JPH11148050A - Coating composition, coating finishing and coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of giving excellent cured products having excellent staining resistance, excellent stain removability and the like by including a specific carboxyl group-having compound, a compound having a functional group capable of reacting with the carboxyl group, and a specific organosilicate as essential components. SOLUTION: This coating composition contains (A) a compound having two or more functional groups of the formula (R<1> -R<3> are each H or a 1-18C organic group; R<4> is a 1-18C organic group; Y" is oxygen atom or sulfur atom), (B) a compound having two or more functional groups capable of forming chemical bonds with the functional groups of the formula in the molecule, and (C) an organosilicate of the formula: (R<5> )n -Si-(OR<6> )4n [R<5> and R<6> are each H, a 1-10C alkyl or an aryl; (n) is 0 or 1] and/or its condensate as essential components. The composition may further contain (D) a thermally potential acid catalyst and/or (E) at least one kind of inorganic oxide sol selected from aluminum trioxide sol and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel coating composition, a coating finishing method and a coated article. More specifically, the present invention relates to stain resistance, stain removal property, weather resistance (light).
Gives a cured product with excellent properties, chemical resistance, moisture resistance and appearance,
The present invention also relates to a coating composition, a coating finishing method, and a coated article having high environmental preservation and safety.

[0002]

2. Description of the Related Art Conventionally, a compound having a carboxyl group and a reactive functional group capable of forming a chemical bond with the carboxyl group, such as an epoxy group, an oxazoline group, a hydroxyl group, an amino group, an imino group, an isocyanate group, Coating compositions comprising a combination with a compound having an isocyanate group, a cyclocarbonate group, a vinyl ether group, a vinyl thioether group, an aminomethylol group, an alkylated aminomethylol 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.
No. 14,429, EP-A-29,595, U.S. Pat. Nos. 4,371,667 and 4,650,718.
No. 4,681,811, No. 4,703,
Nos. 101 and 4,764,430. Further, as a composition comprising a combination of a carboxyl group and an oxazoline group, US Pat.
No. 97, Japanese Patent Application Laid-Open No. 60-88038.
And JP-A-2-115238. These coating compositions are excellent in chemical performance, physical performance, and weather resistance of the obtained cured product, and are widely used.

However, since a 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 waking up and shortening the pot life. In addition, the carboxyl group-containing compound used in the conventional coating composition is, due to the strong hydrogen bonding of the carboxyl group, has low solubility in general-purpose organic solvents, or a compound having a functional group that reacts with the carboxyl group. Has the disadvantage of poor compatibility. When this coating composition is used as a top coating, there is a problem that it is difficult to form a so-called high solid with a small discharge amount of the organic solvent, or the finished appearance is poor. As a method for solving such a problem, for example, a carboxyl group is blocked as a t-butyl ester, and the ester is decomposed by heating,
A method has been proposed in which a free carboxyl group is regenerated by elimination of isobutene (Japanese Patent Laid-Open No. 1-1046).
No. 46).

However, this method requires a high temperature of about 170 to 200 ° C. for the thermal decomposition of the t-butyl group, and cannot be said to be a method that is sufficiently satisfactory from the viewpoint of resource saving and energy saving in recent years. . Furthermore, there is a problem that defoaming traces remain on the surface of the cured product due to foaming of isobutene gas, which is a decomposition reaction product, and it cannot be said that this method is necessarily satisfactory. In addition, in recent years, oil droplets and dust contained in the air have increased due to changes in the environment such as air pollution and the like, and coatings applied to buildings and automobiles are more likely to be contaminated than before, and the contamination has been increased. Are difficult to remove. Therefore, as the performance of the coating film, resistance to contamination, that is, stain resistance, and the ability to remove contaminants from the contaminated coating film, that is, stain removal property, have been desired. Under these circumstances, excellent stain resistance, stain removal properties, weather (light) resistance, gloss, appearance, water resistance,
It has been desired to create a coating composition having excellent chemical resistance, environmental preservation, and safety.

Conventionally used stain-resistant paints include:
The mainstream is a resin containing a fluorine-containing resin as a main component, and its stain resistance is due to the high weather resistance and water repellency of the fluorine-containing resin described below. Fluororesin,
(1) stability against light, heat, chemicals, and the like due to the fact that the bond energy between the fluorine atom and the carbon atom is larger than the bond energy between the hydrogen atom and the carbon atom; The atomic radius of the fluorine atom is large and the polarizability between the fluorine molecules is low (0.68 × 1
0 ^-24 cc), the function is exhibited by water repellency and oil repellency resulting from low surface free energy.

Further, in order to use a fluororesin for a coating material, the purpose is to improve the solubility in a solvent and the like.
Copolymers of fluoroolefins with vinyl ether monomers such as cyclohexyl vinyl ether (JP-A-57-34107), and those used in the form of a resin mixture of a fluorinated copolymer and an acrylic copolymer (JP-A-61-12760). However, at present, the portion based on the fluorine-containing monomer is reduced, and the high weather resistance and stain resistance inherent to the fluorine-containing resin are not sufficiently exhibited. Further, to improve the weather resistance and stain resistance of the fluorine-containing resin for coatings, a fluoroolefin, a β-methyl-substituted α-olefin, a monomer having a chemically curing reactive group, and an ester group having a side chain. (Japanese Patent Application Laid-Open No. 4-279612). However, the decontamination properties are not yet sufficient.

On the other hand, as a stain-resistant composition, there has been proposed a coating composition comprising a blend of a partial condensate of an organosilicon compound and a specific silica fine particle (Japanese Patent Laid-Open No. Hei 2 (1994)).
-3468). However, this publication does not provide a detailed description of the resin component used in the coating composition. In order to solve the above-mentioned problems, the present inventors have developed a coating composition comprising a compound having a functional group in which a carboxyl group is blocked with vinyl ether or the like, and a compound having a reactive functional group that reacts with the functional group. (EP 643112, WO 97/13809).
No.), but depending on the application, more stain resistance,
There is a need for a coating composition that provides excellent coating performance such as moisture resistance.

[0008]

SUMMARY OF THE INVENTION The present invention provides a cured product excellent in weatherability, chemical performance, physical performance, particularly, stain resistance and stain removal properties at a relatively low temperature, and has good storage stability. The purpose of the present invention is to provide a coating composition which can be used as a high-solid one-pack type. Still another object of the present invention is to provide a paint finishing method capable of giving an excellent finish appearance with a small discharge amount of an organic solvent and a coated article obtained by the method.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to develop a coating composition having the above-mentioned preferable properties. As a result, (A) a specific vinyl ether group, vinyl thioether group, or oxygen atom Or a compound having, in one molecule, two or more carboxyl groups blocked with a heterocyclic group having a vinyl double bond having a sulfur atom as a hetero atom, and (B) a chemical bond with the blocked carboxyl group. A compound having two or more reactive functional groups capable of forming a compound, (C) a specific organosilicate and / or a condensate thereof as an essential component, and optionally (D) a heat-latent acid having activity upon heat curing. Catalyst and / or (E)
It has been found that a coating composition comprising a dispersion of at least one inorganic oxide sol selected from among aluminum oxide sol, silicon oxide sol, zirconium oxide sol and antimony oxide sol can achieve the object. ,
The present invention has been completed based on these findings. That is, the present invention relates to (A) a compound represented by the general formula (1)

[0010]

Embedded image

(Wherein R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is a 1 to 1 carbon atom)
In organic group 8, R ³ and R ⁴ may combine with each other to form a heterocyclic ring having Y ¹ as a hetero atom, and Y ¹ is an oxygen atom or a sulfur atom. A) a compound having two or more functional groups represented by formula (B), (B) a compound having two or more reactive functional groups capable of forming a chemical bond with the functional group in one molecule, and (C) a general formula. (2)

[0012]

Embedded image (R ⁵ ) _n —Si— (OR ⁶ ) _4-n (2)

(Wherein R ⁵ and R ⁶ are a hydrogen atom or an alkyl or aryl group having 1 to 10 carbon atoms, respectively)
n is 0 or 1. And (E) an aluminum oxide sol, a silicon oxide sol, and (D) a heat-latent acid catalyst having activity during heat curing. A coating composition comprising a dispersion of at least one inorganic oxide sol selected from zirconium oxide sol and antimony oxide sol.

[0014] The present invention also relates to a coating composition containing 0 to 300 parts by weight of a pigment per 100 parts by weight of the total nonvolatile components of the components (A) and (B) of the coating composition described above. An object of the present invention is to provide a paint finishing method characterized by painting. Further, the present invention provides a coating method 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. In the method of applying a composite coating on a body, only the topcoat clear film-forming composition, or any of the topcoat clear film-forming composition and the colored film-forming composition, may be any of the above-described coating compositions. It is intended to provide a paint finishing method characterized by containing any of them.

Further, the present invention provides a coating method in which a colored base coat paint is applied on a substrate, a clear coat paint is applied in an uncrosslinked state, and after baking the applied paint, an over clear coat paint is further applied and baked. Wherein the clear coat paint is an acrylic resin / aminoplast resin paint, and the overclear coat paint contains any of the paint compositions described above. . further,
The present invention provides a coated article characterized by being coated by the above-mentioned coating finishing method. Still other objects, aspects and advantages of the present invention will be made clear from the following description.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the coating composition of the present invention,
As the compound used as the component (A), a compound represented by the general formula (1)

[0017]

Embedded image

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

[0019]

Embedded image

(Wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹ are
It has the same meaning as above. ) Can be easily formed by reaction with a vinyl ether compound, a vinyl thioether compound or a heterocyclic compound having a vinyl double bond having an oxygen atom or a sulfur atom as a hetero atom. R ¹ in the general formulas (1) and (3),
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;
Organic groups such as alkaryl groups, these organic groups may have a suitable substituent, and R ³ and R ⁴ are
It may combine with each other to form a heterocyclic ring having no or having a substituent having Y ¹ as a hetero atom. Preferred examples of R ¹ , R ² and R ³ include a hydrogen atom and a carbon atom of 1 to 1.
10 alkyl group, an aryl group, an alkaryl group, as for R ⁴ preferably is an alkyl group, an aryl group having 1 to 10 carbon atoms, alkaryl groups.

Suitable specific examples of the above alkyl group include:
For example, methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 2-methylbutyl, n-hexyl, isohexyl, 3-methylpentyl, ethylbutyl, n-heptyl, 2-methylhexyl, n -Octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, methyloctyl, ethylheptyl, n-decyl, n-undecyl,
n-dodecyl, n-tetradecyl, n-heptadecyl,
Examples thereof include an n-octadecyl group, and the alkyl group also includes a cycloalkyl group such as a cyclobutyl group and a cyclohexyl group. Preferred alkyl groups are alkyl groups having 1 to 10 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 2-methylbutyl, n-hexyl, isohexyl, 3-methylpentyl, ethylbutyl, n-heptyl, 2-methylhexyl, n-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, methyloctyl, Ethylheptyl, n-decyl and cyclohexyl groups are mentioned.

The alkyl group also includes an aralkyl group. Suitable examples include benzyl, 1
-Phenylethyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl,
-(4-methylphenyl) ethyl, 2- (4-methylphenyl) ethyl, 2-methylbenzyl and the like. Suitable specific examples of the above aryl group and alkaryl group include aryl groups such as phenyl, tolyl, xylyl, and naphthyl; 4-methylphenyl, 3,4-dimethylphenyl, 3,4,5-trimethylphenyl,
-Ethylphenyl, n-butylphenyl, tert-butylphenyl, amylphenyl, hexylphenyl, nonylphenyl, 2-tert-butyl-5-methylphenyl, cyclohexylphenyl, cresyl, oxyethylcresyl, 2-methyl-4- alkaryl groups such as tert-butylphenyl and dodecylphenyl; and the like, preferably phenyl having 6 to 10 carbon atoms, tolyl,
Aryl groups such as xylyl, 4-methylphenyl, 3,4-dimethylphenyl, 3,4,5-trimethylphenyl, 2-ethylphenyl, n-butylphenyl and tert-butylphenyl, and alkaryl groups are preferred.

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

The compound of the component (A) is obtained by reacting a compound having two or more, preferably 2 to 50 carboxyl groups in one molecule with the compound represented by the general formula (3). be able to. Examples of the compound having two or more carboxyl groups in one molecule include succinic acid, adipic acid, azelaic acid, sebacic acid, aliphatic polycarboxylic acids such as decamethylene dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, Aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid, alicyclic polycarboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid and methylhexahydrophthalic acid, and having two or more carboxyl groups in one molecule Examples include a polyester resin, an acrylic resin, a maleated polybutadiene resin, and a fluororesin having a polyfluoro (alkyl or alkylene) group. Furthermore, carboxyl group-containing silicone oils such as X-22-162A and X-22-1
62C (both trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

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

Examples of the polyol having two or more hydroxyl groups per molecule include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, diethylene glycol, pentanediol, dimethylbutanediol, hydrogenated bisphenol A,
Glycerin, sorbitol, neopentyl glycol,
1,8-octanediol, 1,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol,
Polyhydric alcohols such as 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, quinitol, mannitol, trishydroxyethylisocyanurate, and dipentaerythritol; Ring-opened adducts of polyhydric alcohols with lactone compounds such as γ-butyrolactone and ε-caprolactone; alcohols of the polyhydric alcohols with isocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate Adduct under excess; said polyhydric alcohol and ethylene glycol divinyl ether, polyethylene glycol divinyl ether, butanediol divinyl ether, pen Tandiol divinyl ether,
Adducts of vinyl ether compounds such as hexanediol divinyl ether and 1,4-cyclohexane dimethanol divinyl ether in excess of alcohol are exemplified.

The fluorinated polyol having a fluorine atom introduced into the polyol is, for example, copolymerized with a hydroxyl group-containing vinyl ether and a fluorinated α, β-unsaturated monomer, or optionally, with another α, β-unsaturated monomer. A polyol obtained by copolymerizing a β-unsaturated monomer is exemplified. Examples of the hydroxyl group-containing vinyl ether include various hydroxy vinyl ethers such as hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyheptyl vinyl ether, and hydroxycyclohexyl vinyl ether.

As the fluorine-containing α, β-unsaturated monomer,
For example, CF_Two= CF_Two, CHF = CF_Two, CH_Two= C
F_Two, CH_Two= CHF, CCIF = CF_Two, CHCl = C
F_Two, CCl_Two= CF_Two, CCIF = CCIF, CHF =
CCl_Two, CH_Two= CCIF, CCl_Two= CCIF, CF_Three
CF = CF_Two, CF_ThreeCF = CHF, CF_ThreeCH = CF_Two,
CF_ThreeCF = CH_Two, CHF_TwoCF = CHF, CH_ThreeCF =
CF_Two, CH_ThreeCF = CH_Two, CF_TwoClCF = CF_Two, C
F_ThreeCCl = CF_Two, CF_ThreeCF = CF Cl, CF_TwoClC
Cl = CF_Two, CF_TwoClCF = CF Cl, CF Cl_TwoC
F = CF_Two, CF_ThreeCCl = CCIF , CF_ThreeCCl = C
Cl_Two, CCIF_TwoCF = CCl_Two, CCl_ThreeCF = C
F_Two, CF_TwoClCCl = CCl_Two, CF Cl_TwoCCl = C
Cl_Two, CF_ThreeCF = CHCl, CCIF_TwoCF = CHC
1, CF_ThreeCCl = CHCl, CHF_TwoCCl = CC
l_Two, CF_TwoClCH = CCl_Two, CF_TwoClCCl = CH
Cl, CCl_ThreeCF = CHCl, CF_TwoClCF = C
F_Two, CF_TwoBrCH = CF_Two, CF_ThreeCBr = CHBr,
CF_TwoClCBr = CH_Two, CH_TwoBrCF = CCl_Two, C
F_ThreeCBr = CH_Two, CF_ThreeCH = CHBr, CF_TwoBrC
H = CHF, CF_TwoBrCF = CF_Two, CF_ThreeCF_TwoCF =
CF_Two, CF_ThreeCF = CFCF_Three, CF_ThreeCH = CF C
F_Three, CF_Two= CF CF_TwoCHF_Two, CF_ThreeCF_TwoCF = CH
_Two, CF_ThreeCH = CHCF_Three, CF_Two= CF CF_TwoCH_Three, C
F_Two= CF CH_TwoCH_Three, CF_ThreeCH_TwoCH = CH_Two, CF_Three
CH = CH CH_Three, CF_Two= CHCH_TwoCH_Three, CH_ThreeCF_Two
CH = CH_Two, CFH_TwoCH = CH CF H_Two, CH_ThreeCF_Two
CH = CF_Two, CH_Two= CF CH_TwoCH_Three, CF_Three(CF_Two)
_TwoCF = CF_Two, CF_Three(CF_Two)_ThreeCF = CF_TwoOr CH
_Two= C (CH_Three) COOC_TwoH_FourC_FourF₉, CH_Two= C (C
H_Three) COOC_TwoH_Four(CF_Two)₆C F (CF_Three)_Three, CH_Two=
C (CH_Three) COOC_TwoH_FourC₈F₁₇, CH_Two= C (CH_Three)
COOC_TwoH_FourC_TenF_{twenty one}And the like.

Examples of other α, β-unsaturated monomers include olefins such as ethylene, propylene, butylene, isoprene, chloroprene, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, t-butyl vinyl ether, Pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, cyclohexyl vinyl ether, octyl vinyl ether, 4-methyl-1
-Vinyl ethers such as pentyl vinyl ether, cyclopentyl vinyl ether, phenyl vinyl ether, o-, m-, p-tolyl vinyl ether, benzyl vinyl ether, phenethyl vinyl ether, and allyl ethers, vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, and caproic acid Vinyl, vinyl isocaproate,
Vinyl esters and propenyl esters such as vinyl pivalate, vinyl caprate, isopropenyl acetate, and isopropenyl propionate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate , N-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate, ethoxyethyl (meth) acrylate, styrene, α-methylstyrene, p -Vinyltoluene, p-chlorostyrene, acrylonitrile, methacrylonitrile and the like.

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, and pyromellitic acid. Acid anhydrides of polycarboxylic acids such as acids, tetrahydrophthalic acid, hexahydrophthalic acid and methylhexahydrophthalic acid can be mentioned. Examples of the polyisocyanate compound having two or more isocyanate groups per molecule include, for example, p-phenylene diisocyanate,
Biphenyl diisocyanate, tolylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, methylene bis (Phenyl isocyanate), lysine methyl ester diisocyanate, bis (isocyanate ethyl)
Examples thereof include fumarate, isophorone diisocyanate, methylcyclohexyl diisocyanate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate, and burettes and isocyanurates thereof.

Examples of the hydroxycarboxylic acid include lactic acid, citric acid, hydroxypivalic acid, 12-hydroxystearic acid and malic acid. Examples of the amino acid include DL-alanine, L-glutamic acid and glycine. , L-theanine, glycylglycine, γ-aminocaproic acid, L-aspartic acid, L-
Examples include titrulline, L-arginine, L-leucine, L-serine and the like. Furthermore, carboxyl group-containing α,
Examples of the β-unsaturated monomer include, for example, acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, and the like. As other α, β-unsaturated monomers, for example, The same thing as the above-mentioned thing can be mentioned, Furthermore, fluorine-containing (alpha), (beta)-unsaturated monomer, such as 2,2,2-trifluoromethyl acrylate and 2,2,2-trifluoromethyl methacrylate, etc. are mentioned. Can be mentioned.

A homopolymer of a carboxyl group-containing α, β-unsaturated monomer or a copolymer of a carboxyl group-containing α, β-unsaturated monomer and another α, β-unsaturated monomer The fluorine-containing polymer into which a fluorine atom is introduced is, for example, a copolymer obtained by copolymerizing a carboxyl group-containing α, β-unsaturated monomer and a fluorine-containing α, β-unsaturated monomer, or Copolymers obtained by copolymerizing these and other α, β-unsaturated monomers are also included. Carboxyl group-containing α,
Examples of the β-unsaturated monomer, fluorine-containing α, β-unsaturated monomer, and other α, β-unsaturated monomers include the same as described above.

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 of the thus obtained compound having two or more carboxyl groups in one molecule with the compound represented by the general formula (3) is usually carried out in the range of room temperature to 100 ° C. in the presence of an acid catalyst. Done at temperature. The compound of the component (A) is a compound having a carboxyl group-containing α,
It can also be obtained by homopolymerizing the reaction product of the β-unsaturated monomer and the compound represented by the general formula (3) or copolymerizing the reaction product with another α, β-unsaturated monomer. .

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. As the saturated monomer, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, cyclohexyl acrylate, 2-
Ethylhexyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, n
-Propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate,
Examples include stearyl methacrylate, styrene, α-methylstyrene, p-vinyltoluene, acrylonitrile, and the like. Further, fluorine-containing α such as 2,2,2-trifluoromethyl acrylate and 2,2,2-trifluoromethyl methacrylate can be used. , Β-unsaturated monomers and the like.

In the coating composition of the present invention, the compound of the component (A) may be used alone or in combination of two or more. In the coating 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) regenerates a free carboxyl group, 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 hydroxyl group, an amino group, an imino group, an isocyanate group, a blocked isocyanate group, and 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 resin, alicyclic epoxy resin, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexyl. Homopolymers or copolymers such as methyl methacrylate, copolymers of glycidyl allyl ether and vinylidene fluoride and vinyl ether, polyglycidyl compounds and epoxy group-containing silicone oil obtained by reacting polycarboxylic acid or polyol with epichlorohydrin, For example, KF-101, KF-103, KF-105, X-2
2-169AS (All brand names, Shin-Etsu Chemical Co., Ltd.)
Epoxy-containing compounds such as 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, An oxazoline compound in which an oxazoline ring is bonded to an alkyl chain such as 4-bis (2-oxazolinyl-2) 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-oxazolinyl-2) benzene,
1,3-bis (5-methyl-2-oxazolinyl-2)
Oxazoline compounds in which two oxazoline rings are bonded to an aromatic nucleus such as benzene, 1,4-bis (5-methyl-2-oxazolinyl-2) benzene, and 2,2′-bis (2-oxazoline); 2'-bis (4-methyl-
2-oxazoline), 2,2'-bis (5-methyl-2
-Oxazoline), a polyvalent oxazoline compound obtained by reacting a hydroxyalkyl-2-oxazoline with the polyisocyanate compound, further, 2-vinyl-2-oxazoline, 2-vinyl-4 -Methyl-2-oxazoline, 2-
Vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-
Methyl-2-oxazoline, 2-isopropenyl-5-
An oxazoline group-containing compound such as a homopolymer or a copolymer such as ethyl-2-oxazoline, and a commercially available oxazoline group-containing compound such as CX
-RS-1200, CX-RS-3200 (all manufactured by Nippon Shokubai Co., Ltd.), aliphatic polyols, phenols, polyalkyleneoxy glycols, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy Hydroxyl-containing α, such as propyl acrylate and 2-hydroxypropyl methacrylate,
Hydroxyl group-containing compounds such as homo- or copolymers of β-unsaturated compounds and ε-caprolactone adducts of these polyols; aliphatic and aromatic diamino compounds and polyamino compounds, and cyanoethylation of the polyols Amino group-containing compounds such as polyamino compounds obtained by reducing the product; imino group-containing compounds such as aliphatic and aromatic polyimino compounds; p-phenylenediisocyanate, biphenyldiisocyanate, tolylenediisocyanate, 3,3′-dimethyl- 4,4′-biphenylene diisocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate,
2,2,4-trimethylhexane-1,6-diisocyanate, methylenebis (phenylisocyanate), lysine methylester diisocyanate, bis (isocyanateethyl) fumarate, isophorone diisocyanate, methylcyclohexyl diisocyanate, 2-isocyanateethyl-2,6-diisocyanate Hexanoates and their burettes and isocyanurates, and further isocyanate group-containing compounds such as adduct compounds of these isocyanates and the polyols; phenols of the isocyanate group-containing compounds;
Lactams, active methylenes, alcohols, acid amides, imides, amines, imidazoles, ureas, imines, blocked isocyanate group-containing compounds such as oximes; 3-acryloyloxypropylene carbonate; A cyclocarbonate group-containing compound such as a homopolymer or copolymer of 3-methacryloyloxypropylene carbonate, a polyvalent cyclocarbonate group-containing compound obtained by reacting the epoxy group-containing compound with carbon dioxide; Polyvalent vinyl ether compounds obtained by the reaction of a compound with a halogenated alkyl vinyl ether, polyvinyl compounds obtained by the reaction of a hydroxyalkyl vinyl ether with a polyvalent carboxyl group-containing compound or the polyisocyanate compound Vinyl ether compounds such as vinyl ether compounds, vinyl ether compounds such as homopolymers or copolymers of vinyloxyalkyl acrylates and vinyloxyalkyl methacrylates, and vinyl ether groups and vinyl thioether group-containing compounds such as vinyl thioether compounds corresponding thereto; melamine formaldehyde resins, Glycolyl formaldehyde resin, urea formaldehyde resin, aminomethylol group or alkylated aminomethylol group-containing α, β-unsaturated compound homopolymer or copolymer such as aminomethylol group or alkylated aminomethylol group-containing compound; polyvalent; Ketones, polyhydric aldehyde compounds, polyhydric acetal compounds obtained by reacting the above polyhydric vinyl ether compounds with alcohols or orthoacid esters, and polyol compounds with these Condensates, more like the vinyloxyalkyl acrylate or vinyloxyalkyl methacrylate with alcohols or homopolymer or copolymer acetal group such as or ketal group-containing compound of an adduct of ortho ester.

As the compound of the component (B), a fluorine-containing compound into which a fluorine atom has been introduced can also be used.
As the fluorine-containing compound as the component (B), for example, an α, β-unsaturated monomer having a reactive functional group, a fluorine-containing α,
Copolymers of β-unsaturated monomers and optionally other α, β-unsaturated monomers are mentioned.

Specific examples of the α, β-unsaturated monomer having a reactive functional group include, for example, p-glycidyloxystyrene and p-glycidyloxystyrene as an α, β-unsaturated monomer having an epoxy group. Glycidyloxy-α-methylstyrene, p- (3,4-epoxycyclohexylmethyloxy) styrene, p- (3,4-epoxycyclohexylmethyloxy) -α-methylstyrene, glycidylethylene, 3,4-epoxycyclohexylmethyl Ethylene, glycidyl vinyl ether, 3,4-epoxycyclohexylmethyl vinyl ether, glycidyl allyl ether, 3,4-epoxycyclohexylmethyl allyl ether, and the like.
As β-unsaturated monomers, for example, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxycyclohexyl vinyl ether, hydroxyethyl allyl ether,
Examples of the α, β-unsaturated monomer having an acetal group include 1 mol of ethylene glycol divinyl ether, methanol, ethanol, and the like.
Acetalized product of 1 mol of monohydric alcohol such as propanol and butanol, acetalized product of 1 mol of polyethylene glycol divinyl ether and 1 mol of the above monohydric alcohol, acetal of 1 mol of cyclohexane dimethanol divinyl ether and 1 mol of the above monohydric alcohol And the like. The other α, β-unsaturated monomers used in the copolymer include the same as those described above.

The compound of the component (B) may contain one or more, preferably 1 to 50, blocked functional groups represented by the general formula (1) in addition to the reactive functional groups described above. It may be a material that has self-crosslinking. The compound capable of self-crosslinking is a compound having one or more carboxyl groups in one molecule, preferably 1 to 50 and the reactive functional group 2 or more, preferably 2 to 50, as a starting material, The compound can be produced by the same method as described in the method for producing the compound of the component (A), or the unsaturated compound having the functional group represented by the general formula (1) and the reactive compound It can also be produced by copolymerizing an unsaturated compound having a group. The compound capable of self-crosslinking may contain two or more kinds of the reactive functional groups together with the functional groups represented by the general formula (1). Combinations which are mutually active impair the storage stability and are not preferred.

Examples of such unfavorable combinations include, for example, a combination of a functional group selected from an epoxy group, an isocyanate group, a vinyl ether group, a vinyl thioether group and a cyclocarbonate group with an amino group or an imino group, an isocyanate group or a vinyl ether group. And a combination of a group with a hydroxyl group. In the coating 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, as described above, a combination in which the respective functional groups are mutually active is not preferred because storage stability is impaired.

In the coating composition of the present invention, the component (A) and / or the component (B) is preferably a polymer of an α, β-unsaturated compound or a polyester resin. The mixing ratio of the component (B) is 1/5 in the molar ratio of the functional group represented by the general formula (1) to the reactive functional group.
It is desirably within the range of ５5/1. The functional group represented by the general formula (1) in the present invention regenerates a free carboxyl group and forms a chemical bond with the reactive functional group of the component (B). As a so-called active ester based on the polarization structure, an addition reaction can be caused to the reactive functional group of the component (B). In this case, since no elimination reaction is involved during the cross-linking reaction, it can contribute to a reduction in the emission of volatile organic substances. In the coating composition of the present invention, the compound used as the component (C) is represented by the general formula (2):

[0042]

(R ⁵ ) _n —Si— (OR ⁶ ) _4-n (2)

(Wherein R ⁵ and R ⁶ are each a hydrogen atom or an alkyl or aryl group having 1 to 10 carbon atoms,
n is 0 or 1. ) And / or a condensate thereof, and a condensate of an organosilicate is particularly preferable. Suitable specific examples of the alkyl group of the general formula (2) include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, te
rt-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 2-methylbutyl, n-
Hexyl, isohexyl, 3-methylpentyl, ethylbutyl, n-heptyl, 2-methylhexyl, n-octyl, 2-ethylhexyl, 3-methylheptyl, n-
Examples thereof include nonyl, methyloctyl, ethylheptyl and n-decyl groups. The alkyl group also includes cycloalkyl groups such as cyclobutyl and cyclohexyl.

The alkyl group also includes an aralkyl group. Suitable examples include benzyl, 1
-Phenylethyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 4-phenylbutyl, 1- (4-methylphenyl) ethyl, 2- (4-methylphenyl) ethyl, 2-methylbenzyl and the like. No. Preferred alkyl groups are alkyl groups having 1 to 4 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert.
-Butyl group. Suitable specific examples of the aryl group include, for example, phenyl, tolyl, xylyl, naphthyl and the like, and preferably a phenyl group. A plurality of R ⁶ in one molecule may be the same or a combination of two or more.

Preferred specific examples of the organosilicate (C) include, for example, tetrahydroxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, dimethoxydiethoxysilane, methyltrimethoxysilane. Silane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, ethoxytrimethoxysilane, propoxytrimethoxysilane, butoxytrimethoxysilane, etc. , Preferably tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, ethoxytrimethoxysilane, propoxy Trimethoxysilane include butoxy trimethoxysilane.

The condensate of the organosilicate is a branched or linear condensate of the organosilicates represented by the general formula (2), and has a weight average molecular weight of 200 to 10,000. Certain are preferred, and those in the range of 300-5000 are particularly preferred. Commercially available condensates of organosilicates include:
Mitsubishi Chemical MKC silicate MS51, MS56, M
S56S, MS56SB5, ES40, EMS31, B
TS, methyl silicate 51, ethyl silicate 40, 40T, 48, manufactured by Colcoat Co., Ltd., ORGATICS SI series manufactured by Matsumoto Kosho, ethyl silicate 4 manufactured by Tama Chemical Co., Ltd.
0, 45 and the like.

In the coating composition of the present invention, the organosilicate (C) and the condensate thereof may be used alone or in combination of two or more. Both silicates and condensates thereof may be combined. The amount of component (C) is
The amount is preferably from 1 to 50 parts by weight, particularly preferably from 2 to 30 parts by weight, per 100 parts by weight of the total nonvolatile components of the components (A) and (B). When the amount of the component (C) is less than 1 part by weight,
The coating film is poor in stain resistance, whereas if it exceeds 50 parts by weight, the coating film is hard and undesirably causes defects such as cracking and gloss reduction.

In the present invention, these coating compositions are provided with good long-term storage stability of the composition,
When curing at a low temperature in a short time, accelerates the curing reaction,
For the purpose of imparting good chemical performance and physical performance to the cured product, a heat-latent acid catalyst having activity during heat curing can be contained as a component (D) in some cases. The thermal latent acid catalyst is preferably a compound exhibiting catalytic activity at a temperature of 60 ° C. or higher. If the heat-latent acid catalyst exhibits catalytic activity at a temperature lower than 60 ° C., the resulting composition may cause undesirable situations such as thickening or gelling during storage.

Examples of the component (D) as a heat-latent acid catalyst include a compound obtained by neutralizing a Bronsted acid or a Lewis acid with a Lewis base, a mixture of a Lewis acid and a trialkyl phosphate, a sulfonate ester, a phosphate ester, An onium compound, and (i) a compound containing an epoxy group,
(Ii) a sulfur-containing compound and (iii) a Lewis acid as essential components, and optionally (iv) a carboxylic acid compound and / or
Alternatively, a compound comprising a carboxylic anhydride compound is preferably exemplified.

As the heat-latent acid catalyst of the component (D), for example, those described in JP-A-8-41208 can be mentioned. In the coating composition of the present invention, one kind of the heat-latent acid catalyst of the component (D) may be used, or two or more kinds thereof may be used in combination.
With respect to 100 parts by weight of the total non-volatile content of the component and the component (B),
Usually in the range of 0.01 to 20 parts by weight, preferably 0.02
It is selected so that it is blended in the range of 10 to 10 parts by weight.

When the amount of the heat-latent acid catalyst is less than 0.01 part by weight, the amount of the catalyst is too small to sufficiently exert the effect of accelerating the reaction. On the other hand, if the amount of the heat-latent acid catalyst exceeds 20 parts by weight, the effect of accelerating the reaction will not be improved in spite of the amount, but rather the catalyst will remain in the coating composition in a large amount and the coating film will not be formed. Physical properties may be reduced, which is not preferable. In the coating composition of the present invention, an aluminum oxide sol, a silicon oxide sol, a zirconium oxide sol, and an oxide may be optionally used as the component (E) for the purpose of further improving the stain resistance, stain removal property, and weather resistance of the coating film. A dispersion of at least one inorganic oxide sol selected from dispersions of inorganic oxide sols of antimony sol can be contained. Preferred of these inorganic oxide sols are
It is a silicon oxide sol.

These inorganic oxide sols are generally supplied as an aqueous dispersion, but can be added to the coating composition of the present invention by phase inversion into a desired organic solvent. Preferred organic solvents to be used are ketone solvents such as methyl isobutyl ketone, methyl amyl ketone and cyclohexanone. As the phase inversion method, for example, a method in which a water-soluble organic solvent is added to an aqueous dispersion and the operation of distilling off water is repeated to perform a phase inversion into a desired organic solvent may be used. it can.

The dispersion of the silicon oxide sol can be obtained by adding silicon tetrahalide into water, adding an acid to an aqueous solution of sodium silicate, or the like. As a commercial product, for example, as an aqueous dispersion, Snowtex-
O [trade name, manufactured by Nissan Chemical Industry Co., Ltd.] and Snowtex-N [trade name, manufactured by Nissan Chemical Industry Co., Ltd.], etc., as the organic solvent dispersion, are Snowtex MIBK-ST, Snowtex IPA- ST (both are trade names, manufactured by Nissan Chemical Industries, Ltd.). The dispersion of the inorganic oxide sol is preferably a surface-treated with a silane coupling agent, and particularly preferably the surface of a dispersion of a silicon oxide sol with a silane coupling agent. This surface treatment improves the dispersibility of the inorganic oxide sol in the coating composition.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane,
γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Aminopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane and the like, preferably methyltrimethoxysilane, dimethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane , Γ-methacryloyloxypropyltrimethoxysilane and diphenyldimethoxysilane.
As commercial products, A-162, A-163, AZ
-6122 (all trade names, manufactured by Nippon Unicar Co., Ltd.)
And the like. Further, condensates of the above compounds, for example, KR-9218 and KR-9202 (both trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) as commercial products can also be used as the silane coupling agent. These silane coupling agents can be used alone or in combination of two or more. When the surface treatment is performed with a silane coupling agent, the amount of the silane coupling agent is preferably 1 to 50% by weight, and more preferably 5 to 3% by weight based on the nonvolatile content of the inorganic oxide sol.
0% by weight is more preferred.

As a dispersion of the inorganic oxide sol treated with the silane coupling agent, water contained in the aqueous inorganic oxide sol is subjected to azeotropic distillation and dehydration with an azeotropic solvent with water, and then the inorganic oxide sol is dispersed. It is preferable to use a dispersion of an azeotropic solvent-dispersed inorganic oxide sol obtained by subjecting the dispersion to a surface treatment with a silane coupling agent. In particular, the dispersion of the inorganic oxide sol is preferably a dispersion of a silicon oxide sol. The dispersion of the inorganic oxide sol obtained by this manufacturing method is improved in stain resistance, stain removal properties, weather resistance, etc., and furthermore, it is possible to increase the concentration of the inorganic oxide sol. Is also easily non-volatile. Therefore, the range of selecting the viscosity adjusting thinner at the time of coating is wide, and the coating film can be made thick.

Examples of the azeotropic solvent include water-soluble alcohols, carboxylic esters, and cyclic ethers. Examples of the water-soluble alcohol include ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, and s.
ec-butyl alcohol, t-butyl alcohol, methyl cellosolve, ethyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether, 3-methyl-3-methoxybutanol, propylene glycol monomethyl ether, ethylene glycol, propylene glycol and the like can be mentioned. Examples of the water-soluble carboxylic acid ester include methyl acetate,
Butyl acetate and the like. Examples of the water-soluble cyclic ether include 1,4-dioxane.

These azeotropic solvents can be used alone or in combination of two or more. In addition, a solvent that is immiscible with water may be used for the purpose of increasing the azeotropic distillation dehydration efficiency by using a solvent that is miscible with water. Examples of the solvent include benzene, toluene, xylene, cyclohexanone, diphenyl ether, dibutyl ether and the like. These solvents can be used alone or in combination of two or more. However, the amount used is limited to a range that does not cause aggregation of the sol, and varies depending on the solvent. The azeotropic distillation dehydration is preferably performed while dropping an azeotropic solvent.

The azeotropic distillation dehydration is preferably carried out in the range of 30 to 100 ° C., particularly preferably in the range of 40 to 80 ° C. Further, the azeotropic distillation dehydration can be performed under normal pressure or under reduced pressure, but it is particularly preferable to perform it under reduced pressure. The water content in the azeotropic solvent-dispersed inorganic oxide sol after azeotropic distillation dehydration is usually preferably 2% by weight or less, particularly preferably 1% by weight or less. The concentration of the dispersion of the azeotropic solvent-dispersed inorganic oxide sol after the azeotropic distillation dehydration is preferably such that the heating residue is 55% by weight or less,
Particularly, the content is preferably 25 to 55% by weight.

The surface treatment with the silane coupling agent is as follows.
It can be performed by mixing a silane coupling agent with a dispersion of the solvent-dispersed inorganic oxide sol after azeotropic distillation and dehydration. The surface treatment temperature with the silane coupling agent is not particularly limited, but is usually preferably performed in the range of 20 to 100 ° C, more preferably in the range of 30 to 90 ° C, and particularly preferably in the range of 40 to 80 ° C. It is preferred to be performed. The water content in the solvent-dispersed inorganic oxide sol after the surface treatment with the silane coupling agent is usually preferably 1% by weight or less, particularly preferably 0.5% by weight or less.

Further, the solvent of the solvent-dispersed inorganic oxide sol can be replaced with a desired solvent, if necessary. Examples of the solvent that can be used for this solvent replacement include the above-mentioned alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, dimethylacetamide, dimethylformamide and the like. The solvent substitution is preferably performed in a temperature range of 30 to 120 ° C, particularly preferably in a temperature range of 40 to 110 ° C, depending on the type of the solvent used in the substitution.

The dispersion of the inorganic oxide sol preferably has an average particle diameter of 100 nm or less, particularly preferably 50 nm or less. The lower limit of the average particle size is not particularly limited as long as an inorganic oxide sol can be formed, but is preferably 5 nm or more. When the average particle size is larger than 100 nm,
The transparency of the clear film may be impaired, and the stain resistance and stain removal of the coating film may decrease. In the coating composition of the present invention, the dispersion of the inorganic oxide sol of the component (E) may be used alone or in combination of two or more. The nonvolatile content of the dispersion of the product sol is preferably 1 to 100 parts by weight per 100 parts by weight of the total nonvolatile components of the components (A) and (B). The nonvolatile content of the dispersion of the inorganic oxide sol has a total nonvolatile content of 1
When the amount is less than 1 part by weight per 00 parts by weight, the effect of adding the dispersion of the inorganic oxide sol is not sufficiently exhibited, and the effect of improving the stain resistance, stain removal property and weather resistance of the coating film is not so much recognized. On the other hand, if it exceeds 100 parts by weight, the flexibility of the coating film tends to decrease.

The temperature and time required for curing the coating composition of the present invention include the temperature at which the blocked functional group represented by the general formula (1) regenerates a free carboxyl group, the type of reactive functional group, Although it varies depending on the type of the thermal latent acid catalyst, the temperature is usually in the range of 50 to 300 ° C. for 5 seconds to 2 seconds.
Curing is completed by heating for about 4 hours. The coating composition of the present invention, as it is, or if necessary,
Mixing various additives such as coloring pigments, fillers, solvents, ultraviolet absorbers, antioxidants, flow regulators, etc., and using them in various applications that utilize curability such as paints, inks, adhesives, and molded products Can be.

The coating composition of the present invention can be produced by mixing the above-mentioned components and blending various additives as required. The method of compounding each component and the method of adding various additives are not particularly limited, and can be performed by various methods, and the mixing order and the addition order can be performed in various orders. The coating composition of the present invention can be used as a coating used in a method for preparing an article having a single-layer top coating or a multi-layer coating (composite coating) composed of a colored base coat and a clear top coat, Automotive coatings, railway / vehicle coatings, precoat / postcoat metal product coatings, electrical equipment coatings, steel structure coatings, mechanical coatings, building material coatings, as well as insulation, moisture and rust prevention of electrical and electronic components It is extremely useful in paints and other industrial coatings. For these paints,
Total non-volatile content of component (A) and component (B) of coating composition 1
It is preferable to mix the pigment in an amount of 0 to 300 parts by weight, particularly preferably 0 to 100 parts by weight, per 100 parts by weight. When a pigment is blended, it is preferable to blend at least 0.1 part by weight.

As the pigment, various pigments such as organic pigments and inorganic pigments are used. For example, aluminum, copper, brass, bronze, stainless steel, mica-like iron oxide, flaky metallic powder Metal pigments such as mica pieces coated with titanium oxide or iron oxide 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.

As an example of the composite coating film, for example, a colored film-forming composition is applied on a substrate to form a base coat film, and then the clear film-forming composition of the present invention is formed on the base coat film. There is a composite coating film obtained by a coating finishing method comprising applying a composition to form a transparent top coat film. The colored film-forming composition of the base coat film contains a resin binder and a pigment. Examples of the resin binder include various binders such as known acrylic polymers, polyesters (including alkyd resins), polyurethanes and melamine resins.

The colored film-forming composition for the base coat film may contain at least one of commonly used additives such as a surfactant, a leveling agent, a thixotropic agent, a filler, an antifoaming agent, an organic solvent, and a catalyst. Seeds can be added. In the colored film-forming composition of the base coat film, the pigment is preferably blended in an amount of 1 to 80% by weight, particularly preferably 3 to 60% by weight. As the pigment, various pigments such as organic pigments and inorganic pigments are used.For example, aluminum, copper, brass, bronze, stainless steel, or mica-like iron oxide, flaky metallic powder, oxidized Metal pigments such as mica pieces coated with titanium or iron oxide 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.

In the above-mentioned method for finishing the coating of the composite coating film, the viscosity of the composition for forming a colored film of the base coat film is adjusted to a desired viscosity by heating or adding an organic solvent or a reactive diluent as required. After the coating, the coating film after drying using a commonly used coating machine such as an air spray, an electrostatic air spray, a roll coater, a flow coater, a dipping type coating machine, or a brush, a bar coater, or an applicator is used. It is applied so as to have a thickness of 5 to 300 μm, and is usually cured by heating at a temperature of 50 to 300 ° C. for 5 seconds to 24 hours. After diluting to a desired viscosity with a suitable diluent such as a solvent, the film thickness after drying using the above method is usually 5 to 40 μm, preferably 7 to 35 μm. And then left at a temperature of room temperature to 100 ° C. for 1 to 20 minutes. Then, the clear film-forming composition of the clear coat film has a thickness of 10 to 100 μm, preferably 10 to 100 μm after drying using the above method. ~ 60
μm, and curing by heating at a temperature of 50 to 300 ° C. for 5 seconds to 24 hours. The coating method is preferably spray coating among the above methods.

As another example of the composite coating film, for example, a colored base coat paint is applied on a substrate, a clear coat paint is applied in an uncrosslinked state, and after baking it,
Further, in a coating method in which an overclear coat paint is applied and baked, an acrylic resin / aminoplast resin paint is used as the clearcoat paint, and the coating composition of the present invention is used as the overclearcoat paint. There are composite coatings obtained by finishing methods. As the colored base coat paint, the same as the above-mentioned composite paint film can be used. An acrylic resin / aminoplast resin paint is used as a clear coat paint to be applied in an uncrosslinked state on the colored base coat paint film. Examples of the acrylic resin include (a) an ester of (meth) acrylic acid of an alkyl alcohol having 1 to 12 carbon atoms, (b) a hydroxyl group-containing monomer having a polymerizable double bond, and (c) a polymerizable polymer. Carboxyl group-containing monomer having a double bond as the main component,
Further, if necessary, those obtained by copolymerizing (d) styrene, (e) acrylonitrile, and (f) other monomers may be mentioned.

Examples of aminoplast resins include:
For example, a melamine resin, a guanamine resin and the like are preferably exemplified. One of these aminoplast resins may be used, or two or more thereof may be used in combination. More specifically, there is no particular limitation as long as two or more reactive groups are contained in one molecule, and one or more triazine rings are present in one molecule of melamine or guanamine resin. No problem. As the reactive group present in those resins, preferably, a methylol group, an imino group, or a group obtained by etherifying a methylol group with methanol, butanol, or the like is used. In the acrylic resin / aminoplast resin paint, the mixing ratio of the acrylic resin and the aminoplast resin is not particularly limited, but the weight ratio of the acrylic resin to the aminoplast resin is 90:10.
A range of 50:50 is preferred, especially 80:20 to 60:
A range of 40 is preferred.

In the acrylic resin / aminoplast resin paint, a curing reaction catalyst for the aminoplast resin may be blended. Preferred examples of the curing reaction catalyst for the aminoplast resin include, for example, phosphoric acid-based curing catalysts, sulfonic acid-based curing catalysts such as toluenesulfonic acid and dodecylbenzenesulfonic acid, and amine block bodies thereof. These compounds may be used alone or in combination of two or more, and the curing time can be adjusted in combination with other compounds. Further, the addition amount of these compounds in the acrylic resin / aminoplast resin paint is preferably in the range of 0.01 to 2% by weight based on the total nonvolatile components.

Further, the clear coat paint in the method for finishing the above-mentioned composite paint film may optionally contain additives such as a flow regulator, a leveling agent, an anti-gelling agent, an antioxidant, an ultraviolet absorber and a radical scavenger. Can also be blended. A preferred example of the method for finishing the coating of the composite coating is to heat the colored base coat paint as needed,
After adjusting to a desired viscosity by adding an organic solvent or a reactive diluent, a commonly used coating machine such as an air spray, an electrostatic air spray, a roll coater, a flow coater, a dipping type coating machine, or a brush The film thickness of the coating film after drying using a bar coater, an applicator or the like is usually 5 to 40 μm, preferably 7 to 35 μm.
μm, and at room temperature to 100 ° C.
Leave for 20 minutes, and then apply a clear coat paint using the above method so that the film thickness of the dried film is 10 to 100 μm, preferably 10 to 60 μm.
Heat and cure at a temperature of 00C for 5 seconds to 24 hours. Next, the film thickness of the coating film after drying the over-clear coating paint using the above method is 5 to 50 μm, preferably 5 to 20 μm.
It is applied so as to have a thickness of μm, and cured by heating at a temperature of 50 to 300 ° C. for 5 seconds to 24 hours.

The substrate on which the coating composition of the present invention is applied is not particularly limited, and various substrates can be used, for example, wood, glass, metal, cloth, plastic, foam, Organic materials and inorganic materials such as elastic materials, paper, ceramics, concrete, and gypsum board are exemplified. These substrates may be those which have been subjected to a surface treatment in advance, or those having a coating film formed on the surface in advance. Examples of the coated articles obtained by applying the coating composition of the present invention include buildings, structures, wooden products, metal products, plastic products, rubber products, processed paper, ceramic products, glass products, and the like. More specifically, automobiles, automobile parts (for example, parts such as bodies, bumpers, spoilers, mirrors, wheels, and interior materials, of various materials), metal plates such as steel plates, motorcycles, and motorcycles Parts, road materials (for example, guardrails, traffic signs, etc.), tunnel materials (for example, side walls), ships, railway vehicles, aircraft, printing equipment, printing equipment parts, furniture, musical instruments, home appliances, building materials , Containers, office supplies, sporting goods, toys and the like.

EXAMPLES Next, the present invention will be described more specifically with reference to examples.
The present invention is not limited by these examples. In addition, the coating film performance of the coating film obtained by the coating composition of the present invention was determined as follows. (1) Sharpness: Evaluated by visual observation according to the following criteria. ；: When a fluorescent light is projected on the coating film, the fluorescent light is clearly reflected. Δ: When a fluorescent lamp is projected on the coating film, the periphery (outline) of the fluorescent lamp is slightly blurred. ×: When a fluorescent lamp is projected on the coating film, the periphery (outline) of the fluorescent lamp is significantly blurred. (2) Weather resistance: Sunshine carbon arc lamp type weather resistance tester (JIS K-5400 (1990) 9.8.
After exposure for 1000 hours or 3000 hours using 1), the 60-degree specular gloss value of the coating film (JIS K-5400 (199)
0) 7.6 Specular gloss) was measured, and the abnormality of the coating film was visually judged or compared with the gloss value at the time of non-exposure.

(3) Outdoor contamination resistance: JIS K-540
0 (1990) 9.9, 60 and 120
After exposure outdoors for one day, the color of the uncleaned surface of the coating film (JIS K
-5400 (1990) 7.4.2 measurement method).
By subtracting the unexposed L value from the exposed L value, ΔL
The value was calculated and the contamination of the coating film was determined. (4) Oil resistance marker stain: A line is drawn on the coating film of the test piece with an oil marker, heated at 80 ° C. for 5 hours, and then the surface state is changed after wiping the line with a xylene-soaked flannel. Was visually observed, and the staining property of the oily marker was evaluated according to the following criteria. ；: The line of the oily marker on the test piece was completely wiped off, and no trace was left. Δ: A trace of the oil marker line on the test piece is slightly left. ×: Traces of the line of the oily marker on the test piece clearly remain.

(5) Moisture resistance: After exposing the test piece at a relative humidity of 95% or more at 40 ± 1 ° C. for 240 hours, the surface state of the test piece 2 hours after removal was visually observed. The evaluation was performed according to the following criteria. ；: There is no change in the gloss and the surface condition of the test specimen as compared with the original test specimen. Δ: There is a slight change in gloss and blistering of the test specimen as compared to the original test specimen. ×: The test specimen has a noticeable change in gloss and blisters as compared to the original test specimen. (6) Acid resistance: 2 ml of 40% by weight sulfuric acid was spotted on the test piece, heated at 60 ° C. for 30 minutes, and then the abnormality of the coating film was visually determined. (7) Adhesion: JIS K-5400 (1990)
5.1 An adhesion test was performed according to a cross cut method, and the adhesion was evaluated according to the following criteria. ○: 10 points △: 8 points ×: 6 points or less

Production Example 1 (A) Production of Component Compound A-1 Solution (1) Production of Polycarboxylic Acid Compound A-1 (a) Solution Four units equipped with a thermometer, reflux condenser, stirrer, and dropping funnel The following components were charged into a neck flask and heated under stirring.
The temperature was raised to 0 ° C. 136.0 parts by weight of pentaerythritol 538.7 parts by weight of methyl isobutyl ketone Next, 672.0 parts by weight of methyl hexahydrophthalic anhydride was added dropwise over 2 hours while maintaining the temperature at 120 ° C., and the acid value of the mixture (pyridine / water (Weight ratio) = Continue to heat and stir until the solution diluted about 50 times by weight with a 9/1 mixture and heat-treated at 90 ° C for 30 minutes is titrated with a potassium hydroxide standard solution) to 170 or less. As a result, a tetrafunctional polycarboxylic acid compound A-1 (a) solution was obtained.

(2) Preparation of Compound A-1 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 parts by weight of the polycarboxylic acid compound solution of the above (1) 120.2 parts by weight of isobutyl vinyl ether 0.2 parts by weight of hydrochloric acid 35 parts by weight 46.3 parts by weight of methyl isobutyl ketone 46.3 parts by weight When the acid value of the mixture became 12 or less, The reaction was completed, and after standing to cool, the product was transferred to a separating funnel. The obtained product is washed with 100 parts by weight of a 10% by weight aqueous solution of sodium hydrogen carbonate in a separating funnel, and then the pH of the washing solution is adjusted to 7%.
Washing with 300 parts by weight of deionized water was repeated until the amount of water became the following. After that, the molecular sieve 4A1
/ 16 was added and dried at room temperature for 3 days to obtain a compound A-1 solution having the properties shown in Table 1.

[0078]

[Table 1]

Note 1) Non-volatile content: 50 ° C., 0.1 mmHg
And Gardner viscosity (25 ° C): JIS K-5400 (1
995) 4.5.1. According to Gardner-type foam viscometer method. Production Example 2 (A) Production of Component Compound A-2 Solution (1) Production of Polycarboxylic Acid Compound A-2 (a) Solution In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel. , The following ingredients were charged and heated under stirring.
The temperature was raised to 0 ° C. 134.2 parts by weight of trimethylolpropane Next, 420.4 parts by weight of methylhexahydrophthalic anhydride dissolved by heating in advance while maintaining 140 ° C. were added.
The mixture was added dropwise over a period of time, diluted with the acid value of the mixture (pyridine / water (weight ratio) = 9/1 to about 50 times by weight and heated at 90 ° C. for 30 minutes), and titrated with a potassium hydroxide standard solution. ) Was kept at 285 or less to obtain a polycarboxylic acid compound A-2 (a) solution.

(2) Preparation of Compound A-2 Solution Using the polycarboxylic acid compound solution obtained by the above method, a mixture having the following composition was charged into an autoclave, and the mixture was first thoroughly mixed at 130 ° C. The temperature was lowered to 50 ° C. and stirred. Polycarboxylic acid compound A-2 (a) solution 272.3 parts by weight n-propyl vinyl ether 120.2 parts by weight 2-ethylhexyl phosphate 0.2 parts by weight Methyl isobutyl ketone 46.3 parts by weight The acid value of the mixture is 10 The reaction was terminated when the following conditions were satisfied, and a compound A-2 solution having the properties shown in Table 2 was obtained.

[0081]

[Table 2] Note 1) Non-volatile content: dried at 50 ° C and 0.1 mmHg for 3 hours

Production Example 3 Production of (A) Component Compound A-3 Solution Into a stainless steel autoclave equipped with a stirrer, each of the following monomers, a catalyst solution and sodium borate were charged, and nitrogen replacement, cooling and solidification were performed. After degassing, the fluorine-containing monomer was introduced into the autoclave, and the temperature was gradually raised until the internal temperature of the autoclave reached 60 ° C. Then, 20
After continuing the reaction at the same temperature for a period of time, the internal pressure of the autoclave becomes 1
At the time of the decrease to kg / cm ² or less, the reaction was stopped by cooling. The obtained resin solution was poured into a large excess of heptane, and after the generated resin was precipitated, washed and dried,
A fluorinated compound was obtained. All of the obtained resins were dissolved in xylene to obtain a resin solution having a nonvolatile content of 50% by weight. Hydroxybutyl vinyl ether 33.5 parts by weight Ethyl vinyl ether 4.3 parts by weight Cyclohexyl vinyl ether 4.3 parts by weight Methyl isobutyl ketone 200.0 parts by weight 2,2'-azobisisobutyronitrile 2.0 parts by weight Sodium borate 0 5.5 parts by weight Fluorine-containing monomer (CF ₂ = CFCl) 57.9 parts by weight

Next, the resin solution 2 was placed in a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen gas inlet tube.
00 parts by weight, 44.5 parts by weight of hexahydrophthalic anhydride, and 44.5 parts by weight of methyl isobutyl ketone were charged, and heated at 120 ° C. under stirring with a nitrogen stream. During the reaction, an acid value (a solution obtained by diluting 50 times by weight with a mixed solution of pyridine / water = 9/1 and heated at 90 ° C. for 30 minutes by titration with a potassium hydroxide standard solution) with time was measured. The reaction was terminated when the acid value of the mixture became 57 or less.
The obtained resin solution is a polycarboxyl compound solution having a nonvolatile content of 50% by weight. Next, using the polycarboxyl compound solution obtained by the above reaction, a mixture having the following composition was charged into the same four-necked flask as above, and stirred at room temperature. After terminating the reaction when the acid value of the mixture became 1 or less, Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.)
3 parts by weight of a synthetic acid adsorbent) were added thereto, and the mixture was stirred at room temperature for 48 hours. A fluorine-containing compound A-3 having a molecular weight of 5,200 was obtained. Polycarboxyl compound solution 200.0 parts by weight Ethyl vinyl ether 18.7 parts by weight Monooctyl phosphate 0.2 parts by weight Xylene 10.0 parts by weight

Production Examples 4 and 5 (B) Production of Component Compound B-1 Solution and B-2 Solution Into a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, the initially charged solvent ( Xylene) 4
0.0 parts by weight were charged, and the mixture was heated under stirring and kept at 100 ° C. Next, at a temperature of 100 ° C., a monomer / polymerization initiator mixture (dropping component) having the composition shown in Table 3 was dropped at a constant rate from the dropping funnel over 2 hours. After completion of the dropwise addition, the temperature was kept at 100 ° C. for 1 hour, a polymerization initiator solution (additional catalyst) having the composition shown in Table 3 was added, and the reaction was terminated when the temperature was kept at 100 ° C. for 2 hours. A compound B-1 solution and a compound B-2 solution having the following characteristics were obtained.

[0085]

[Table 3] Note 1) Non-volatile content: dried at 50 ° C and 0.1 mmHg for 3 hours

Production Example 6 Production of (B) Component Compound B-3 Solution Into a stainless steel autoclave equipped with a stirrer, each of the following monomers, a catalyst solution and sodium borate were charged, and replaced with nitrogen, cooled and solidified. After degassing, the following fluorine-containing monomer was introduced into the autoclave, and the temperature was gradually raised until the autoclave internal temperature reached 60 ° C. Thereafter, the reaction was continued for 20 hours at the same temperature, and when the internal pressure of the autoclave dropped to 1 kg / cm ² or less, the reaction was stopped by cooling. The obtained resin solution was poured into a large excess of heptane to precipitate the formed resin, followed by washing and drying to obtain a fluorine-containing compound B-3 at a yield of 90% by weight. The number average molecular weight of the obtained resin determined by gel permeation chromatography (GPC) was 6,300. Further, all of the obtained resins were dissolved in xylene to obtain a resin solution having a nonvolatile content of 50% by weight. Glycidyl vinyl ether 20.0 parts by weight Ethyl vinyl ether 15.0 parts by weight Cyclohexyl vinyl ether 15.0 parts by weight Methyl isobutyl ketone 200.0 parts by weight 2,2'-azobisisobutyronitrile 2.0 parts by weight Sodium borate 0. 5 parts by weight Fluorine-containing monomer (CF ₂ = CFCl) 57.9 parts by weight

Production Example 7 (B) Production of Component Compound B-4 (1) Production of α, β-Unsaturated Compound Table 4 shows a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer. A mixture having the composition of
While stirring. 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 is 10 wt% in a separating funnel.
After alkali washing with 100 parts by weight of an aqueous solution of sodium hydrogen carbonate, 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.
An α, β-unsaturated compound having the described active ingredient was obtained.

[0088]

[Table 4] Note 1) The effective component content was determined by gas chromatography.

(2) Production of Component (B) Compound B-4 A four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel was charged with the initially charged solvent (xylene) in the amount shown in Table 5. 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 5 was dropped at a constant speed from the dropping funnel over 2 hours. After completion of the dropwise addition, the temperature of 80 ° C. was maintained for 1 hour, and the polymerization initiator solution having the composition shown in Table 5 (additional catalyst)
Was added, and the reaction was terminated when the temperature was further maintained at 80 ° C. for 4 hours to obtain a compound B-4 having the properties shown in Table 5 respectively.

[0090]

[Table 5] Note 1) Non-volatile content: 50 ° C., dried at 0.1 mmHg for 3 hours Gardner viscosity (25 ° C.): JIS K-5400 (1
995) 4.5.1. According to Gardner-type foam viscometer method.

Production Examples 8 and 9 Production of D-1 Solution and D-2 Solution of Component (D) of the Heat Latent Acid Catalyst In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel. A compound having an epoxy group as the component (i) and a Lewis acid solution as the component (iii) shown in Table 6 were added, and the mixture was stirred at room temperature. Next, Table 6 shows (i
i) A sulfur-containing compound as a component is added dropwise, and then 70 ° C.
For 2 hours. Further, the mixture was left to cool, and when the temperature reached room temperature, a carboxylic acid compound as a component (iv) shown in Table 6 was added thereto, and the mixture was stirred at room temperature for about 1 hour to obtain a heat latent acid catalyst D-1 solution shown in Table 6 and A D-2 solution was obtained.

[0092]

[Table 6]

Production Example 10 Production of (E) Component Compound E-1 Snowtex MIBK-ST (trade name, Nissan Chemical Industries, Ltd.) Industrial Co., Ltd.
Dispersion of silicon oxide sol (average particle size: 15 nm), solid content: 30% by weight, solvent: methyl isobutyl ketone) 10
00 parts by weight and 40 parts by weight of A-163 (manufactured by Nippon Unicar Co., Ltd., silane coupling agent) were charged and heated to 8 parts by weight.
By maintaining at 0 ° C. for 8 hours, 1020 parts by weight of silica sol surface-treated with a silane coupling agent was obtained.

Application to 2-coat 1-bake metallic color Examples 1 to 6 (1) Production of clear paint A raw material having the composition shown in Table 7 was mixed to obtain a one-pack clear paint. (2) Preparation of test piece and examination of coating film performance Cathodic electrodeposition paint Aqua No.
4200 (registered trademark, manufactured by NOF Corporation) with a dry film thickness of 2
0 μm, and baked at 175 ° C. for 25 minutes. 100 Sealer (registered trademark, manufactured by NOF CORPORATION) with a dry film thickness of 30 μm
And sprayed at 140 ° C. for 30 minutes. Then, Bellcoat No. 6000 silver metallic base coat paint (registered trademark, manufactured by NOF CORPORATION) by air spray at intervals of 1 min 30
The coating was performed in two stages for a dry film thickness of 15 μm and set at 20 ° C. for 3 minutes to obtain a test plate. Further, each of the raw paints of the above (1) was applied with a thinner (xylene) to a coating viscosity (Ford Cup No. 4, 20 ° C.).
5 seconds), and then applied to the test plate prepared by the above method by air spray so as to have a dry film thickness of 40 μm.
A test piece was prepared by baking at 0 ° C. under curing conditions for 30 minutes. The coating film performance is shown in Table 8. In each case, a uniform and glossy coating film was obtained, and excellent clarity, weather resistance, outdoor stain resistance, and oil-resistant marker stain were obtained under the baking conditions of 140 ° C. Properties, moisture resistance, acid resistance and adhesion.

(3) Examination of Storage Stability The raw paint of the above (1) was measured at 20 ° C. with a thinner (xylene) by 1 poise (JIS K-5400 (1995) 4.5.3 rotational viscometer method). After dilution to 40)
Stored sealed at 0 ° C. After the storage at 40 ° C. for 30 days in a sealed state, the viscosity was measured again. As shown in Table 7, almost no increase in the viscosity was observed, indicating excellent storage stability.

[0096]

[Table 7]

Note 1) MKC silicate MS56: trade name, a condensate of organosilicate, manufactured by Mitsubishi Chemical Corporation
Weight average molecular weight: 1000-1500 Note 2) MKC silicate MS56SB5: trade name, manufactured by Mitsubishi Chemical Corporation, condensate of organosilicate, weight average molecular weight: 1500-2000

[0098]

[Table 8]

Comparative Example 1 In the compositions shown in Table 9, Comparative Examples 1 and 2 were the same as in Examples 1 to 6 except that the condensate of the organosilicate as the component (C) was omitted.
It was made into a paint in the same manner as above. Example 1 using the obtained paint
As shown in Table 10, in Comparative Example 1, the condensate of the organosilicate as the component (C) and the inorganic oxide sol as the component (E) were removed as shown in Table 10. Therefore, the coating film was poor in outdoor stain resistance and oil resistance marker stain resistance. In Comparative Example 2, since only the inorganic oxide sol as the component (E) was blended, the coating film had poor initial outdoor stain resistance.

[0100]

[Table 9]

[0101]

[Table 10]

Comparative Example 3 In the composition shown in Table 11, in Comparative Example 3, a clear paint was prepared using a non-blocked polycarboxylic acid compound, and a storage stability test was conducted in the same manner as in Examples 1 to 6. However, as shown in Table 12, although the coating film performance was the same as that of the Example, in the crosslinking reaction between the carboxyl group and the epoxy group, neither of the functional groups was blocked at all. It gelled later.

[0103]

[Table 11]

[0104]

[Table 12]

Application to Precoated Steel Sheet Example 7 (1) Production of Paint Raw materials having the composition shown in Table 13 were mixed and charged into a sand mill.
The particles were dispersed until the particle size became 10 μm or less to obtain a one-pack type paint. (2) Preparation of test pieces and examination of coating film performance Undercoat paint precolor primer SP-7 (registered trademark, Nippon Oil & Fats Co., Ltd.) on galvanized steel sheet treated with zinc phosphate
Was coated with a roll coater so as to have a dry film thickness of 5 μm, and baked at a metal temperature of 200 ° C. for 40 seconds during baking to prepare a test plate. Next, the raw paint of the above (1) was coated with Solvesso # 150 (manufactured by Esso Corporation, aromatic petroleum naphtha) to obtain a coating viscosity (Ford Cup No. 4, 20).
(120 ° C. at 120 ° C.), coated on a test plate prepared by the above method using a roll coater so as to have a dry film thickness of 15 μm, and baked at a metal temperature of 230 ° C. for 50 seconds at a baking condition. It was created. The coating film performance is shown in Table 14, and a uniform and glossy coating film was obtained, and good clarity,
It showed weather resistance, outdoor stain resistance, oil resistance marker stain resistance, moisture resistance, acid resistance, and adhesion.

(3) Examination of Storage Stability The raw paint of the above (1) was subjected to 1 poise (JIS K) with Solvesso # 150 (aromatic petroleum naphtha manufactured by Esso Corporation).
-5400 (1995) 4.5.3, measured at 20 ° C. by a rotational viscometer method) and stored tightly closed at 40 ° C. After sealing at 40 ° C. for 30 days, the viscosity was measured again. As shown in Table 13, almost no increase in viscosity was observed, indicating excellent storage stability.

[0107]

[Table 13]

[0108]

[Table 14] Note 1) Titanium dioxide JR-602: trade name, manufactured by Teica Co., Ltd., rutile type titanium dioxide

Application to Composite Coating Film Including Overclear Coat Examples 8 to 13 (1) Production of Overclear Coat Paint The paints produced in Examples 1 to 6 were used as overclear coat paints. (2) Preparation of test piece and examination of coating film performance Cathodic electrodeposition paint Aqua No.
4200 (registered trademark, manufactured by NOF Corporation) with a dry film thickness of 2
0 μm, and baked at 175 ° C. for 25 minutes. 100CP sealer (registered trademark, manufactured by NOF CORPORATION) with a dry film thickness of 30
μm and spray at 140 ° C for 30
Bake for a minute. Then, Bellcoat No. 6000 silver metallic base coat paint (registered trademark, manufactured by NOF CORPORATION) by air spray at intervals of 1 min 30
After coating for 2 seconds at a dry film thickness of 15 μm and setting at 20 ° C. for 3 minutes, Bellcoat No. which is a clear coat paint composed of an acrylic resin / aminoplast resin paint. 6000 clear paint (registered trademark, manufactured by NOF CORPORATION, weight ratio of acrylic resin / aminoplast resin: 70/30) is applied by air spray coating so that the dry coating thickness becomes 30 μm, and the coating is performed at 140 ° C. for 30 minutes. It was baked under curing conditions. Further, the raw paint of the above (1) was applied as an overclear coat paint with a thinner (xylene) (Ford Cup No. 4, 25 seconds at 20 ° C.)
After dilution, the test plate prepared by the above method was applied with an air spray so that the dry coating film thickness became 10 μm.
The composition was cured at 30 ° C. for 30 minutes to prepare a test piece of the composite coating film. The coating film performance is shown in Table 15. In each case, a uniform and glossy coating film was obtained, and excellent clarity, weather resistance, outdoor stain resistance, and oil-resistant marker stains were obtained under baking conditions at 140 ° C. Properties, moisture resistance, acid resistance and adhesion.

[0110]

[Table 15]

[0111]

Industrial Applicability The coating composition of the present invention provides a cured product having excellent chemical performance, physical performance, stain resistance, stain removal properties, weather (light) resistance, chemical resistance and moisture resistance, as well as storage stability. Give excellent paint. In particular, when used as a topcoat, the present invention is applicable to a clear coat paint or an over clear coat paint of a composite coating film, in which a small amount of organic solvent is emitted and a paint finish having an excellent finish appearance can be performed. By using the coating composition of (1), a composite coating film having not only excellent appearance properties but also excellent weather resistance, stain resistance, stain removal properties, chemical resistance, and moisture resistance can be obtained.
Therefore, it is extremely useful in the field of industrial coating such as automotive coating and pre-coated steel sheet.

Claims (11)

[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 the said compound having a reactive functional group 2 or more capable of forming a functional group chemically bonded, and (C) the general formula (2) ## STR2 ## _{^{(R 5) n -Si- (oR}} 6) 4- _n (2) (wherein R ⁵ and R ⁶ each represent a hydrogen atom or a
10 alkyl groups or aryl groups, and n is 0 or 1.
It is. The organosilicate represented by the formula (1) and / or a condensate thereof is used as an essential component, and is optionally used (D).
A dispersion of a heat-latent acid catalyst and / or (E) at least one inorganic oxide sol selected from aluminum oxide sol, silicon oxide sol, zirconium oxide sol and antimony oxide sol, which is active during heat curing. A coating composition characterized by comprising: 2. The reactive functional group of component (B) is an epoxy group, an oxazoline group, a hydroxyl group, an amino group, an imino group, an isocyanate group, a blocked isocyanate group, a cyclocarbonate group, a vinyl ether group, a vinyl thioether group, or an amino group. A functional group represented by at least one selected from a methylol group, an alkylated aminomethylol group, an acetal group and a ketal group, wherein the mixing ratio of the component (A) and the component (B) is represented by the general formula (1) The coating composition according to claim 1, wherein the molar ratio of the reactive functional group to the reactive functional group is in the range of 1/5 to 5/1. 3. The weight average molecular weight of the organosilicate condensate of the component (C) is in the range of 200 to 10,000, and the component (C) per 100 parts by weight of the total nonvolatile components of the components (A) and (B). Is contained in an amount of 1 to 50 parts by weight.
Or the coating composition according to 2. 4. A compound obtained by neutralizing a Bronsted acid or a Lewis acid with a Lewis base, a mixture of a Lewis acid and a trialkyl phosphate,
Sulfonic acid esters, phosphoric acid esters, onium compounds, and (i) a compound containing an epoxy group, (i
3. The method according to claim 1, wherein at least one selected from the group consisting of i) a sulfur-containing compound and (iii) a Lewis acid as essential components and optionally (iv) a carboxylic acid compound and / or a carboxylic anhydride compound. 3. The coating composition according to 3. 5. The component (E) is a dispersion of a silicon oxide sol, and has a total non-volatile content of the components (A) and (B) of 100.
The coating composition according to claim 1, 2, 3 or 4, comprising 1 to 100 parts by weight of the component (E) per part by weight. 6. The coating composition according to claim 1, wherein the dispersion of the inorganic oxide sol of the component (E) has been surface-treated with a silane coupling agent. 7. The component (A) and / or (B) component,
7. The coating composition according to claim 1, which is a polymer of an α, β-unsaturated compound or a polyester resin. 8. A top coat containing 0 to 300 parts by weight of a pigment per 100 parts by weight of the total nonvolatile components of the components (A) and (B) of the coating composition according to claim 1. A paint finishing method characterized by applying a paint to an object to be coated. 9. 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. 8. The method according to claim 1, wherein the composition comprises a topcoat clear film-forming composition alone, or both the topcoat clear film-forming composition and a colored film-forming composition. A paint finishing method comprising any one of compositions. 10. A coating method in which a colored base coat paint is applied on a base material, a clear coat paint is applied in an uncrosslinked state, baked, and then an over clear coat paint is applied and baked. The coat paint is an acrylic resin / aminoplast resin paint, and the over-clear coat paint is in claim 1.
A paint finishing method comprising any one of the coating compositions according to claim 7. 11. A coated article coated by the coating finishing method according to claim 8. Description: