 4.5.1 According to Gardner-type foam viscometer method.

Production Examples 7 and 8 (D) Production of Component Compound D-1 and D-2 Solutions In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, each was prepared as shown in Table 4. A quantity 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 (dropping component) having the composition shown in Table 4 was dropped at a constant rate from the dropping funnel over 2 hours. After completion of the dropwise addition, the temperature was kept at 80 ° C. for 1 hour, a polymerization initiator solution (additional catalyst) having the composition shown in Table 4 was added, and the reaction was terminated when the temperature was kept at 80 ° C. for 4 hours. Compound D-1 and D-2 solutions having the properties shown in Table 4 were obtained.

[0059]

[Table 4]

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

Application to 1-coat solid color Examples 1 to 11 (1) Production of paint In the composition shown in Table 5, in Example 1, Denacol EX-
421, compound B-2 in Example 2, chemitite PZ-33 in Example 3, compound A-4 in Example 4, coronate EH in Example 5, Cymel 303 in Example 6,
Compound B-1 in Example 7 and KR-21 in Example 8
4. In Example 9, compound B- 3 , in Example 11, the mixture excluding Cymel 303, and in Example 10, all the raw materials were charged into a sand mill, and dispersed until the particle size became 10 μm or less. Thereafter, the raw materials removed during the dispersion of the pigment were added and mixed in Example 10 as they were, and in Examples 1 to 9 and Example 11, a one-pack type paint was obtained. Each of the obtained paints was diluted to 1 poise (measured at 20 ° C. with a Brookfield viscometer) using xylene and butyl acetate, and then deionized water was added to adjust the water concentration to 0.3% by weight. Stored sealed at 0 ° C. After storage at 30 ° C for 30 days,
When the viscosity was measured again, as shown in Table 6, excellent storage stability was exhibited despite the presence of a considerable amount of moisture.

[0062]

[Table 5]

[0063]

[Table 6]

Note 1) Denacol EX-421: trade name, manufactured by Nagase Chemical Industry Co., Ltd., polyepoxy compound, epoxy equivalent: 155 2) Chemitite PZ-33: trade name, manufactured by Nippon Shokubai Chemical Co., Ltd., polyaziridine , Aziridine content 6.2m
ol / kg 3) Coronate EH: trade name, manufactured by Nippon Polyurethane Industry Co., Ltd., hexamethylene diisocyanate trimer, isocyanate content 21 wt% 4) Cymel 303: trade name, Mitsui Cyanamid Co., Ltd.
5) KR-214: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., silicone varnish, hydroxyl equivalent 490, nonvolatile content 70 wt.
%) 6) Titanium dioxide JR-602: trade name, manufactured by Teikoku Chemical Co., Ltd., rutile type titanium dioxide 7) Modaflow: trade name, manufactured by Monsanto Co., Ltd. 8) 10% PTSA: 10w of p-toluenesulfonic acid
t) Isopropyl alcohol solution 9) 10% N-methylmorpholine: 10 wt% xylene solution of N-methylmorpholine 10) B-3: Acetate obtained by the following production method
Group-containing compounds. 4 equipped with thermometer, reflux condenser, stirrer, dropping funnel
206.0 parts by weight of methyl orthoformate and
Charge 0.3 parts by weight of boron fluoride diethyl ether,
Keep the mixture in the flask at 0 to 5 ° C by cooling on ice with stirring.
Was. Next, butyl vinyl ether at a temperature of 5 ° C. or less.
7 parts by weight was dropped at a constant speed from the dropping funnel over 2 hours.
After completion of dropping, keep the temperature below 5 ° C for 1 hour
0.4 parts by weight of a 30% by weight methanol solution of methylate
The reaction was terminated by addition. The product obtained is 75-8
By distilling at 0 ° C. (4 mmHg), the effective component 9
8% by weight of acetalized product was obtained. Next, a thermometer,
Reflux condenser, stirrer,
In a four-neck flask equipped with a dropping funnel, resulting purified A
618 parts by weight of cetalized compound, trimethylolpropane 1
Charge 34 parts by weight and 4 parts by weight of p-toluenesulfonic acid
And heated at 90 ° C. with stirring. As the reaction progresses
A methanol removal reaction occurs, and 96 parts by weight of methanol are recovered.
When collected, the reaction was terminated to obtain compound B-3.

(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
m, and baked at 175 ° C. for 25 minutes, and air-sprayed with an intermediate coating paint Epico No. 1500CP sealer (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) to a dry film thickness of 40 μm. A test plate was prepared by baking at ℃ for 30 minutes. Then, (1)
Each of the raw paints was coated with a thinner (xylene / n-butyl acetate = 8/2 weight ratio) and applied with a coating viscosity (Ford Cup No. 1).
After dilution at 4, 20 ° C. for 25 seconds), the test plate prepared by the above method was applied by air spray and baked under the conditions shown in Table 6 to prepare a test piece. The coating performance is shown in Table 6. In each case, a uniform and glossy coating was obtained.
Under the conditions of baking at 40 ° C., excellent acid resistance, impact resistance, weather resistance, and hardness were exhibited.

[0066]

[Table 7]

[0067]

[Table 8]

[0068]

[Table 9]

[0069]

[Table 10]

Note 1) Weather resistance: Sunshine weather meter [JIS
K-5400 (1990) 9.8.1].
After 60 hours of exposure, the coating film has a 60 ° specular gloss value [JISK-5]
400 (1990) 7.6 Specular gloss] and compared with the unexposed gloss value.

Comparative Examples 1 to 11 In the compositions shown in Table 5, in Comparative Examples 1 to 11, paints containing no component (E) were prepared in the same procedure as in Examples 1 to 11. In Comparative Examples 1 to 11, when adjusting the viscosity of the coating material, xylene was used for the portion corresponding to the component (E).
When the obtained paint was subjected to a storage stability test in the same manner as in Examples 1 to 11, in Comparative Examples 1 to 11, a free carboxyl group was regenerated by a considerable amount of water, and this was used to block it again. Since the component (E) was not contained, the viscosity increased remarkably with time, and finally, all of them gelled in 20 days.

Response to 2-coat 1-baked metallic color
Examples 12 to 17 for use (1) Production of clear paint A raw material having the composition shown in Table 7 was mixed to obtain a one-pack clear paint. Each of the obtained paints was subjected to a storage stability test in the same manner as in Examples 1 to 11. As shown in Table 8, in each case, although a considerable amount of water was present, And showed excellent storage stability.

(2) Preparation of Test Specimens Each raw paint obtained was diluted in the same manner as in Examples 1 to 11. Then, on a test plate prepared in the same manner as in Examples 1 to 11, Bellcoat No. 6000 silver metallic basecoat paint [trade name, manufactured by Nippon Oil & Fats Co., Ltd.] was air-sprayed at intervals of 1 minute and 30 seconds, and two stages. , And then set at 20 ° C. for 3 minutes. Then, each of the diluted clear paints was applied by air spray and baked under the conditions shown in Table 13 to prepare test pieces.
The coating film performance is shown in Table 8. In each case, a uniform and glossy coating film was obtained, and excellent acid resistance, impact resistance, weather resistance, and hardness were obtained under baking conditions at 140 ° C.

[0074]

[Table 11]

Note 1) CX-RS-3200: manufactured by Nippon Shokubai Co., Ltd., polyoxazoline compound, solid content 50%, glass transition point 10 ° C.
Weight average molecular weight 18,000, oxazoline equivalent molecular weight 5
55

[0076]

[Table 12]

[0077]

[Table 13]

[0078]

[Table 14]

Note 1) Weather resistance was measured by the same method as in Table 6.

Comparative Examples 12 to 17 In the compositions shown in Table 7, in Comparative Examples 12 to 17, paints containing no component (E) were prepared in the same procedure as in Examples 12 to 17. In Comparative Examples 12 to 17, when adjusting the viscosity of the coating material, xylene was used for the portion corresponding to the component (E). When the obtained paint was subjected to a storage stability test in the same manner as in Examples 12 to 17, in Comparative Examples 12 to 17, free carboxyl groups were regenerated due to the presence of a considerable amount of water, and this was reblocked. Since component (E) was not contained, the viscosity increased remarkably with time, and finally gelled in 20 days.

Examples 18 to 21 Production of Heat Latent Acid Catalysts F-1 to F-4 Into test tubes were charged 50.0 parts by weight of a mixed solvent of methyl isobutyl ketone / ethyl acetate (weight ratio 1/1).
The respective compounds were mixed with each other while stirring so as to obtain the compositions shown in Table 9. Thereafter, the test tubes were allowed to stand for 3 hours to obtain 50% by weight solutions of the heat-latent acid catalysts F-1 to F-4.

[0082]

[Table 15]

Application to one-coat solid color Examples 22 to 26 (1) Production of paint In the composition shown in Table 10, in Example 22, Denacol E was used.
X-421, Example 23: Compound B-2, Example 24
In Example 25, a mixture except for the compound B-1 and Example 25 were charged into a sand mill, and in Example 26, all the raw materials were charged in a sand mill, and dispersed until the particle size became 10 μm or less. Thereafter, in Example 26, as it is, and in Examples 22 to 25
Then, the raw materials removed during the pigment dispersion were added and mixed to form a one-pack type paint. Each of the obtained paints was diluted with a thinner (xylene / n-butyl acetate = 8/2 weight ratio) to 1 poise (measured at 20 ° C. with 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 11, almost no increase in viscosity was observed, and excellent storage stability was exhibited.

[0084]

[Table 16]

Note 1) Denacol EX-421: trade name, Nagase Chemical Industries
2) Titanium dioxide JR-602: trade name, Teikoku Kako Co., Ltd.
Made, rutile type titanium dioxide 3) Modaflow: trade name, manufactured by Monsanto, leveling agent

(2) Preparation of test piece Cationic electrodeposition paint Aqua No.
4200 [trade name, manufactured by NOF CORPORATION] with a dry film thickness of 20 μm
m, and baked at 175 ° C. for 25 minutes, and air-sprayed with an intermediate coating paint Epico No. 1500CP sealer (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) to a dry film thickness of 40 μm. A test plate was prepared by baking at ℃ for 30 minutes. Then, (1)
Each raw paint is thinner (xylene / butyl acetate =
8/2 weight ratio) and the coating viscosity (Ford Cup No. 4,
After dilution at 20 ° C. for 25 seconds), the test plate prepared by the above method was applied by air spray and baked under the conditions shown in Table 11 to prepare a test piece. The properties of the coating film are shown in Table 11. In each case, a uniform and glossy coating film was obtained, showing excellent acid resistance, impact resistance, weather resistance and hardness.

[0087]

[Table 17]

[0088]

[Table 18]

Note 1) Weather resistance was measured by the same method as in Table 6.

Comparative Examples 18 and 19 In the composition shown in Table 12, Comparative Example 18 shows Production Example A-4.
(A) polycarboxylic acid, in Comparative Example 19, compound A-4
Except for the above, pigments were dispersed in the same manner as in Examples 22 to 26, and then formed into a paint. The resulting paint was subjected to a storage stability test in the same manner as in Examples 22 to 26. In Comparative Example 18, since the carboxyl group and the epoxy group were not blocked at all as shown in Table 13, the crosslinking reaction between the two was carried out. As a result, the viscosity increased remarkably with time, and finally gelled in 5 days.

[0091]

[Table 19]

[0092]

[Table 20]

Note 1) Weather resistance was measured by the same method as in Table 6.

Response to 2-coat 1-baked metallic color
Examples 27 to 29 for use (1) Production of clear paint The raw materials having the compositions shown in Table 14 were mixed to obtain a one-pack clear paint. Each of the obtained paints was subjected to a storage stability test in the same manner as in Examples 22 to 26. As shown in Table 15, almost no increase in viscosity was observed in any case, and excellent storage stability was obtained. showed that.

[0095]

[Table 21]

(2) Preparation of test piece Each of the obtained raw paints was diluted in the same manner as in Examples 22 to 26. Then, a test plate prepared in the same manner as in Examples 22 to 26 was provided with Bellcoat No. 6000 Silver metallic base coat paint [trade name, manufactured by NOF CORPORATION] is applied by air spray at intervals of 1 minute and 30 seconds, and with two stages to a dry film thickness of 15 μm. Each diluted clear paint was applied by air spray and baked under the conditions shown in Table 15 to prepare test pieces. The coating film performance is shown in Table 15. In each case, a uniform and glossy coating film was obtained, and excellent acid resistance, impact resistance,
It showed weather resistance and hardness.

[0097]

[Table 22]

Note 1) Weather resistance was measured by the same method as in Table 6.

Comparative Examples 20 and 21 Clear coating materials were prepared using the raw materials having the compositions shown in Table 16 and subjected to storage stability in the same manner as in Examples 22 to 26. As shown in the table, since the carboxyl group and the epoxy group were not blocked at all, the viscosity increased significantly with the lapse of time due to the cross-linking reaction between the two, and finally gelled in 5 days. Comparative Example 21
In Table 18, as shown in Table 18, the organometallic compound is not made to be latent heat at all. Therefore, the viscosity significantly increases with time due to a regeneration reaction of a free carboxyl group and a cross-linking reaction between the carboxyl group and the epoxy group. Gelled in 2 days.

[0100]

[Table 23]

[0101]

[Table 24]

Note 1) Weather resistance was measured by the same method as in Table 6.

Examples 30 to 47 Production of Heat Latent Acid Catalysts F-5 to F22 A test tube was charged with 10% by weight of a mixed solvent of methyl isobutyl ketone / ethyl acetate (1/1 by weight), and the mixture was added thereto. Each compound was mixed with stirring so as to have the composition shown in Table 18. The test tube was allowed to stand for 3 hours, and then the solvent used was removed under reduced pressure to obtain the heat latent acid catalysts F-5 to F21 in the yields and yields shown in Table 18.

[0104]

[Table 25]

[0105]

[Table 26]

[0106]

[Table 27]

[0107]Application to one coat solid color  Examples 48 to 57 (1) Production of paint In the composition shown in Table 19, in Example 48, Denacol E was used.
X-421, Example 49 shows compound B-2, Example 50
In Example 51, the compound A-
4. In Example 52, coronate EH, and in Example 53, coronate EH.
Compound B-1 in Example 53 and Example 5 in Immel 303 and Example 54
KR-214 in Example 5, Cymel 303 in Example 57
The mixture removed and in Example 56 all raw materials were sanded.
Charge into a mill and disperse until particle size is less than 10μm
Was. Thereafter, in Example 56, as it is, and in Example 48
In Examples 55 to 55 and Example 57, the raw materials removed during the dispersion of the pigment were used.
Each was added and mixed to obtain a one-pack type paint. Each paint obtained
Is thinner (xylene / butyl acetate = 8/2 weight ratio)
1 poise (at 20 ° C by Brookfield viscometer)
, And sealed and stored at 50 ° C. 5
After storing at 0 ° C for 30 days, the viscosity was measured again.
As shown in Table 20, almost all viscosity increases were observed.
And showed excellent storage stability.

[0108]

[Table 28]

[0109]

[Table 29]

Note 1) Denacol EX-421: trade name, Nagase Chemical Industries
2) Chemitite PZ-33: trade name, Nippon Shokubai Chemical Co., Ltd.
Co., Ltd., polyaziridine, aziridine content 6.2 mol /
kg 3) Coronate EH: trade name, Nippon Polyurethane Industry
Hexamethylene diisocyanate trimer, isocyanate content 21 wt% manufactured by Co., Ltd. 4) Cymel 303: trade name, Mitsui Cyanamid Co., Ltd.
5) KR-214: trade name, Shin-Etsu Chemical Co., Ltd., silicone varnish, hydroxyl equivalent 490, non-volatile content 70 wt% 6) Titanium dioxide JR-602: trade name Imperial Chemical Industry Co., Ltd.
7) Modaflow: trade name, manufactured by Monsanto, leveling agent

(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
m, and baked at 175 ° C. for 25 minutes, and air-sprayed with an intermediate coating paint Epico No. 1500CP sealer (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) to a dry film thickness of 40 μm. A test plate was prepared by baking at ℃ for 30 minutes. Then, (1)
Each raw paint is thinner (xylene / butyl acetate =
8/2 weight ratio) and the coating viscosity (Ford Cup No. 4,
After dilution at 20 ° C. for 25 seconds), the test plate prepared by the above method was applied by air spray and baked under the conditions shown in Table 20 to prepare a test piece. The coating film performance is shown in Table 20. In each case, a uniform and glossy coating film was obtained, showing excellent acid resistance, impact resistance, weather resistance and hardness.

[0112]

[Table 30]

[0113]

[Table 31]

[0114]

[Table 32]

[0115]

[Table 33]

Note 1) Weather resistance was measured by the same method as in Table 6.

[0117]For 2 coats and 1 bake metallic color
for  Examples 58 to 64 (1) Production of clear paint A raw material having the composition shown in Table 21 was mixed to obtain a one-pack clear paint.
Was. Each of the obtained paints was prepared in the same manner as in Examples 48 to 57.
The results of the storage stability test were as shown in Table 22.
In each case, almost no increase in viscosity was observed,
Exhibited excellent storage stability.

[0118]

[Table 34]

(2) Preparation and preparation of test pieces Each of the obtained raw paints was diluted in the same manner as in Examples 48 to 57. Then, a test plate prepared in the same manner as in Examples 48 to 57 was coated with Bellcoat No. 6000 silver metallic basecoat paint (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) by air spray at intervals of 1 minute and 30 seconds and two stages. , And then set at 20 ° C. for 3 minutes. Then, each of the diluted clear paints was applied by air spray and baked under the conditions shown in Table 22 to prepare test specimens. The coating film performance is shown in Table 22. In each case, a uniform and glossy coating film was obtained, and excellent acid resistance, impact resistance,
It showed weather resistance and hardness.

[0120]

[Table 35]

[0121]

[Table 36]

Note 1) Weather resistance was measured by the same method as in Table 6.

Examples 65 to 71 10 parts by weight of ethyl acetate were charged into test tubes for heat latent acid catalysts F-23 to F-29 , and each compound was stirred to obtain the composition shown in Table 23. While mixing. Thereafter, the test tube was allowed to stand for 3 hours, and then the solvent was distilled off to obtain heat latent acid catalysts F-23 to F-29 shown in Table 23.

[0124]

[Table 37]

Note 1) Mixture of monomethyl phosphate and dimethyl phosphate

Example 72 Production Example 9 Synthesis of Carboxyl Group-Containing Acrylic Resin H-1 2 equipped with a cooling pipe, a thermometer, a stirrer, and a dropping funnel
4 liters of methyl isobutyl ketone
After charging 88 parts by weight and heating to 100 ° C., 77 parts by weight of methacrylic acid and 194 of methyl methacrylate were added thereto.
Parts by weight, n-butyl acrylate, 221 parts by weight, 2,
A mixture of 20 parts by weight of 2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, at 100 ° C for 2.
As a result of continuing the reaction for 5 hours, a resin solution having an acid value of 100 mgKOH / g, a solid content of 51.6% by weight, a number average molecular weight of 3,000,
-1 was obtained. Polycarboxylic acid solution H obtained in Production Example 1
-1 100 parts by weight and epoxy curing agent ERL-4221
To a mixture of 11.9 parts by weight (manufactured by Union Carbide Co., Ltd.) and 45 parts by weight of xylene, 3.85 parts by weight of the heat-latent catalyst F-23 obtained in Example 65 was added, A thermosetting composition was prepared. Next, the composition was flow coated on a tin plate and baked at 140 ° C. for 30 minutes. The thus obtained knoop hardness (AST)
(According to MD-1474) to evaluate its catalytic activity. The number of days until gelling when each composition was stored at 30 ° C. was determined, and the thermal potential of the catalyst was evaluated. Table 24 shows the composition of the thermosetting composition and the evaluation results.

Examples 73 to 78 The same processes as in Example 69 were carried out using the catalysts obtained in Examples 66 to 71 as the heat latent catalyst. The results are shown in Table 24.

[0128]

[Table 38]

Note 1) ERL-4221: trade name, manufactured by Union Carbide Co., Ltd., epoxy curing agent

Comparative Example 22 The procedure of Example 69 was repeated, except that the heat latent catalyst was not used. The results are shown in Table 24. Comparative Example 23 The same procedure was performed as in Example 69 except that zinc chloride was used instead of the heat-latent catalyst. The results are shown in Table 24. As can be seen from the results in Table 24, the thermosetting composition using the heat latent catalyst of the present invention has excellent storage stability and a sufficient thermosetting reaction occurs. On the other hand, no catalyst was used. In Comparative Example 22, although there was no problem in storage stability, the thermosetting reaction was insufficient, and in the case of using a zinc chloride catalyst (Comparative Example 23), the thermosetting reaction had no problem. , Storage stability is inadequate.

Examples 79 to 81 Application to 2-coat, 1-baked metallic color The raw materials having the compositions shown in Table 25 were mixed to obtain a one-pack clear paint. Each of the obtained paints was subjected to a storage stability test at 30 ° C., and as shown in Table 26, almost no increase in viscosity was observed in any case, and excellent storage stability was exhibited.

[0132]

[Table 39]

(2) Preparation of Test Specimens Each raw paint obtained was diluted in the same manner as in Examples 1 to 11. Then, on a test plate prepared in the same manner as in Examples 1 to 11, Bellcoat No. 6000 silver metallic basecoat paint [trade name, manufactured by Nippon Oil & Fats Co., Ltd.] was air-sprayed at intervals of 1 minute and 30 seconds, and two stages. , And then set at 20 ° C. for 3 minutes. Then, each of the diluted clear paints was applied by air spray and baked under the conditions shown in Table 26 to prepare test pieces.
The coating film performance is shown in Table 26. In each case, a uniform and glossy coating film was obtained, showing excellent acid resistance, impact resistance, weather resistance and hardness.

[0134]

[Table 40]

Note 1) Weather resistance was measured by the same method as in Table 6.

Examples 82 to 85 Application of Oxazone Group-Containing Compound (1) Production of Clear Coating Raw materials having the compositions shown in Table 27 were mixed to obtain a one-pack clear coating. Each of the obtained paints was diluted with a thinner (xylene / butyl acetate = 8/2 weight ratio) to 1 poise (measured at 20 ° C. by a Brookfield viscometer), and then diluted with 30 wt.
Stored sealed at 0 ° C. After storage at 30 ° C. for 30 days, the viscosity was measured again. As shown in Table 27, almost no increase in viscosity was observed, indicating excellent storage stability.

(2) Preparation of test piece Cationic electrodeposition paint Aqua No. was applied to mild steel sheet treated with zinc phosphate.
4200 [trade name, manufactured by NOF CORPORATION] with a dry film thickness of 20 μm
m, and baked at 175 ° C. for 25 minutes, and air-sprayed with an intermediate coating paint, High Epico No. 1500 Sealer (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) to a dry film thickness of 40 μm. A test plate was prepared by baking at ℃ for 30 minutes. Next, Bellcoat No. 6000 silver metallic base coat paint [trade name, manufactured by NOF CORPORATION] was applied by air spray at intervals of 1 minute and 30 seconds and a two-stage process to a dry film thickness of 15 μm. After setting for 1 minute,
Of each clear coating paint (Ford Cup No.
(4, 25 seconds at 20 ° C.) was applied by air spray coating and baked at 140 ° C. for 30 minutes to prepare test specimens. The coating film performance is shown in Table 27. In each case, a uniform and glossy coating film was obtained, and excellent acid resistance, impact resistance,
It showed weather resistance and hardness.

[0138]

[Table 41]

Note 1) CX-RS-1200: a polyoxazoline compound manufactured by Nippon Shokubai Co., Ltd., solid content 50%, glass transition point 10 ° C., weight average molecular weight 18,000, oxazoline equivalent molecular weight 55
5. 2) CX-RS-3200: Nippon Shokubai Co., Ltd. polyoxazoline compound, solid content 50%, glass transition point 10 ° C, weight average molecular weight 14000, oxazoline equivalent molecular weight 55
5. 3) Acid catalyst A: zinc octylate and triethyl phosphate complex, zinc octylate content 12% by weight 4) Acid catalyst B: 45% by weight solution of N-methylmorpholine salt of dodecylbenzenesulfonic acid in ethyl acetate

Comparative Examples 24 to 25 Clear coatings were prepared using the raw materials having the compositions shown in Table 28.
A storage stability test was carried out in the same manner as in Examples 82 to 85. As a result, no latent carboxyl compound was used.

[0141]

[Table 42]

Note 1) CX-RS-1200: a polyoxazoline compound manufactured by Nippon Shokubai Co., Ltd., solid content: 50%, glass transition point: 10 ° C., weight average molecular weight: 18,000, oxazoline equivalent molecular weight: 55
5. 2) CX-RS-3200: Nippon Shokubai Co., Ltd. polyoxazoline compound, solid content 50%, glass transition point 10 ° C, weight average molecular weight 14000, oxazoline equivalent molecular weight 55
5. 3) Acid catalyst B: a 45% by weight solution of N-methylmorpholine salt of dodecylbenzenesulfonic acid in ethyl acetate

[0143]

The thermosetting composition of the present invention has a chemical performance,
While giving a cured product with excellent physical performance and weather resistance,
It has excellent storage stability, and is suitably used for, for example, paints, inks, adhesives, and molded products. In particular, when used as a topcoat, the organic solvent emission is small and a paint finish having excellent finished appearance can be performed, which is extremely useful in the field of industrial coating such as automobile coating. Further, when used in a thermosetting composition, the heat-latent acid catalyst of the present invention has excellent storage stability and thermosetting reactivity, and is extremely useful.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 167/02 C09D 167/02 201/06 201/06 // (C08K 13/02 3:10 5:56 5: 057 5: 04 5:17 5:49 3:24) (31) Priority claim number Japanese Patent Application No. 3-287129 (32) Priority date Hei 3 (1991) October 7 (33) Priority claim country Japan (JP) ( (31) Priority claim number Japanese Patent Application No. 4-91985 (32) Priority Date Hei 4 (1992) March 18, (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-92240 (32) Priority date Hei 4 (1992) March 18 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-97058 (32) Priority date Hei 4 (1992) March 24 (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-97057 (32) Priority date Hei 4 (1992) March 24 (33) Priority claim country Japan (JP) (31) Priority claim number 4-97055 (32) Priority Date Hei 4 (1992) March 24 (33) Priority Country Japan (JP) Preliminary Examination (72) Inventor Mitsuyuki Mashimo Higashi Serigaya, Konan-ku, Yokohama, Kanagawa Prefecture 13-1-1308 (72) Inventor Osamu Oe 1-74-2 Hodogaya-cho, Hodogaya-ku, Yokohama-shi, Kanagawa 702 Obel Hodogaya 702 (56) References JP-A-4-175375 (JP, A) JP-A-4-175376 (JP, A) JP-A-4-218561 (JP, A) JP-A-4-227763 (JP, A) JP-A-5-86298 (JP, A) JP-A-5-86297 (JP, A)

Claims (29)

(57) [Claims] (A) A molecule represented by the 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.) (B) a compound having two or more functional groups A compound having two or more reactive functional groups capable of forming a chemical bond with the above functional group by heating, (E) a compound represented by the general formula [2]: (Wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹ have the same meaning as described above) and optionally (C) a heat potential exhibiting activity upon heat curing. A thermosetting composition comprising an acid catalyst as an essential component. 2. The thermosetting composition according to claim 1, which contains the component (C) as a heat-latent acid catalyst. 3. The reactive functional group of component (B) is an epoxy group, oxazoline group, silanol group, alkoxysilane group, hydroxyl group, amino group, imino group, isocyanate group, blocked isocyanate group, cyclocarbonate group, vinyl ether. The thermosetting composition according to claim 1, wherein the thermosetting composition is at least one member selected from the group consisting of a group, a vinylthioether group, an aminomethylol group, an alkylated aminomethylol group, an acetal group and a ketal group. 4. A compound obtained by neutralizing a Bronsted acid or a Lewis acid with a Lewis base, or a complex compound comprising a Lewis acid and a Bronsted acid or a Lewis acid and a Bronsted salt as the component (C). 4. The thermosetting composition according to claim 1, wherein the composition is at least one selected from the group consisting of sulfonic acid esters, phosphoric acid esters, and onium compounds. 5. The method according to claim 1, wherein the component (A) and / or the component (B) is α,
5. The thermosetting composition according to claim 1, which is a polymer of a β-unsaturated compound. 6. The thermosetting composition according to claim 1, wherein component (A) and / or component (B) is a polyester resin. 7. (D) In one molecule, (a) a compound represented by the following general formula [3]: (Wherein 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 heterocyclic ring having Y ² as a hetero atom, and Y ² is an oxygen atom or a sulfur atom.
(B) a self-crosslinking compound having the functional group and at least one reactive functional group capable of forming a chemical bond by heating, (E)
General formula [2] (Wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹ have the same meaning as described above) and optionally (C) a heat potential exhibiting activity upon heat curing. An acid catalyst is an essential component, and in some cases, (A) a molecule of the 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. A compound having two or more functional groups represented by the formula (B): wherein Y ¹ is a heterocyclic ring having Y ¹ as a hetero atom, and Y ¹ is an oxygen atom or a sulfur atom. The molecule has two or more reactive functional groups capable of forming a chemical bond by heating with a functional group represented by the general formula [3] or a functional group represented by the general formula [1] or both. A thermosetting composition comprising a compound. 8. The thermosetting composition according to claim 7, which contains the component (C) as a heat-latent acid catalyst. 9. The reactive functional group of the component (D) and the optional component (B) may be an epoxy group, an oxazoline group, a silanol group, an alkoxysilane group, a hydroxyl group, an amino group, an imino group, an isocyanate group, or a block. 9. The thermosetting composition according to claim 7, which is at least one member selected from the group consisting of an 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. Composition. 10. A compound obtained by neutralizing a Bronsted acid or a Lewis acid with a Lewis base, or a complex compound comprising a Lewis acid and a Bronsted acid or a Lewis acid and a Bronsted salt as the component (C). 10. At least one selected from the group consisting of sulfonic acid esters, phosphoric acid esters and onium compounds.
The thermosetting composition according to the above. 11. The polymer according to claim 7, wherein at least one selected from the component (D) and optionally the component (A) and / or the component (B) is a polymer of an α, β-unsaturated compound. 11. The thermosetting composition according to 8, 9 or 10. 12. The polyester resin according to claim 7, wherein at least one selected from the component (D) and the optionally used component (A) and / or the component (B) is a polyester resin.
Or the thermosetting composition according to 10. (A) A molecule represented by the 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.) A thermosetting composition comprising, as essential components, a compound having two or more oxazoline groups, and (C) a heat-latent acid catalyst having activity during heat curing. 14. The thermosetting composition according to claim 13, which always contains the heat latent acid catalyst of the component (C). 15. A compound obtained by neutralizing a Bronsted acid or a Lewis acid with a Lewis base, or a complex compound comprising a Lewis acid and a Bronsted acid or a Lewis acid and a Bronsted salt as the component (C). 15. At least one member selected from the group consisting of sulfonic acid esters, phosphoric acid esters and onium compounds.
The thermosetting composition according to the above. 16. The component (A) and / or component (G) is a polymer of an α, β-unsaturated compound.
Or the thermosetting composition according to 15. 17. The thermosetting composition according to claim 13, 14 or 15, wherein the component (A) and / or the component (G) is a polyester resin. 18. The component (A) is a latent carboxyl compound obtained by reacting a half-esterified product of a polyol having two or more hydroxyl groups per molecule and an acid anhydride with a vinyl ether compound. The thermosetting composition according to 2, 3, 4, 7, 8, 9, 10, 13, 14, or 15. 19. The thermosetting composition according to claim 1, wherein the component (B) is a compound having two or more epoxy groups per molecule. 20. The composition according to claim 1, wherein the component (B) is an epoxy group-containing α, β
20. The thermosetting composition according to claim 19, which is a copolymer of an unsaturated monomer. 21. The thermosetting composition according to claim 19, wherein the component (B) is an epoxy resin. 22. The heat according to any one of claims 1 to 12 and 13 to 17, wherein the heat latent acid catalyst as the component (C) is contained in an amount of 0.01 to 10% by weight based on 100 parts by weight of the total solid content. Curable composition. 23. An acid catalyst comprising a complex of at least one selected from Lewis acids and at least one selected from Bronsted salts.
A latent heat acid catalyst for a thermosetting composition . 24. A Lewis acid having the general formula (R ⁹ ) _n -M wherein R ⁹ is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group, an acyloxy group, or an active methylene group. One or more organic groups selected from adjacent carbonyl groups, M is B, Mg, Al, C
a, Sn, Pb or the fourth to sixth periods in the long-period table
A transition metal atom belonging to Group 3A to Group 7A, Group 8, Group 1B or Group 2B of the period, and n is an integer of 1 to 6. Wherein the Bronsted salt is at least one Bronsted acid component selected from sulfuric acid, sulfonic acid, phosphoric acid, carboxylic acid, boric acid and derivatives thereof; Phosphines, phosphites,
24. The heat-latent acid catalyst according to claim 23, which is obtained by combining at least one base component selected from an alkali metal, an alkali metal compound, an alkaline earth metal and an alkaline earth metal compound. . 25. An acid catalyst comprising a complex of at least one selected from Lewis acids and at least one selected from Bronsted acids.
A latent heat acid catalyst for a thermosetting composition . 26. A Lewis acid having the general formula (R ⁹ ) _n -M wherein R ⁹ is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group, an acyloxy group, or an active methylene group. One or more organic groups selected from adjacent carbonyl groups, M is B, Mg, Al, C
a, Sn, Pb or the fourth to sixth periods in the long-period table
A transition metal atom belonging to Group 3A to Group 7A, Group 8, Group 1B or Group 2B of the period, and n is an integer of 1 to 6. 26. The method according to claim 25, wherein the Bronsted acid is at least one Bronsted acid selected from sulfuric acid, sulfonic acid, phosphoric acid, carboxylic acid, boric acid, and derivatives thereof. Thermal latent acid catalyst. 27. An object to be coated is coated with an overcoat containing 0 to 100 parts by weight of a pigment per 100 parts by weight of the thermosetting composition according to any one of claims 1 to 22. And paint finish method. 28. An object to be coated comprising applying a colored film-forming composition on a substrate to form a base coat, and then applying a clear film-forming composition to the base coat to form a transparent top coat. The method for applying a composite film to the composition according to any one of claims 1 to 22, wherein only the topcoat clear film-forming composition or any of the topcoat clear film-forming composition and the colored film-forming composition is used. A finish method comprising a topcoat containing any one of the thermosetting compositions described above. 29. An article coated by the coating finishing method according to claim 27 or 28.