JPH1088065A - Curable composition for top-coat paint and coated product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition for a solvent-based top-coat paint which exhibits excellent appearance properties, thermosetting properties, etc., and extremely excellent stain resistance, and which can be suitably used particularly for an automotive top-coat paint. An object and a coated object using the same are provided. SOLUTION: (A) 100% by weight of a base resin containing a polyoxyalkylene group, wherein at least one kind is a resin composed of a single or a mixture of two or more kinds, A silicon compound represented by the formula (I) and / or a partially hydrolyzed condensate thereof
Mix parts by weight. Embedded image (In the formula, R ¹ and R ^{2 each} represent a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, and b represents an integer of 0 to 3.)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an automobile,
Industrial machinery, steel furniture, building interior and exterior, home appliances,
The present invention relates to a curable composition for a top coat suitably used for a plastic product and the like, and a coated product using the same. More specifically, while exhibiting excellent appearance properties, thermosetting properties, etc., and exhibiting extremely excellent stain resistance, a curable composition for a solvent-based topcoat paint which can be suitably used particularly for an automotive topcoat paint, and using the same. Related to painted objects.

[0002]

2. Description of the Related Art Conventionally, acrylic melamine resin, fluororesin, and acrylic urethane resin have been used for painting automobiles, industrial machines, steel furniture, building interior and exterior, home appliances, plastic products, and the like. Paints containing such as main components have been used. By using such a coating material, a coating film having excellent performance such as high appearance and high weather resistance is formed on a substrate.

However, when the above-mentioned acrylic melamine resin coating, fluororesin coating, acrylic urethane resin coating, etc. are used and heat-cured in a two-coat one-bake system or a two-coat two-bake system, the resulting coating film is Although it has excellent appearance and weather resistance, it can be seen that the adhered dirt tends to be less likely to come off, especially in the case of light-colored paints, so that the tendency is more conspicuous, so it is more aesthetically pleasing and easier to clean. In view of the reduction in the number of times of cleaning and the like, improvement in stain resistance is desired.

As a method for preventing these stains, the present inventors have found that by adding a silicate compound to a resin having a hydrolyzable silyl group, excellent stain resistance can be imparted, and a patent application has already been filed. (JP-A-6-145453). These are not only room temperature curing,
It was also found that baking hardening was effective, but in the case of baking, since the initial contact angle was hard to decrease, a satisfactory result was not obtained.

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a coating film having not only excellent appearance and weather resistance but also excellent stain resistance. It is an object of the present invention to provide a curable composition for a solvent-based top coat which can be sufficiently satisfied even when used as a clear paint for automobiles, and a coated article using the same.

[0006]

That is, the curable composition for a solvent-based top coat according to claim 1 is a resin comprising (A) a resin alone or a mixture of two or more, and at least one of them is a resin. (B) 0 to 200 parts by weight of a silicon compound represented by the following general formula (I) and / or a partially hydrolyzed condensate thereof is blended with 100 parts by weight of an oxyalkylene group-containing base resin. It is.

[0007]

Embedded image (In the formula (I), R ¹ and R ^{2 each} represent a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group having 1 to 10 carbon atoms, and may be the same or different. And b is an integer of 0 to 3.) In the curable composition for a solvent-based top coat according to claim 1, the resin containing the polyoxyalkylene group of the component (A) is preferably used. And a monovalent organic group represented by the following general formula (II).

[0008]

Embedded image (In Formula (II), R ³ and R ⁴ each represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, which may be the same or different, and R ⁵ is a hydroxyl group or 1 to 4 carbon atoms.
4 alkoxy groups, p is an integer of 2 to 4, q is 1 to 200
Are respectively shown. According to a third aspect of the present invention, in the curable composition for a solvent-based top coat according to the second aspect, the resin containing a polyoxyalkylene group as the component (A) is a monovalent resin represented by the formula (II). Is obtained by copolymerizing a compound having an organic group of 1 to 30% by weight.

In a fourth aspect of the present invention, there is provided a curable composition for a solvent-based top coat according to any one of the first to third aspects, wherein the resin containing a polyoxyalkylene group as the component (A) is hydrolyzed. It contains at least one of a decomposable silyl group, a hydroxyl group (excluding a polyoxyalkylene group), an epoxy group, a carboxyl group and an amino group.

According to a fifth aspect of the present invention, in the curable composition for a solvent-based top coat according to any one of the first to fourth aspects, the resin containing a polyoxyalkylene group as the component (A) is an acrylic resin. And / or fluorine-based copolymers.

In a sixth aspect of the present invention, in the curable composition for a solvent-based top coating composition according to any one of the first to fifth aspects, the resin containing a polyoxyalkylene group as the component (A) is light-sensitive. An acrylic and / or fluorine-based copolymer obtained by copolymerizing a stable monomer and an ultraviolet absorbing monomer.

According to a seventh aspect of the present invention, the curable composition for a solvent-based top coat according to any one of the first to sixth aspects further contains an amino resin or an isocyanate compound (including a blocked product).

According to an eighth aspect of the present invention, there is provided the curable composition for a solvent-based top coat according to any one of the first to seventh aspects, wherein the component (B) is a partially hydrolyzed condensate of a tetraalkyl silicate. Yes, two or more composite systems.

According to a ninth aspect of the present invention, there is provided a coated product obtained by applying a topcoat clear coating to a coating surface on which a coating containing at least one of a metallic powder, a mica powder and a coloring pigment is applied. The topcoat clear coating composition contains the curable composition for a solvent-based topcoat coating composition according to any one of claims 1 to 8 as a main component.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the base resin (A) used in the composition of the present invention will be described.

The base resin (A) used in the present invention is a resin containing a polyoxyalkylene group as an essential component, but may further have another functional group.

The polyoxyalkylene group, which is an essential functional group, has, for example, the following general formula (II):

Embedded image (Wherein, R ³ and R ⁴ represent a hydrogen atom or a carbon number of 1 to 4)
R ⁵ is a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, p is an integer of 2 to 4, and q is an integer of 1 to 200, respectively. ) Is a monovalent organic group. The base resin (A) is a compound having this functional group, for example, polypropylene glycol methacrylate, polyethylene glycol monomethacrylate, polyethylene glycol polypropylene glycol methacrylate, polypropylene glycol monoacrylate, polyethylene glycol monoacrylate, polypropylene glycol polytrimethylene monoacrylate, polyethylene glycol. Contains (meth) acrylates such as polytetramethylene glycol monomethacrylate, methoxypolyethylene glycol methacrylate, perfluoroalkylethyl polyoxyalkylene methacrylate, and allyl compounds such as polyethylene glycol monoallyl ether and polypropylene glycol monoallyl ether as copolymerization components. Let It can be obtained by.

These polyoxyalkylene group-containing compounds may be used alone or in combination of two or more.

The amount of the polyoxyalkylene group-containing compound used is preferably 2 to 40% of the total amount of the copolymer components, and is preferably 5 to 40%.
More preferably, it is で 30%. If the amount of such a monomer is less than 2%, the effect of imparting hydrophilicity to the resulting composition is low, and the stain resistance is not sufficient. If it exceeds 40%, the water resistance and weather resistance are reduced. .

The functional components other than the polyoxyalkylene group used in the base resin (A) used in the present invention include a hydrolyzable silyl group, a hydroxyl group (excluding the polyoxyalkylene group), an epoxy group, a carboxyl group, Examples thereof include an amino group, which can be used as an acrylic and / or fluorine-based copolymer. These base resins (A) will be described in order.

[1] Reactive silyl group-containing vinyl resin (A-1) Among the base resins (A), the resin (A-1) having a reactive silyl group has the following general formula (III):

Embedded image (Wherein, R ⁶ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ⁷ is a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group; a represents an integer of 0 to 2, provided that when a plurality of R ⁶ or R ⁷ are contained, they need not be the same.) A reactive silyl group bonded to a carbon atom represented by It has at least one, and its main chain substantially consists of a vinyl copolymer chain. Here, the reactive silyl group is a concept combining a hydrolyzable silyl group and a silanol group. In addition, "vinyl" in the present specification
“Vinyl” is a word indicating that the compound is derived from a compound having a polymerizable C ＝ C bond such as a vinyl group and a vinylidene group.

The curable resin composition obtained by using the resin (A-1) having the above structure has excellent weather resistance, chemical resistance and the like of the formed coating film, and also has a reactive silyl property. Since the group is bonded to a carbon atom, the water resistance of the coating film,
Excellent in alkali resistance, acid resistance, etc.

In the component (A), the number of the reactive silyl group represented by the general formula (III) may be one or more in the molecule, and more preferably 2 to 10, so that the resulting curable composition is It is preferable because the solvent resistance of the coating film formed by using it is excellent.

R ⁶ in the general formula (III) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is preferably, for example, methyl, ethyl, n-propyl, i-propyl, n-propyl. -Butyl group, i-butyl group, t
-An alkyl group having 1 to 4 carbon atoms such as a butyl group. If the alkyl group has more than 10 carbon atoms, the reactivity of the reactive silyl group will decrease. In addition, the above R
It is not preferable that ⁶ is a group other than an alkyl group such as a phenyl group and a benzyl group, because the reactivity of the reactive silyl group is reduced.

Further, R ⁷ in the general formula (III)
Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, is a monovalent hydrocarbon group selected from aryl and aralkyl groups, preferably has a carbon number of 1 to, for example showing a specific example in the R ⁶ An alkyl group having 4 to 25 carbon atoms, for example, an aryl group having 6 to 25 carbon atoms such as a phenyl group; and an aralkyl group having 7 to 12 carbon atoms such as a benzyl group. Among these, the resulting composition has excellent curability. In this respect, an alkyl group is preferable.

The resin (A-1) is obtained by copolymerizing a monomer having a reactive silyl group with another vinyl monomer copolymerizable therewith.

Examples of the monomer having a reactive silyl group include the following monomers.

[0028]

Embedded image

Embedded image

Embedded image .

Examples of other copolymerizable vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth)
Perfluoroalkyl (meth) acrylates such as acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, perfluorobutylethyl methacrylate, perfluorooctylethyl methacrylate, (meth) acrylonitrile, (meth) acrylamide, α -Ethyl (meth)
Acrylamide, N-methyl (meth) acrylamide,
Examples include N, N-dimethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, styrene, α-methylstyrene, chlorostyrene, and aromatic hydrocarbon vinyl compounds such as vinyltoluene. These may be used alone or in combination of two or more.

The above-mentioned silyl group-containing monomers may be used alone or in combination of two or more kinds.
Preferably, it is 60% (% by weight, hereinafter the same).
More preferably, it is 50%. When the amount of such a monomer is less than 5%, the acid resistance of a coating film formed using the curable composition obtained tends to be insufficient. There is a tendency for the storage stability of the hydrophilic composition to decrease.

[2] Reactive silyl group / hydroxyl group-containing vinyl resin (A-2) Vinyl resin having a reactive silyl group and a hydroxyl group (A-
2) can be obtained by copolymerizing the reactive silyl group-containing monomer with a hydroxyl group-containing monomer and another vinyl monomer.

Examples of the hydroxyl group-containing monomer include 2
-Hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, Alonix 5700 (Toa Gosei Chemical Industry Co., Ltd.)
Manufactured), 4-hydroxystyrene, HE-10, HE-2
Acrylic ester oligomer having a hydroxyl group at the terminal such as 0, HP-1, HP-20 (all manufactured by Nippon Shokubai Chemical Industry Co., Ltd.), Blemmer GLM (glycerol monomethacrylate) (Nippon Yushi Co., Ltd.), hydroxyl group Ε-caprolactone-modified hydroxyalkylvinyl-based copolymerizable compounds obtained by the reaction of a contained vinyl compound with ε-caprolactone.

As a typical example of the ε-caprolactone-modified hydroxyalkylvinyl copolymerizable compound, for example, the following general formula (IV):

Embedded image (Wherein, R ⁸ represents a hydrogen atom or a methyl group, and q represents an integer of 1 or more). Specific examples thereof include, for example, Placel FA-1 (R
⁸ is a hydrogen atom, q is 1), Placel FA-4
(R ⁸ is a hydrogen atom, q is 4), Placel FM-
1 (R ⁸ is a methyl group, q is 1), Placel FM
-4 (R ⁸ is a methyl group, q is 4) (all produced by Daicel Chemical Industries, Ltd.), TONE M-100 (R ⁵ is a hydrogen atom, q is 2), TONE M-201 (R ⁸ is methyl Group, q is 1) (all manufactured by UCC), and these may be used alone or in combination of two or more.

Among the above-mentioned monomers, 2-hydroxypropyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate are preferred in that the coating formed using the curable composition obtained has excellent acid resistance and water resistance. ) Acrylates and ε-caprolactone-modified hydroxyalkylvinyl-based copolymerizable compounds are preferred.

The amount of the monomer used is preferably 5 to 50%, more preferably 7 to 35% of the total amount of the copolymer components. If the amount of such a monomer is less than 5%, the resulting composition tends not to exhibit sufficient curability, and if it exceeds 50%, the coating formed using the curable composition tends to be insufficient. Water resistance and acid resistance of the film tend to decrease.

The equivalent of the alcoholic hydroxyl group in the resin (A-2) (the amount (g) of the resin (A-2) containing one mole of the alcoholic hydroxyl group) is from 400 to 2,000 g / mol, preferably from 400 to 2,000 g / mol. , 500 g / mol, more preferably 50
0-1,000 g / mol. If the alcoholic hydroxyl group equivalent is less than 400 g / mol, the acid resistance of the coating film formed using the curable composition obtained will decrease, and if it exceeds 2,000 g / mol, In addition, the thermosetting property of the composition and the scratch resistance and impact resistance of the coating film tend to be reduced.

The equivalent of the reactive silyl group in the resin (A-2) (the amount (g) of the resin (A-2) containing 1 mol of the reactive silyl group represented by the general formula (III)) is excellent. 380-5,000 g / mol from the viewpoint that a curable composition exhibiting thermosetting, acid resistance, weather resistance and the like can be obtained.
It is preferably from 410 to 3,000 g / mol, more preferably from 450 to 1,500 g / mol. When the reactive silyl group equivalent is less than 380 g / mol, the internal stress increases, and when it exceeds 5,000 g / mol, the curability tends to decrease.

Furthermore, the molar ratio of the alcoholic hydroxyl group to the reactive silyl group in the resin (A-2) gives a curable composition exhibiting excellent thermosetting properties, acid resistance, weather resistance, water resistance and the like. From the viewpoint of being able to perform the reaction, the number of moles of the alcoholic hydroxyl group to 1 mole of the reactive silyl group (referred to as “alcoholic hydroxyl group / reactive silyl group”; the same applies hereinafter) is preferably 0.1 to 3, and 0.1 to 0.3. 5 to 2.5 is more preferred, and 0.7 to 2 is even more preferred.

In order to make the molar ratio fall within the above range, for example, a reactive silyl group-containing vinyl monomer and an alcoholic hydroxyl group-containing vinyl monomer used in producing the resin (A-2) are used. What is necessary is just to adjust the usage-amount of a monomer.

[3] Reactive silyl group / epoxy group-containing vinyl resin (A-3) A vinyl resin having a reactive silyl group and an epoxy group (A-3)
-3) is obtained by copolymerizing the reactive silyl group-containing monomer with the epoxy group-containing monomer and other vinyl monomers.

The type of the epoxy group-containing vinyl monomer is not particularly limited, and examples thereof include those represented by the following general formulas (1) to (14).

[0042]

Embedded image

Embedded image (In each formula, R ⁹ represents a hydrogen atom or a methyl group;
¹⁰ represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms. The use amount of the epoxy group-containing vinyl monomer is preferably from 10 to 70% of the total amount of the copolymer components, and more preferably from 20 to 60%. The amount of the monomer used is 1
If the amount is less than 0%, the resulting composition tends not to exhibit sufficient curability and acid resistance, and if it exceeds 70%, the compatibility with other resins and the weather resistance tend to decrease. It is in.

The epoxy group equivalent (the amount (g) of the resin (A-3) containing 1 mol of epoxy group) in the resin (A-3) is 2
40-3,000 g / mol, preferably 240-2.0 g / mol
00 g / mol, more preferably 300 to 1,500 g
/ Mol. When the epoxy group equivalent is less than 240 g / mol, the compatibility between the component (B) and the component (C) is reduced. There is a tendency that the thermosetting property, the scratch resistance and the appearance of the coating film are reduced.

[4] Reactive Silyl Group / Epoxy / Hydroxy Group-Containing Vinyl Resin (A-4) The vinyl resin (A-4) having a reactive silyl group, epoxy group and hydroxyl group is the above reactive silyl group. It can be obtained by copolymerizing a monomer containing a monomer, a monomer containing an epoxy group, a monomer containing a hydroxyl group, and another vinyl monomer.

[5] Vinyl resin having epoxy group and hydroxyl group (A-5) Vinyl resin having epoxy group and hydroxyl group (A-5)
Can be obtained by copolymerization of the epoxy group-containing monomer and the hydroxyl group-containing monomer with another vinyl monomer.

The epoxy group-containing resins (A-3), (A
-4), the compound containing a carboxyl group used in the reaction with (A-5) contains two carboxyl groups in one molecule obtained by half-esterifying a polyol compound and an acid anhydride compound. A compound having two or more hydroxyl groups per molecule, preferably 2 to 2, in terms of weather resistance and acid resistance of a coating film obtained from the composition of the present invention.
It is preferably a compound containing at least two carboxyl groups in one molecule (hereinafter referred to as “carboxylic acid oligomer”) obtained by subjecting a polyol compound having 10 and an acid anhydride compound to a half esterification reaction. .

The polyols having two or more hydroxyl groups per molecule for synthesizing the carboxylic acid oligomer include ethylene glycol, 1,2- and 1,3-propylene glycol, 1,3-butanediol, 4-butanediol, 2,3-butanediol, 1,6-hexanediol, diethylene glycol, pentanediol, dimethylbutanediol, hydrogenated bisphenol A, glycerin, sorbitol, neopentyl glycol, 1,3-octanediol, 1, 4
-Cyclohexanedimethanol, 2-methyl-1,3-
Propanediol, 1,2,6-hexanetriol,
1,2,4-butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol,
Polyhydric alcohols such as quinitol, mannitol, trishydroxyethyl isocyanurate, dipentaerythritol, and trishydroxymethylethane; ring-opened adducts of these polyhydric alcohols with lactone compounds such as γ-butyrolactone and ε-caprolactone; Adducts of the polyhydric alcohols with isocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate in excess of alcohol; polyhydric alcohols with ethylene glycol divinyl ether, polyethylene glycol divinyl ether, butane Diol divinyl ether, pentanediol divinyl ether, hexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl Adducts of vinyl ether compounds such as ethers in excess of alcohol and polyhydric alcohols and alkoxysilicone compounds such as KR-21
3, KR-217, KR-9218 (all trade names,
And Shin-Etsu Chemical Co., Ltd.) in excess of alcohol.

On the other hand, preferred acid anhydrides for reacting with these polyols include hexahydrophthalic anhydride, phthalic anhydride, methylhexahydrophthalic anhydride,
Examples include tetrahydrophthalic anhydride and trimellitic anhydride.

The hydroxyl group-containing carboxylic acid oligomer can be obtained by adjusting the ratio of the polyol and the acid anhydride to be reacted.

The molecular weight of the carboxylic acid oligomer is 2,000
0 or less. If it exceeds 2,000, there is a possibility that a problem that curability is reduced may occur. The preferred range is 100 to 1,800.

The compounding amount of the carboxylic acid oligomer is (A)
0.001 to 100 parts per 100 parts of the component. A preferred range is 0.1 to 90 parts, and a more preferred range is 1.0 to 80 parts.

If the amount of the carboxylic acid oligomer exceeds 100 parts, the water resistance and weather resistance may decrease,
If the amount is less than 0.001 part, the problem that the curability is reduced tends to occur.

Further, the molar ratio of the epoxy group in the component (A) to the carboxyl group in the carboxylic acid oligomer is such that a curable composition exhibiting excellent curability, acid resistance, weather resistance, water resistance and the like can be obtained. Epoxy group /
The carboxyl group is preferably 0.2 to 3.0, more preferably 0.5 to 2.5, and even more preferably 0.6 to 2.0.

The curing catalyst used for accelerating the reaction between the epoxy group and the carboxyl group may be any of those usually used in an esterification reaction (acid-epoxy reaction). For example, a quaternary ammonium salt is preferable. . Specific examples include benzyltriethylammonium chloride or bromide, tetrabutylammonium chloride or bromide, and the like.

The compounding amount of the above curing catalyst is as follows:
0.001 to 10% by weight based on 0 parts is preferable.

[6] Hydroxyl group-containing vinyl resin (A-6) The hydroxyl group-containing vinyl resin (A-6) can be obtained by copolymerizing the hydroxyl group-containing monomer with another vinyl monomer.

[7] Hydroxyl-Containing Fluororesin (A-7) Hydroxyl-containing fluororesin (A-7) includes hydroxyalkyl ethyl vinyl ethers such as hydroxyethyl vinyl ether and full hydroxypropyl vinyl ether, vinyl fluoride, vinylidene fluoride, and the like. Fluoroolefins such as ethylene tetrafluoride, olefins such as ethylene and propylene, vinyl ethers such as ethyl vinyl ether and isobutyl vinyl ether, vinyl acetate,
It can be obtained by copolymerization of fatty acid vinyl esters such as vinyl butyrate and vinyl lactate, and perfluoroalkyl (meth) acrylates such as perfluorobutylethyl methacrylate and perfluorooctylethyl methacrylate.

[8] Amino group-containing vinyl resin (A-
8) The vinyl resin having an amino group (A-8) can be obtained by copolymerizing an amino group-containing monomer with the other vinyl monomer.

Examples of the amino group-containing monomer include basic nitrogen such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, vinylpyridine and aminoethyl vinyl ether. Atom-containing vinyl compounds,
These can be used alone or in combination of two or more.

[9] Carboxyl group-containing vinyl resin (A-9) The carboxyl group-containing vinyl resin (A-9) can be obtained by copolymerizing a carboxyl group-containing monomer with the other vinyl monomers. .

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, maleic acid and fumaric acid, and alkali metal salts thereof.
Salts such as ammonium salts and amine salts are exemplified.

[10] Resin having a carboxyl group and a carboxylic ester group (A-10) The resin having a carboxyl group and a carboxylic ester group (A-10) is a resin having the above-mentioned acid anhydride group and another vinyl Of a polymer obtained by copolymerization with a monomer,
It can be obtained by half esterification with an alcohol.

[11] Non-Aqueous Dispersion Polymer Having a Hydroxyl Group (A-11) The non-aqueous dispersion polymer having a hydroxyl group (A-11) is described in the literature (KEJ Barrett. Dispersi).
on Polymerization inOrgan
ic Media, John Wiley & Son
s. London. (1975)), it is a polymer stably dispersed in an organic medium. This polymer is formed from (1) a core portion and (2) an arm portion, and both are covalently bonded by, for example, a reaction between a carboxylic acid and an epoxy group.

The core part (1) is composed of a polymer dispersed in an organic medium. The arm portion (2) itself is a polymer that is soluble in an organic medium and is a stabilizer that forms a steric barrier by binding to the core portion (1).

The core part (1) has a number average molecular weight of 15,0
From 100 to 300,000 macromolecular polymers,
The arm portion (2) is a stabilizer that forms a steric barrier, and is a macromer chain attached to the core portion (1).

The core part (1) is made of a copolymer of a vinyl monomer. Examples of this monomer are not particularly limited, and include, for example, acrylic acid and methacrylic acid and their alkyl esters, hydroxyalkyl esters, allyl esters, glycidyl esters; styrene; acrylonitrile.

The arm part (2) attached to the core part (1) makes up 90 to 10%, preferably 50 to 20%, of the dispersed polymer. If the proportion of the arm portion (2) exceeds 90% of the dispersed polymer, it is difficult to obtain a durable cured product. On the other hand, if it is less than 10%, the viscosity of the dispersed polymer may be increased, or the stability of the dispersed polymer may be deteriorated to cause precipitation.

The polymer soluble in an organic solvent in the arm portion (2) is at least one vinyl monomer having a hydroxyl group.
Parts, preferably 5 to 25 parts, and at least 70 to 95 parts, and preferably 75 to 95 parts, of at least one other vinyl monomer having no hydroxyl group. If the amount of the vinyl-based monomer having a hydroxyl group is less than 5 parts, the curability tends to decrease. On the other hand, when the amount exceeds 30 parts, the solubility in the organic solvent is reduced, or the stability of the dispersed polymer is insufficient.

[12] Resin Using Light-Stable Monomer and UV-Absorptive Monomer (A-12) The resin containing a polyoxyalkylene group as the component (A) is a light-stable monomer and a resin. An acrylic and / or fluorine copolymer obtained by copolymerizing an ultraviolet absorbing monomer may be used.

Specific examples of the polymerizable photostable monomer include:
For example, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, 2,2,6,6-
Tetramethyl-4-piperidyl methacrylate, 2,
2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidyl methacrylate, 2,2,6,6-tetramethyl-4-iminopiperidyl methacrylate, -Cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-cyano-1,2,2,6,6-pentamethyl-4-piperidyl methacrylate and the like, but are not limited thereto. Not something.

Specific examples of the polymerizable UV-absorbing monomer include, for example, 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone, 2-hydroxy-4-
(Acryloyloxyethoxy) benzophenone, 2-
Examples include, but are not limited to, hydroxy-4-methacryloyloxymethylaminobenzophenone, 2-hydroxy-4-methacryloyloxymethoxybenzophenone, 2-hydroxy-4-methacryloyloxymethylthiobenzophenone, and the like.

The amount of the polymerizable light-stable monomer and the polymerizable ultraviolet-stable monomer used is 0.5 to 10 of the total amount of the copolymer components.
% Is preferable, and 1 to 5% is more preferable.

Next, the component B will be described.

The component (B) used in the present invention is represented by the general formula (I):

Embedded image The silicon compound represented by and / or the partial hydrolysis condensate (B) functions to improve the stain resistance of a coating film formed using the obtained curable composition.

In the above formula (I), R ¹ is an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an aryl group, preferably an aryl group having 6 to 9 carbon atoms and an aralkyl group. preferably is a monovalent hydrocarbon group selected from aralkyl group having a carbon number of 7 to 9, R ²
Is an alkyl group having 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
4 alkyl groups and aryl groups, preferably 6 to 9 carbon atoms
Aryl and aralkyl groups, preferably having 7 carbon atoms
A monovalent hydrocarbon group selected from aralkyl groups of 1 to 9; Further, b is because it is 0 or 1, but in the same molecule ^(R 1 O) groups are present 4-3 pieces, 4-3 pieces present in the same molecule of ^(R 1 O) groups is in the same No need to be.

Specific examples of the above silicon compound include, for example, tetramethyl silicate, tetraethyl silicate, tetra n-propyl silicate, tetra i-propyl silicate, tetra n-butyl silicate, tetra i
Tetraalkyl silicates such as -butyl silicate and tetra-t-butyl silicate; alkyls such as methyltrimethoxysilane, methyltriethoxysilane, octadecyltriethoxysilane, methyltrisec-octyloxysilane, methyltriisopropoxysilane and methyltributoxysilane Trialkoxysilanes; alkyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; alkylmonoalkoxysilanes such as trimethylmethoxysilane; aryltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; methyltriphenoxysilane; Alkyltriaryloxysilane of 3-
Examples include trialkoxysilanes such as glycidoxytrialkoxysilanes such as glycidoxypropyltrimethoxysilane and triaryloxysilanes.

As the partially hydrolyzed condensate of the silicon compound, for example, water is added to the above-mentioned tetraalkylsilicate, trialkoxysilane, dialkoxysilane, monoalkoxysilane, triaryloxysilane, etc. by a usual method. Examples include those obtained by partial hydrolysis and condensation. As a specific example, for example, MS
Partially hydrolyzed condensates of tetraalkyl silicates such as I51, ESI40, HAS-1 and HAS-10 (all manufactured by Colcoat Co., Ltd.), and trialkoxysilanes such as AFP-1 (manufactured by Shin-Etsu Chemical Co., Ltd.) And partially hydrolyzed condensates.

The above-mentioned component (B) may be used alone, but it is more preferable to use two or more kinds together.

The MSI 51 has a high compatibility with the component (A), a high curability of the composition obtained, and a high hardness of the coating film formed by using the composition, which suppresses fixing of contaminants. Such a partially hydrolyzed condensate of tetramethyl silicate is preferred, and ESI40, HAS-1, HAS-10 are preferred in that they impart hydrophilicity to the composition.
Preferred are partially hydrolyzed condensates of tetraethyl silicate.

Component (B) is used in an amount of 0 to 200 parts, preferably 3 to 100 parts, per 100 parts of component (A).
Parts, more preferably 5 to 50 parts. If the component (B) exceeds 200 parts, the impact resistance decreases.

The composition of the present invention preferably further contains an amino resin and / or a polyisocyanate compound for improving curability.

Examples of the amino resin include amino resins (melamine resin) obtained by reacting an amino component such as melamine, urea, benzoguanamine, glycol urea, acetoguanamine and dicyandiamide with an aldehyde such as formaldehyde, paraformaldehyde, acetaldehyde and benzaldehyde. , A urea resin, a methylolated amino resin such as a guanamine resin) and the like.

Among the amino resins, a melamine resin is preferably used from the viewpoint of improving the finished appearance and having good curability.

Further, the amino resin (for example, a methylolated amino resin) is prepared by adding methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol,
Those further etherified with an alcohol such as -ethylbutanol or 2-ethylhexanol may be used.

Specific examples of the above-mentioned amino resin include Uvan 20SE and 20SE-60 manufactured by Mitsui Toatsu Chemicals, Inc.
U-Van 128, U-Van 220, U-Van 225, U-Van 20SB, U-Van 20SE-60, U-Van 2
1R, U-Van 22R, U-Van 122, U-Van 28
N-butylated melamine resins such as -60, U-Van 20HS, U-Van 2028, U-Van 202, U-Van 120, U-Van 62, U-Van 69-1, and U-Van 16
9, isobutylated melamine resin such as Uban 2061, butylated urea resin such as Uban 10S-60 and Uban 10R, Cymel 30 manufactured by Mitsui Cytec Co., Ltd.
3, Cymel 232, Cymel 370, Cymel 32
5, Cymel 236, Cymel 738, Cymel 77
1, Cymel 327, Cymel 703, Cymel 70
1, Cymel 266, Cymel 267, Cymel 28
5, Cymel 235, Cymel 238, Cymel 114
1, Cymel 272, Cymel 254, Cymel 20
2, Cymel 1156, Cymel 1158, Cymel 3
00, Cymel 301, Cymel 350, Cymel 73
Melamine resin such as No. 6; Of these, Cymel 235, Cymel 238, Cymel 1158
Alkyl etherified melamine resins such as the above are preferred from the viewpoint of curability.

The polyisocyanate compound is a compound having two isocyanate groups in one molecule, for example, an aliphatic compound such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone. Examples include alicyclic compounds such as diisocyanate and cyclohexane diisocyanate, and aromatic compounds such as tolylene diisocyanate and diphenylmethane diisocyanate.

The isocyanate compound used in the present invention may be a blocked product. As the blocked polyisocyanate compound, the above polyisocyanate compound may be used by converting a lactam blocking agent such as ε-caprolactam, ethanol, propanol, butanol and the like. Examples include those blocked with an alcohol-based blocking agent, an oxime-based blocking agent such as acetoxime, and the like.

Preferred specific examples of the blocked polyisocyanate include those in which the isocyanate group of hexamethylene diisocyanate is blocked with methyl ethyl ketoxime or the like.

The amino resin and the polyisocyanate compound can be used in combination with a hydroxyl group-containing resin.

The mixing ratio of the hydroxyl group-containing resin to the amino resin is preferably 90 to 50% by weight of the hydroxyl group-containing resin and 10 to 50% by weight of the amino resin. Outside of the above range, contamination resistance, weather resistance, water resistance, etc. are undesirably reduced.

The mixing ratio of the hydroxyl group-containing resin to the polyisocyanate compound is such that the ratio of hydroxyl group / isocyanate group is 0.1.
A range of 6 to 1.5 equivalents is preferred. Outside of the above range, contamination resistance, weather resistance, water resistance, etc. are undesirably reduced.

The curing catalyst used in the present invention can be used without any particular limitation as long as it is used as a curing catalyst for a reactive silyl group-containing compound.

Specific examples of the curing catalyst include organic tin compounds such as dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate and tin octylate; phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl Phosphates or phosphates such as phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, didecyl phosphate; propylene oxide, butylene oxide,
Cyclohexene oxide, glycidyl methacrylate, glycidol, acrylic glycidyl ether, γ-
Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, Cardura E manufactured by Yuka Shell Epoxy, Epicoat manufactured by Yuka Shell Epoxy 828, an addition reaction product of an epoxy compound such as Epikote 1001 with phosphoric acid and / or a monophosphate ester; an organic titanate compound; an organoaluminum compound; an organozinc compound;
Carboxylic acid compounds (organic carboxylic acid compounds) such as azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, phthalic acid, trimellitic acid and pyromellitic acid, and their acid anhydrides; dodecylbenzenesulfonic acid, paratoluene Sulfonic acid compounds (organic sulfonic acid compounds) such as sulfonic acid, 1-naphthalenesulfonic acid and 2-naphthalenesulfonic acid, and nitrogen compounds containing the sulfonic acid compounds (eg, 1-amino-2-propanol, monoethanolamine, diethanolamine) , 2- (methylamino) ethanol, 2-dimethylethanolamine, 2-
Amino-2-methyl-1-propanol, diisopropanolamine, 3-aminopropanol, 2-methylamino-2-methylpropanol, morpholine, oxazolidine, 4,4-dimethyloxazolidine, 3,4,4
-A reaction product of an acid and an amine (for example, NACURE 5225, NACURE 5543, NAC manufactured by KING INDUSTRIES)
URE5925); hexylamine, di-2-ethylhexylamine, N, N-dimethyldodecylamine,
Amines such as dodecylamine, DABCO, DBU, morpholine, diisopropanolamine; reactants of these amines with acidic phosphate esters; sodium hydroxide;
Examples include alkaline compounds such as potassium hydroxide. The curing catalysts may be used alone or in combination of two or more.

Among the above-mentioned curing catalysts, a sulfonic acid compound blocked with a nitrogen-containing compound is preferred because it has a good balance between curability at the time of baking and storage stability at room temperature. Further, the nitrogen-containing compound is a primary or secondary amine compound having one or more and two or less hydroxyl groups in one molecule (for example, 2-amino-2-methyl-1-propanol, diisopropanolamine, etc.); Preferably, it is one or more compounds of morpholine and oxazolidine. Specific examples of such a sulfonic acid compound blocked with a nitrogen-containing compound include, for example, NACURE5225 and NACURE5225 manufactured by King Industries.
ACURE5543, NACURE5925 and the like. Further, the preferred curing catalyst may be used in combination with the organotin compound, phosphoric acid or phosphoric ester.

The equivalent ratio of the sulfonic acid compound to the nitrogen-containing compound is preferably 0.75 to 3.0, more preferably 1.0 to 2.0.
More preferably, it is 0. If it is less than 0.75, the storage stability and the appearance at room temperature tend to deteriorate, and if it exceeds 3.0, the curability at the time of baking is inferior and the yellowing of the coating film becomes strong. There is a tendency.

The curing catalyst is used in an amount of 0.001 to 10 parts, preferably 0.05 to 10 parts, per 100 parts of the total solids of the component (A). The amount of curing catalyst used is 0.00
If the amount is less than 1 part, the curability is reduced, and if it exceeds 10 parts, the appearance of the coating film is reduced.

The weatherability can be further improved by adding a weatherability improver such as an ultraviolet absorber and a light stabilizer to the curable composition for a topcoat paint of the present invention. In particular, by using these together, the weather resistance can be further improved.

Examples of the ultraviolet absorber include benzophenone-based, triazole-based, phenyl salicylate-based, diphenylacrylate-based, and acetophenone-based ones. These may be used alone or in combination of two or more.

Examples of the light stabilizer include bis (2,2,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-).
Piperidyl) sebacate, 2- (3,5-di-tert)
Bis (1,2,2,6,6-pentamethyl-4) -butyl-4-hydroxybenzyl) -2-n-butylmalonate
-Piperidyl), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6)
6-pentamethyl-4-piperidyl) -1,2,3,4
-Butanetetracarboxylate and the like. These may be used alone or in combination of two or more.

The amount of the ultraviolet absorber used is usually 0.1 to 10 parts with respect to 100 parts of the resin solid content of the curable composition.
The amount is preferably in the range of 1 to 5 parts, and the light stabilizer is used in an amount of usually 0.1 to 10 parts, preferably 1 to 5 parts with respect to 100 parts of the resin solid content of the curable composition. It is.

Next, an example in which the curable composition of the present invention is applied will be described.

First, a paint containing at least one of a metallic powder, a mica powder and a coloring pigment (hereinafter referred to as a paint containing a metallic powder, etc.) is applied to the object to be coated. A top coat clear paint containing the curable composition of the present invention as a main component is applied.

The paint (base coat) containing the above-mentioned metallic powder and the like is not particularly limited. For example, amino alkyd resin, oil-free alkyd resin, thermosetting acrylic resin, thermosetting urethane resin, nitrified cotton lacquer, modified acrylic lacquer, slate Acrylic lacquer, room temperature-curable urethane resin, acrylic enamel resin, oxidation-curable alkyd resin, oxidation-cured modified (CAB etc.) alkyd resin, room-temperature or heat-curable fluororesin, hydrolyzable silyl group-containing resin, curable composition of the present invention And those containing a mixture of these as a main component, a metallic powder, a mica powder, a coloring pigment, and the like.

The paint containing the metallic powder and the like is as follows:
Any type of paint such as a solution paint, a non-aqueous dispersion paint, a multi-liquid paint, a powder paint, a slurry paint, and a water paint using an organic solvent as a medium may be used.

The metallic powder and the coloring pigment are not particularly limited, and those conventionally used can be used. Specific examples of the metallic powder include, for example, aluminum powder and copper powder, and specific examples of the coloring pigment include, for example, organic pigments such as phthalocyanine blue, toluidine red, and benzidine yellow,
Examples include inorganic pigments such as titanium oxide, carbon black, and red iron oxide. These metallic powder, mica powder and coloring pigment may be used alone or in combination of two or more.

When the above-mentioned ultraviolet absorber and light stabilizer are added to the base coat, the weather resistance of the coated product can be further improved.

Further, in order to improve the adhesion of the paint containing the metallic powder and the like to the top coat clear coat, aminoethylaminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane,
An aminosilane-based compound such as γ-aminopropyldimethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropyldiethoxysilane may be blended.

In this case, the amount of the silicon compound is usually 20 parts or less, preferably 10 parts or less and 0.5 parts or more based on 100 parts of the paint containing metallic powder and the like.

The coated product of the present invention is obtained by further applying a top coat clear coating on the coated surface to which the base coat has been applied. For example, a coating containing the above-mentioned metallic powder or the like is applied to the coated object for several minutes. After setting, apply a top coat clear paint by wet-on-wet method and heat and cure it. Alternatively, apply a paint containing metallic powder and heat and cure it, then apply a top coat clear paint. Can be manufactured by a method such as a two-coat two-bake method of applying and heating and curing.

The application of the top coat clear paint can be performed by various conventional methods such as dipping, spraying, brush coating, a method using a roll coater or a flow coater. Then, it can be cured by heating to 30 ° C. or higher, preferably 55 to 350 ° C.

[0111] The thickness of the coating film of the coating material cannot be specified unconditionally because it differs depending on the application, but the thickness of the coating film containing metallic powder or the like is 10 to 30 µm in view of concealability and the like.
Is preferable, and the thickness of the top coat clear coating film is preferably in the range of 20 to 50 μm from the viewpoint of durability and the like.

As described above, the curable composition for a solvent-based top coat of the present invention has excellent acid resistance, scratch resistance, appearance,
It exhibits thermosetting properties and extremely excellent stain resistance.For example, topcoats used for automobiles, industrial machinery, steel furniture, interior and exterior of buildings, home appliances, plastic products, etc., especially automotive topcoats It can be suitably used for paints and the like.

[0113]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Production Example 1 ( Production of Hydrolyzable Silyl Group-Containing Vinyl Resin (A-1)) 26 parts of xylene was placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel. After heating to 110 ° C. while introducing nitrogen gas,
A mixture consisting of 4.75 parts of 2,2'-azobisisobutyronitrile, 6 parts of toluene, and 6 parts of xylene having the composition and amount shown in Table 1 was dropped at a constant rate from the dropping funnel over 5 hours. .

After the addition of the mixture was completed, 0.25 parts of 2,2'-azobisisobutyronitrile and 10 parts of toluene were added to 1 part of the mixture.
The mixture was cooled at a constant rate over a period of time, polymerized for 2 hours, cooled, and further added with xylene to adjust the resin solids concentration to 60%, and the hydrolyzable silyl group-containing vinyl resin (A-1) was added. ) Got.

The number average molecular weight of the obtained resin (A-2) was determined.

Production Example 2 ( Production of Hydrolyzable Silyl / Hydroxy Group-Containing Vinyl Resin (A-2)) Solvents were placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel. After charging 26 parts of 100 (manufactured by Exxon Chemical Co., Ltd., petroleum aromatic solvent), the temperature was raised to 110 ° C. while introducing nitrogen gas,
4.75 parts of 2,2'-azobisisobutyronitrile copolymer component having the composition and amount shown in Table 1, Solvesso 100
A mixture consisting of 3.5 parts and 2 parts of methanol was dropped at a constant rate from the dropping funnel over 4 hours.

After the addition of the mixture was completed, 0.25 parts of 2,2'-azobisisobutyronitrile and 10 parts of xylene were added dropwise at a constant speed over 30 minutes, and polymerization was carried out for 1 hour and 30 minutes. 4 parts of methyl orthoacetate and 4 parts of methanol were added, and Solvesso 100 was further added to adjust the resin solids concentration to 60% to obtain a hydrolyzable silyl group- and hydroxyl group-containing vinyl resin (A-2). Was.

The number average molecular weight of the obtained resin (A-2) was determined. Further, based on the charged amount of the copolymer component, the hydrolyzable silyl group equivalent (g / mol) and the alcoholic hydroxyl group equivalent (g / mol) were used.
Mol) and the molar ratio of alcoholic hydroxyl group to hydrolyzable silyl group (alcoholic hydroxyl group / hydrolyzable silyl group). Table 1 shows the results.

Production Example 3 ( Production of Hydrolyzable Silyl Group / Epoxy Group-Containing Vinyl Resin (A-3)) A reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel was prepared. Solvesso 100 (produced by Exxon Chemical Co., Ltd., petroleum-based aromatic solvent) was charged with 26 parts and heated to 110 ° C. while introducing nitrogen gas.
4.75 parts of 2,2'-azobisisobutyronitrile copolymer component having the composition and amount shown in Table 1, Solvesso 100
A mixture consisting of 3.5 parts and 2 parts of methanol was dropped at a constant rate from the dropping funnel over 4 hours.

After completion of the dropwise addition of the mixture, 0.25 part of 2,2'-azobisisobutyronitrile and 10 parts of xylene were added dropwise at a constant speed over 30 minutes, and polymerization was carried out for 1 hour and 30 minutes, followed by cooling. 4 parts of methyl orthoacetate and 4 parts of methanol were added, and further, Solvesso 100 was added to adjust the resin solids concentration to 60%, and a vinyl resin containing a hydrolyzable silyl group, a hydroxyl group and an epoxy group (A-3) ) Got.

The number average molecular weight of the obtained resin (A-3) was determined. Further, a hydrolyzable silyl group equivalent (g / mol) and an epoxy equivalent (g / mol) were determined from the charged amounts of the copolymer components. Table 1 shows the results.

Production Example 4 (hydrolyzable silyl group / hydroxyl group
Production of Epoxy Group-Containing Vinyl Resin (A-4)) Solvesso 100 (manufactured by Exxon Chemical Co., Ltd., petroleum fragrance) was placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel. Group solvent) and heated to 110 ° C. while introducing nitrogen gas.
4.75 parts of 2,2'-azobisisobutyronitrile copolymer component having the composition and amount shown in Table 1, Solvesso 100
A mixture consisting of 3.5 parts and 2 parts of methanol was dropped at a constant rate from the dropping funnel over 4 hours.

After the addition of the mixture was completed, 0.25 parts of 2,2'-azobisisobutyronitrile and 10 parts of xylene were added dropwise at a constant speed over 30 minutes, and polymerization was carried out for 1 hour and 30 minutes. 4 parts of methyl orthoacetate and 4 parts of methanol were added, and further, Solvesso 100 was added to adjust the resin solid content to 60%, and a vinyl resin containing a hydrolyzable silyl group, a hydroxyl group and an epoxy group (A-4 ) Got.

The number average molecular weight of the obtained resin (A-4) was determined. Further, based on the charged amount of the copolymer component, the hydrolyzable silyl group equivalent (g / mol) and the alcoholic hydroxyl group equivalent (g / mol) were used.
Mol) The epoxy equivalent (g / mol) and the molar ratio of alcoholic hydroxyl groups to hydrolyzable silyl groups (alcoholic hydroxyl groups / hydrolyzable silyl groups) were determined. Table 1 shows the results.

Production Example 5 ( Production of Epoxy Group-Containing Vinyl Resin (A-5)) Solvesso 100 17 was placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel.
, 10 parts of n-butanol, and the temperature was raised to 110 ° C. while introducing nitrogen gas. Then, 5.7 parts of a copolymer component having the composition and amount shown in Table 1, 5.7 parts of Kayaester O, 13 parts of Solvesso 100, A mixture consisting of 6 parts of n-butanol was dropped at a constant speed from the dropping funnel over 4 hours.

After the completion of the dropping of the mixture, the Kayaester O
0.3 parts, 10 parts of xylene were dropped at a constant speed over 30 minutes,
After polymerization for 1 hour and 30 minutes, the mixture was cooled, and Solvesso 100 was further added to adjust the resin solids concentration to 60% to obtain an epoxy group-containing vinyl resin (A-5).

The number average molecular weight of the obtained resin (A-5) was determined. Further, the epoxy equivalent (g / mol) was determined from the charged amount of the copolymer component. Table 1 shows the results.

Production Example 6 (Hydroxy group-containing vinyl resin (A-
6) Production) Solvesso 100 16 in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel.
And 10 parts of n-butanol, and the temperature was raised to 110 ° C. while introducing nitrogen gas. Then, the copolymerization component and 2,2′-azobisisobutyronitrile having the composition and amount shown in Table 1 were used. A mixture consisting of 75 parts and 10 parts of Solvesso 100 was dropped at a constant speed from the dropping funnel over 5 hours.

After the addition of the mixture was completed, 0.25 parts of 2,2'-azobisisobutyronitrile and 10 parts of xylene were added dropwise at a constant rate over 1 hour, polymerization was carried out for 2 hours, followed by cooling, and 100 was added to adjust the resin solids concentration to 60% to obtain a hydroxyl group-containing vinyl resin (A-6).

The number average molecular weight of the obtained resin (A-6) was determined. The alcoholic hydroxyl group equivalent (g / mol) was determined from the charged amount of the copolymer component. Table 1 shows the results.

Production Example 7 ( Production of Fluororesin (A-7)) Solvesso 100 16 was placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel.
And 10 parts of n-butanol, and the temperature was raised to 110 ° C. while introducing nitrogen gas. Then, the copolymerization component and 2,2′-azobisisobutyronitrile having the composition and amount shown in Table 1 were used. A mixture consisting of 75 parts and 10 parts of Solvesso 100 was dropped at a constant speed from the dropping funnel over 5 hours.

After the addition of the mixture was completed, 0.25 parts of 2,2'-azobisisobutyronitrile and 10 parts of xylene were added dropwise at a constant speed over 1 hour, polymerization was carried out for 2 hours, followed by cooling, and further, 100 was added to adjust the resin solids concentration to 60% to obtain a fluororesin (A-7).

The number average molecular weight of the obtained resin (A-7) was determined. The alcoholic hydroxyl group equivalent (g / mol) was determined from the charged amount of the copolymer component. Table 1 shows the results.

Production Example 8 (Amino group-containing vinyl resin (A
Production of -8)) Solvesso 100 26 in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel.
After the temperature was raised to 110 ° C. while introducing nitrogen gas, the copolymer components and 2,2 ′ having the composition and amount shown in Table 1 were obtained.
-A mixture of 4.75 parts of azobisisobutyronitrile and 10 parts of Solvesso 100 was dropped at a constant speed from the dropping funnel over 5 hours.

After the addition of the mixture was completed, 0.25 part of 2,2'-azobisisobutyronitrile and 10 parts of xylene were added dropwise at a constant speed over 1 hour, polymerization was carried out for 2 hours, followed by cooling, and 100 was added to adjust the resin solids concentration to 60% to obtain an amino group-containing vinyl resin (A-8).

The number average molecular weight of the obtained resin (A-8) was determined.

Production Example 9 ( Production of Carboxyl Group-Containing Vinyl Resin (A-9)) Solvesso 100 26 was placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel.
After the temperature was raised to 110 ° C. while introducing nitrogen gas, the copolymer components and 2,2 ′ having the composition and amount shown in Table 1 were obtained.
-A mixture of 4.75 parts of azobisisobutyronitrile and 10 parts of Solvesso 100 was dropped at a constant speed from the dropping funnel over 5 hours.

After the addition of the mixture was completed, 0.25 parts of 2,2'-azobisisobutyronitrile and 10 parts of xylene were added dropwise at a constant speed over 1 hour, polymerization was carried out for 2 hours, followed by cooling, and furthermore, Solvesso 100 was added to adjust the resin solids concentration to 60% to obtain a carboxyl group-containing vinyl resin (A-9).

The number average molecular weight of the obtained resin (A-9) was determined.

Production Example 10 ( Production of Carboxyl Group / Carboxylic Acid Ester Group-Containing Vinyl Resin (A-10)) Solvesso was placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel. 100 26
After the temperature was raised to 110 ° C. while introducing nitrogen gas, 5.7 parts of a copolymer component having the composition and amount shown in Table 1, 5.7 parts of Kayaester O, 30 parts of 1-methoxy-2-acetoxypropane, A mixture consisting of 10 parts of xylene was dropped at a constant speed from the dropping funnel over 4 hours.

After completion of the dropwise addition of the mixture, Kayaester O
0.3 parts, 10 parts of xylene were dropped at a constant speed over 30 minutes,
After polymerization for 1 hour and 30 minutes, the mixture was cooled, and Solvesso 100 was further added to adjust the resin solids concentration to 50% to obtain a vinyl resin having an acid anhydride group.

The polymer 10 obtained in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was added.
A mixture consisting of 0 parts, 4 parts of methanol, 8 parts of butyl acetate and 0.5 part of triethylamine was reacted at 60 ° C. for 6 hours, and the absorption of acid anhydride groups by infrared absorption spectrum (1,
785 cm ^-1 ) disappeared, and a polymer containing a carboxyl group and a carboxylic acid ester group was obtained.

The number average molecular weight of the obtained resin (A-10) was determined.

Production Example 11 ( Production of Hydroxyl Group-Containing Nonaqueous Dispersion Polymer (A-11)) Using the raw materials shown in Table 2 in the proportions shown in Table 2, the hydroxyl group containing nonaqueous dispersion polymer (B) was prepared as follows. Manufactured.

First, the raw material (1) was charged into a reaction vessel and heated to a reflux temperature (97 ° C.). Then, the raw material (2) was added, and immediately the raw material (3) and the raw material (4) were
After a constant addition over 25 minutes, it was kept at its reflux temperature for 30 minutes. The reaction mixture was initially clear but soon became light blue after the addition of raw materials (3) and (4) and became cloudy white after 40 minutes.

Thereafter, the raw material (5) was added at a constant speed over a period of 30 minutes, and further kept at the reflux temperature for 90 minutes.

Finally, the excess solvent was removed, and the solid content was reduced to 6%.
A stable dispersion having a cloudiness of 3.4% but no layer separation was obtained.

The resulting polymer has a Stormer viscosity of 7
At 6 KU, the average particle size was 300 nm.

The “solution comprising an organic solvent-soluble polymer” in the raw material (1) is obtained by synthesizing the monomers described in parentheses in the solvent described in parentheses. This polymer forms the arm part (2).

Further, methacrylic acid, 2-
Hydroxyethyl acrylate, methyl methacrylate,
A polymer of methyl acrylate, styrene and glycidyl methacrylate forms the core part (1).

Production Example 12 ( Production of vinyl resin (A-12) using light-stable monomer and ultraviolet absorber) Same as Production Example 3 except that the composition was changed as shown in Table 1. The operation was performed to obtain a vinyl resin.

The number average molecular weight of the obtained resin (A-12) was determined.

[0154]

[Table 1] .

The abbreviations and trade names in Table 1 indicate the following. (The same applies to other tables.) ST: Styrene A174: γ-methacryloxypropyltrimethoxysilane Nippon Unicar Co., Ltd. 2EMA: 2-ethylhexyl acrylate BMA: butyl methacrylate MMA: methyl methacrylate BA: butyl acrylate GMA: glycidyl Methacrylate CHMA: cyclohexyl methacrylate IBMA: isobutyl methacrylate HEMA: 2-hydroxyethyl methacrylate AM: acrylamide AA: acrylic acid MAn: maleic anhydride DAEMA: dimethylaminoethyl methacrylate Uniox PKA5004: polyethylene glycol monoallyl ether (average molecular weight 750) Blemmer AE-350: Polyethylene glycol monoacryle BEMMER PME400: Methoxy polyethylene glycol monomethacrylate manufactured by NOF Corporation.

[0156]

[Table 2] .

Comparative Production Example 1 A vinyl resin was obtained in the same manner as in Production Example 2, except that the composition was changed as shown in Table 3.

Comparative Production Example 2 A vinyl resin was obtained in the same manner as in Production Example 5, except that the composition was changed as shown in Table 3.

Comparative Production Example 3 The same operation as in Production Example 7 was carried out except that the composition was changed as shown in Table 3, to obtain a fluororesin.

[0160]

[Table 3] .

Production Example 13 ( Production of carboxylic acid oligomer) A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel was placed in a reaction vessel shown in Table 4 below.
After stirring at 120 ° C. for 15 minutes while introducing nitrogen gas, Portion 2 was added over 15 minutes.

Thereafter, the reaction was carried out at 120 ° C. for 3 hours. I
It was confirmed that the absorption of the acid anhydride group (1,785 cm ^-1 ) disappeared at R.

[0163]

[Table 4] .

Examples 1 to 10 and Comparative Examples 1 to 5 Polymers or compounds shown in Tables 1 to 3 were blended at the solid content ratios shown in Tables 5 and 6.

A leveling agent (Dispalon L-1984-50, manufactured by Kusumoto Kasei Co., Ltd.) 0.4% with respect to the total resin solid content of each Example or Comparative Example, and Tinuvin 384 (manufactured by Ciba Geigy) as an ultraviolet absorber 2 %, And 1% of Tinuvin 123 (manufactured by Ciba-Geigy) as a light stabilizer. Thereafter, the mixture was diluted with Solvesso 100 and adjusted so that the viscosity with a Ford cup (FC # 4) was about 22 seconds to produce a clear coating material for a top coat.

The thermosetting properties of the obtained clear coating for top coat were evaluated according to the following method. In addition, the appearance of the coating film, the contact angle to water, the brightness, and the weather resistance were evaluated. The results are shown in Tables 5 and 6.

[Preparation of Coating Film] (Examples 1 to 3) A coated plate obtained by coating a degreased and phosphorylated chemical-treated steel plate with an epoxyamide-based cationic electrodeposition primer for automobiles and an intermediate coating surfacer was used as a test piece. An acrylic urethane resin paint (white) was applied as a base coat on the surface. After setting for 20 minutes, the clear coating for top coat was applied wet-on-wet, and after setting for 20 minutes, baking was performed at 70 ° C. for 30 minutes to form a coating film.

The dry film thickness of the obtained coating film was about 15 μm for the base coat and about 30 to 40 μm for the top coat clear.
m.

(Examples 4 to 10 and Comparative Examples 1 to 5) A coated plate obtained by coating a degreased and phosphorylated chemical-treated steel plate with an epoxyamide-based cationic electrodeposition primer for automobiles and an intermediately coated surfacer was used as a test piece. An acrylic melamine resin paint (white) was applied as a base coat on the surface. After setting for 5 to 10 minutes, apply the clear paint for top coat
The coating was performed on-wet, set for 10 minutes, and baked at 140 ° C. for 30 minutes to form a coating film.

The dry film thickness of the obtained coating film was about 15 μm for the base coat and about 30 to 40 μm for the top coat clear.
m.

[Appearance] The gloss and sharpness were visually evaluated comprehensively.

○ indicates good, and △ indicates slightly poor.

[Contact Angle to Water] After leaving the obtained coating film at room temperature for 7 days, using a Kyowa Interface Science Model CA-S150, a water droplet of about 0.03 ml of ion-exchanged water was dropped on the coating film surface. Then, the static contact angle after 3 minutes at 23 ° C. was measured.

[Lightness] The lightness expressed in the L * a * b * color system at the initial stage of exposure was measured using a colorimeter (CR-300 manufactured by Minolta).
The outdoor exposure of 30 degrees south side was carried out in Settsu City, Osaka Prefecture for 3 months. L * a * b * after exposure was measured, and the difference in lightness (ΔL * value) before and after exposure was used as a measure of contamination. In addition, a smaller value indicates that the sample is contaminated (a larger value indicates that the stain resistance is superior).

[Weather Resistance] Evaluation is performed using a sunshine carbon arc lamp type weather resistance tester (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K 5400.

Test conditions: Black panel temperature 63 ± 3
After 1,500 hours of rain at 18 ° C. for 18 minutes out of 120 minutes, the evaluation was made visually as follows.

○: No abnormality, ×: Decrease in gloss and adhesion of water marks are clearly observed.

[0178]

[Table 5] .

[0179]

[Table 6] .

From the results shown in Tables 5 and 6, all of the coating films formed using the coating materials obtained in Examples 1 to 10 were excellent in appearance and weather resistance, and at the same time, were excellent in stain resistance. It turns out that it is very excellent.

[0181]

The curable composition for a solvent-based top coat according to any one of claims 1 to 8 exhibits excellent thermosetting properties, and the formed coating film has excellent appearance and weather resistance and is extremely excellent. It is suitable for use as, for example, an overcoat used in automobiles, industrial machines, steel furniture, interior and exterior of buildings, home appliances, plastic products, and the like.

Further, the coated product obtained by applying the curable composition for a solvent-based top coat according to the ninth aspect has excellent characteristics as described above.

Claims (9)

[Claims] 1. A resin comprising a single resin or a mixture of two or more resins, of which at least one resin is based on 100 parts by weight of a base resin containing a polyoxyalkylene group, A curable composition for a solvent-based topcoat paint, comprising 0 to 200 parts by weight of a silicon compound represented by the general formula (I) and / or a partial hydrolyzed condensate thereof. Embedded image (In the formula (I), R ¹ and R ^{2 each} represent a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group having 1 to 10 carbon atoms, and may be the same or different. In many cases, b represents an integer of 0 to 3.) 2. The resin having a polyoxyalkylene group as the component (A), which contains a monovalent organic group represented by the following general formula (II). 2. The curable composition for a solvent-based topcoat paint according to 1. Embedded image (In Formula (II), R ³ and R ⁴ each represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, which may be the same or different, and R ⁵ is a hydroxyl group or 1 to 4 carbon atoms.
4 alkoxy groups, p is an integer of 2 to 4, q is 1 to 200
Are respectively shown. ) 3. The resin containing a polyoxyalkylene group as the component (A) is obtained by copolymerizing 1 to 30% by weight of a compound containing a monovalent organic group represented by the formula (II). The curable composition for a solvent-based topcoat paint according to claim 2, wherein the curable composition is a solvent-based topcoat paint. 4. The resin containing a polyoxyalkylene group as the component (A), wherein the resin is any one of a hydrolyzable silyl group, a hydroxyl group (excluding a polyoxyalkylene group), an epoxy group, a carboxyl group and an amino group. The curable composition for a solvent-based topcoat paint according to any one of claims 1 to 3, comprising the above. 5. The method according to claim 1, wherein the resin containing a polyoxyalkylene group as the component (A) is an acrylic and / or fluorine copolymer. The curable composition for a solvent-based topcoat paint according to the above. 6. The resin containing a polyoxyalkylene group as the component (A) is an acrylic and / or fluorine copolymer obtained by copolymerizing a light-stable monomer and an ultraviolet-absorbing monomer. The curable composition for a solvent-based topcoat paint according to any one of claims 1 to 5, wherein 7. The curable composition for a solvent-based topcoat coating according to claim 1, further comprising an amino resin or an isocyanate compound. 8. The solvent according to claim 1, wherein the component (B) is a partially hydrolyzed condensate of a tetraalkyl silicate, and is a complex of two or more kinds. Curable composition for system topcoat paint. 9. A coated product obtained by applying a top coat clear paint to a coating surface on which a paint containing at least one of a metallic powder, a mica powder and a color pigment is applied, wherein the top coat clear paint is applied. Are claims 1 to 8
A coated article comprising, as a main component, the curable composition for a solvent-based top coating composition according to any one of the above.