JPH09278982A - Curable resin composition and coating film forming method using the same - Google Patents

Abstract

(57) [Summary] (Correction) [Problem] Thermosetting resin composition for paints, which has extremely high practicality, such as excellent yellowing resistance to heat, excellent storage stability, and good workability. I will provide a. A vinyl-based polymer having a carbonate group, a polysiloxane having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, and a curing catalyst are contained as minimum essential components. Alternatively, the above vinyl-based polymer, a polysiloxane having a silicon atom-bonded hydroxyl group and / or a silicon atom-bonded hydrolyzable group, a curing catalyst, and a carboxyl group-containing compound capable of reacting with a carbonate group, A thermosetting resin composition in which a compound having a carbon-bonded hydroxyl group, and further, an amino resin, a polyisocyanate and a blocked polyisocyanate as a curing agent capable of reacting with the hydroxyl group, can be appropriately combined.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful curable resin composition and a method for forming a coating film using the curable resin composition. More specifically, the present invention provides, as an essential component, a vinyl polymer (A) having a specific group, which is a vinyl polymer (A) containing a carbonate group, and a hydroxyl group and / or silicon bonded to a silicon atom. An extremely highly practical curable resin composition comprising a polysiloxane (B) having a hydrolyzable group bonded to an atom and a curing catalyst (C), which is particularly excellent in maintaining the appearance of a coating film for a long period of time. And a method for forming a coating film.

Further, a compound having a carboxyl group and / or a hydroxyl group bonded to a carbon atom, and further various curing agents such as amino resin, polyisocyanate or blocked polyisocyanate are appropriately combined. It is also extremely useful for heat-curing, which gives a cured product with excellent acid resistance, scratch resistance (scratch resistance) and water repellency maintenance, and excellent appearance such as smoothness. And a method for forming a so-called multi-layer coating film, which comprises using the resin composition.

[0003]

2. Description of the Related Art In recent years, mainly in the automobile industry, there is a movement to attach importance to the appearance of a coating film. That is, the finished appearance immediately after coating, the appearance maintained under long-term exposure, and the appearance maintained due to reduction of scratches (scratch resistance) when using a car wash machine.

However, under long-term exposure, the deterioration due to acid rain deteriorates the appearance, and the water repellency also deteriorates, which accelerates the damage to the appearance. become.

Further, in the case of a car to which a dark-colored paint is applied, the marks of scratches caused by car washing are particularly noticeable, and the quality is impaired.

[0006] In order to solve these problems, the above-mentioned various performances can be satisfied and satisfied as long as the current paint system in which an aminoplast-based curing agent is combined with an acrylic polyol is used. I can't do anything.

In such a movement, a curing system by a combination of a polyol type resin and an isocyanate prepolymer; a curing system by a combination system of a silanol group containing resin and an epoxy group containing resin; trialkoxysilyl Moisture curing system based on groups; or hydroxyl-containing resin,
Various kinds of coating materials such as a curing system by combination with an acid anhydride group-containing resin are gradually studied and developed.

However, among these paint systems, the polyol type resin / isocyanate prepolymer system has a short pot life and has a major drawback in terms of workability.

In addition, the curing system of the silanol group-containing resin and the epoxy group-containing resin, the moisture curing system of the trialkoxysilyl group, and the like cause a difference in curability depending on the coating conditions and baking conditions, resulting in an appearance. Again, it's not about satisfaction.

In addition, each of these curable coating materials has a fatal defect that the coating film is often scratched during car washing, resulting in a marked deterioration of the coating film appearance. is there.

[0011]

SUMMARY OF THE INVENTION However, the present inventors intend to solve or solve various drawbacks or problems in the conventional techniques as described above, and, in addition, to meet the above-mentioned needs. The research was earnestly started.

[0012] Therefore, the problem to be solved by the invention of the present invention is, in particular, excellent in heat-resistant yellowing, and is also excellent in storage stability as a one-pack type coating. It is to provide a thermosetting resin composition having extremely high practicality such that workability is also good,

In addition, by carrying out a method for forming a coating film using such a useful thermosetting resin composition,
In particular, it is a highly practical and innovative coating formation that gives a coating excellent in heat yellowing resistance, acid resistance, weather resistance, scratch resistance, and the appearance of the coating film, and especially excellent in smoothness. To provide a way too.

[0014]

Means for Solving the Problems Accordingly, the present inventors have:
Focusing on the problems to be solved by the invention as described above, as a result of intensive studies, as a result, a vinyl polymer having a specific group, which is a carbonate group, and a hydroxyl group and / or silicon bonded to a silicon atom. By using a novel thermosetting resin composition composed of a polysiloxane having a hydrolyzable group bonded to an atom and a curing catalyst, it is particularly excellent in maintaining the appearance of the coating film for a long period of time. The present invention has been completed here by establishing a desired curable resin composition having extremely high practicality and a method for forming a coating film.

That is, according to the present invention, basically, a vinyl polymer (A) having a carbonate group, a hydroxyl group bonded to a silicon atom, and /
Or a polysiloxane (B) having a hydrolyzable group bonded to a silicon atom and a curing catalyst (C),

Alternatively, the carbonate group-containing vinyl polymer (A), the compound (D) containing a carboxyl group and / or a hydroxyl group bonded to a carbon atom, and the silicon atom-bonded hydroxyl group and / or silicon atom described above. The present invention aims to provide a thermosetting resin composition comprising a polysiloxane (B) having a bondable hydrolyzable group and a curing catalyst (C), and the resin composition.

Further, a compound having a carboxyl group and / or a hydroxyl group bonded to a carbon atom and a curing agent such as an amino resin, polyisocyanate and blocked polyisocyanate can be appropriately combined. Curable resin that has excellent acid resistance and water repellency maintenance, excellent scratch resistance (scratch resistance) and smoothness, and has a good balance between low temperature curability and storage stability. Is intended to provide a composition,

In addition, by using various thermosetting resin compositions having the above-mentioned shape as a clear coat, a two-coat one-bake system or a two-coat two-bake system is used. The present invention also intends to provide a new and extremely practical coating finishing method of forming a multilayer coating film by a coating method or an overcoat method.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below.

Only the typical vinyl polymer (A) having a carbonate group, which is one of the essential constituents of the curable resin composition according to the present invention, is exemplified below. Various vinyl polymers such as acrylic polymers, fluoroolefin polymers, vinyl ester polymers, aromatic vinyl polymers and the like.

The carbonate groups present in the vinyl polymer (A) include linear carbonate groups and
Cyclic carbonate groups are mentioned, and among the latter cyclic carbonate groups, particularly desirable ones include those having a 5-membered ring structure and those having a 6-membered ring structure.

To prepare this vinyl-based polymer of the vinyl-based polymer (A) having a carbonate group, at least one polymerizable unsaturated double bond and at least one polymerizable unsaturated double bond in the molecule are prepared. A compound having a carbonate group in combination, and may be obtained by copolymerization with another polymerizable unsaturated monomer,

Alternatively, in the hydroxyl group-containing vinyl polymer,
After adding various isocyanate compounds such as hexamethylene diisocyanate, etc., further adding carbonate monoalcohols such as glyceryl carbonate,

Further, it may be obtained by adding the above-mentioned carbonate monoalcohols to various isocyanate group-containing polymers such as isocyanate ethyl methacrylate copolymer. Good,

Further, it may be obtained by adding the above-mentioned carbonate monoalcohol to the acid chloride group-containing polymer, but one polymer in the molecule is preferable. A compound having both an unsaturated double bond and at least one carbonate group,

That is, it is easier and simpler to copolymerize the carbonate group-containing polymerizable unsaturated monomer with the compound having one polymerizable unsaturated double bond in one molecule. Recommended.

At least one polymerizable unsaturated double bond and a linear group each in one molecule, which can be used in the preparation of the vinyl polymer (A) according to various methods as described above, are used. As a typical example of the compound having a carbonate group, only compounds represented by the following general formula [I]

[0028]

Embedded image

(In the formula, R ¹ is hydrogen or a methyl group, and R ² and R ³ are the same or different alkylene chains having 2 to 8 carbon atoms, (R ⁴ represents a primary alcohol residue having up to 20 carbon atoms, m is 0 or an integer of 1 to 6, and n is an integer of 1 to 100.)

Examples of the acrylic monomer are compounds represented by the formula (1), which can be synthesized by the production method disclosed in JP-A-7-300444.

Concretely, the following various general formulas [I-1] to [I-8] are sequentially described.

[0032]

Embedded image

(However, n in the formula means the number of repeating units and is an arbitrary number within the range of 0.5 to 20.)

[0034]

Embedded image

(However, n in the formula means the number of repeating units and is an arbitrary number within the range of 0.5 to 20.)

[0036]

Embedded image

(However, n in the formula means the number of repeating units, and is an arbitrary number within the range of 0.5 to 20.)

[0038]

Embedded image

(However, n in the formula means the number of repeating units and is an arbitrary number within the range of 0.5 to 20.)

[0040]

[Chemical 6]

(However, n in the formula means the number of repeating units and is an arbitrary number within the range of 0.5 to 20.)

[0042]

Embedded image

(However, n in the formula means the number of repeating units, and is an arbitrary number within the range of 0.5 to 20.)

[0044]

Embedded image

(However, n in the formula means the number of repeating units and is an arbitrary number within the range of 0.5 to 20.)

[0046]

Embedded image

(However, n in the formula means the number of repeating units and is an arbitrary number within the range of 0.5 to 20.)

Various vinyl-based compounds represented by
Various compounds and the like.

Further, one polymerizable unsaturated double bond and at least one cyclic carbonate in one molecule, which can be used in the preparation of the vinyl polymer (A) according to the above-mentioned method, are used. Among the compounds having a group, especially,
To exemplify only typical compounds having a 6-membered ring carbonate group,

5-Ethyl-5- (meth) acryloyloxymethyl-1,3-dioxan-2-one, 4- (5
-Ethyl-2-oxo-1,3-dioxan-5-ylmethoxymethyl) styrene, 5- [N- (2-methacryloyloxy) ethylcarbamoyloxymethyl]-
5-ethyl-1,3-dioxan-2-one or 5-
(N-methacryloylcarbamoyloxy) methyl-
5-ethyl-1,3-dioxan-2-one and the like.

Further, only the representative compounds having one polymerizable unsaturated double bond and at least one 5-membered carbonate group in one molecule will be exemplified below. General formula [II]

[0052]

Embedded image

(However, in the formula, R ⁵ , R ⁶ and R ⁷
Are hydrogen atoms or an alkyl group having 4 or less carbon atoms, which may be the same or different, and R ⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. And p is an integer of 1 to 6. )

It is a vinyl compound represented by the so-called (meth) acrylate monomer.

Specifically, 2,3-carbonate propyl (meth) acrylate, 2-methyl-2,3-carbonate propyl (meth) acrylate, 4-methyl-
3,4-carbonate butyl (meth) acrylate, 3
Various (meth) acrylate systems such as methyl-3,4-carbonate butyl (meth) acrylate, 5-ethyl-5,6-carbonate hexyl (meth) acrylate or 7,8-carbonate octyl (meth) acrylate;

Alternatively, there are various vinyl-based compounds such as 2,3-carbonate propyl vinyl ether, methyl-2,3-carbonate propyl malate and 2,3-carbonate propyl crotonate.

Furthermore, in preparing the carbonate group-containing vinyl polymer (A), only other typical vinyl monomer copolymerizable with the unsaturated monomer having a carbonate group is used. To mention just a few, reactive polar groups such as 2-ethoxyethyl (meth) acrylate or cyclohexyl (meth) acrylate, including alkyl (meth) acrylates having an alkyl group having 1 to 22 carbon atoms. Various (meth) acrylates including;

Styrene, tert-butylstyrene, α
Various aromatic vinyl monomers such as methylstyrene or vinyltoluene; or various (meth) acrylamides such as (meth) acrylamide or N-alkoxymethylated (meth) acrylamide;

Alternatively, various fluorine-containing vinyl monomers such as tetrafluoroethylene or chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, etc., and further, various kinds of methacrylic acid typified by (meth) acrylonitrile can be used. Cyano group-containing vinyl monomers; various vinyl esters represented by vinyl acetate; or various phosphoric acid group-containing (meth) acrylates.

In the carbonate group-containing vinyl polymer (A), for example, a carboxyl group and / or a hydroxyl group bonded to a carbon atom may be introduced as a functional group that reacts with the carbonate group. I can.

In order to introduce a carboxyl group when preparing the vinyl polymer (A) having such a carboxyl group and / or a hydroxyl group bonded to a carbon atom, a carboxyl group-containing monomer is copolymerized. The simplest way is to do so.

As only specific examples of such carboxyl group-containing monomers, various α, β-ethylenic monomers such as (meth) acrylic acid, maleic acid, fumaric acid or itaconic acid can be given. Unsaturated mono- or dicarboxylic acids; various half-esterified products of various α, β-ethylenically unsaturated dibasic acids such as maleic acid, fumaric acid or itaconic acid, and monohydric alcohols having 1 to 4 carbon atoms Or various compounds obtained by adding various hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl (meth) acrylate and various acid anhydrides such as phthalic anhydride. is there.

Also, a vinyl polymer (A) having a carboxyl group and / or a hydroxyl group bonded to a carbon atom.
The most convenient way to introduce the hydroxyl group in the preparation is to copolymerize the hydroxyl group-containing monomers.

As the hydroxyl group-containing unsaturated group-containing monomers used at that time, only typical ones are exemplified, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth). Acrylate or 3-hydroxypropyl (meth) acrylate, 4
Various hydroxyalkyl (meth) acrylates, such as hydroxybutyl (meth) acrylate;

Various hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether or 4-hydroxyalkyl vinyl ether; or allyl compounds such as allyl alcohol or 2-hydroxyethyl allyl ether; or various such as listed above. And a compound obtained by adding ε-caprolactone to the hydroxyl group-containing monomer.

Further, a vinyl polymer (A) having a carboxyl group and / or a hydroxyl group bonded to a carbon atom.
In order to introduce both a carboxyl group and a hydroxyl group in the preparation of the above, as described above, a carboxyl group-containing monomer and a hydroxyl group-containing monomer are used in combination, and so on. do it.

To prepare the vinyl copolymer (A) using various monomers as listed above, any of known and commonly used methods such as solution polymerization method and non-aqueous dispersion polymerization method can be used. Although the polymerization method can be applied, the solution radical polymerization method is
It could be recommended as it is the most convenient.

Here, if it is intended to exemplify only typical solvents as the solvents used in preparing the vinyl copolymer (A) by the solution radical polymerization method, white. Mixtures of various hydrocarbons themselves, such as spirits or mineral spirits, as well as various aliphatic or fatty compounds such as hexane, heptane, octane, cyclohexane, cyclopentane or cyclooctane. Cyclic hydrocarbons;

Various aromatic hydrocarbons such as toluene, xylene or ethylbenzene; various kinds such as ethyl acetate, butyl acetate or amyl acetate, ethylene glycol monomethyl ether acetate or ethylene glycol monoethyl ether acetate or ethylene glycol monobutyl ether acetate Esters of methanol; ethanol, n-propanol, i-
Propanol, n-butanol, i-butanol, se
c-butanol, tert-butanol, n-amyl alcohol, i-amyl alcohol or tert-amyl alcohol

Or various alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or ethylene glycol monobutyl ether; various ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone; or dimethoxy Various ethers such as ethane, tetrahydrofuran, dioxane, diisopropyl ether or di-n-butyl ether;

Or various chlorinated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, trichloroethane or tetrachloroethane;
Of course, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene carbonate and the like can be used alone or in combination of two or more kinds.

As the polymerization initiator that can be used when the solution radical polymerization method is applied, various known and commonly used compounds can be used, of which only typical ones are exemplified. If it is limited to 2,2'-azobis (isobutyronitrile),
Various azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile) or 2,2′-azobis (2-methylbutyronitrile);

Or tert-butyl peroxypivalate, tert-butyl peroxybenzoate, t
ert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-
-Various peroxides such as butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide or diisopropyl peroxycarbonate.

The amount of the carbonate group to be introduced into the vinyl polymer (A) thus prepared is about 0.0 per 1000 g of the solid content of the polymer (A).
Within the range of 5 mol to about 4 mol, preferably 0.27
A suitable range is from mol to 2.5 mol.

When the amount is less than about 0.05 mol, the curability is inferior, and the effects such as scratch resistance cannot easily be expected. On the other hand, when the amount is more than about 4 mol and the amount is too much, The remaining carbonate groups tend to form a hard and brittle coating film, which is not preferable in any case.

When the carboxyl group is also introduced into the vinyl polymer (A), the amount of the carboxyl group is about 10 mgKOH / g (solid content) depending on the acid value.
Within the range of about 200 mgKOH / g (solid content), preferably 20 mgKOH / g (solid content) to 150 mgK
The range of OH / g (solid content) is suitable.

When the amount is less than about 10 mgKOH / g (solid content), it is unavoidable that further improvement in curability, which is an effect of the carboxyl group, cannot be expected, while about 200 mgKOH / g (solid content). If it becomes too high, the paint viscosity tends to increase,
Further, the workability is deteriorated, which is not preferable in any case.

On the other hand, the amount of the hydroxyl group when introducing the hydroxyl group into the polymer (A) is about 5 in terms of the hydroxyl value.
mgKOH / g (solid content) to about 200 mgKOH / g
The range of (solid content) is preferably 10 to 150 m.
The range of gKOH / g is suitable.

When the amount exceeds about 200 mgKOH / g (solid content) and becomes too large, it is inevitable that one of the most promising effects of the present invention, that is, the deterioration of the acid resistance of the coating film becomes remarkable. On the other hand, about 5m
If it is less than gKOH / g (solid content),
In any case, it is difficult to obtain the effect of further improving the curability by introducing the hydroxyl group, which is not preferable.

The vinyl polymer (A) thus obtained
The number average molecular weight of is within the range of about 800 to about 50,000, more preferably 1,000 to 30,0.
A range of 00 is suitable.

When it is less than about 800, it becomes inevitable that it is difficult to obtain a product having desired performance, while when it exceeds about 50,000 and becomes too high, workability is inevitable. In any case, it is not preferable because it is likely to adversely affect the above.

Next, the compound (D) having a carboxyl group and / or a hydroxyl group bonded to a carbon atom, which is used when preparing the composition of the present invention, will be described. Examples of such a compound (D) include various polymers in addition to the low molecular weight compound.

First, as the low molecular weight compound, a low molecular weight polycarboxylic acid, a low molecular weight polyol, a low molecular weight hydroxy acid or the like can be mentioned.

As the low molecular weight polycarboxylic acids, only typical ones are exemplified, such as 1,1-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. , Various alicyclic carboxylic acids;

Various aromatic carboxylic acids such as isophthalic acid, terephthalic acid or trimellitic acid; various aliphatic carboxylic acids such as adipic acid, azelaic acid or sebacic acid; or maleic acid, fumaric acid, itaconic acid And various unsaturated dibasic acids.

Further, only the representative examples of the above-mentioned low molecular weight polyols are exemplified, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-
Hexamethylene glycol, diethylene glycol or dipropylene glycol,

Examples are neopentyl glycol, triethylene glycol, cyclohexanedimethanol, hydrogenated bisphenol A, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol or sorbitol.

Further, only by exemplifying the typical examples of the above-mentioned low molecular weight hydroxy acid,
Various monobasic oxyacids such as glycolic acid, lactic acid, 3-hydroxypropionic acid, glyceric acid, tropic acid, benzylic acid or β-oxyacid; or various such as tartronic acid, malic acid, tartaric acid or citric acid Dibasic oxyacids;

On the other hand, among the above-mentioned compounds (D), only typical polymers are exemplified, and an acrylic polymer, a fluoroolefin polymer,
Various vinyl-based polymers such as vinyl ester-based polymers or aromatic vinyl-based polymers; polyester resins, alkyd resins, polyurethane resins and the like. Among these, vinyl-based polymers with particularly good compatibility And polyester resins are more desirable and are recommended.

For the carboxyl group-containing vinyl polymer as the vinyl polymer of the compound (D), various known and conventional methods can be applied. The simplest method is to homopolymerize the monomers or to copolymerize them with other monomers copolymerizable with them.

The carboxyl group-containing monomer and the other copolymerizable monomer used at that time are described above as those which can be used when preparing the above-mentioned component (A). Such various compounds and the like are particularly representative.

In order to prepare a vinyl polymer having both a carboxyl group and a hydroxyl group bonded to a carbon atom in the compound (D), various known and conventional methods can be applied. It is convenient to copolymerize a monomer containing a carboxyl group and a monomer mixture containing a monomer containing a hydroxyl group bonded to a carbon atom as a body.

The hydroxyl group-containing monomer and the other copolymerizable monomer used at that time are the same as those which can be used when preparing the component (A) as described above. The various compounds as listed above are particularly representative.

Next, various known and conventional methods can be applied when preparing a vinyl polymer having a hydroxyl group bonded to a carbon atom as the vinyl polymer of the component (D). Of these, it is easy to homopolymerize a hydroxyl group-containing monomer bonded to a carbon atom or to copolymerize it with another monomer copolymerizable with them. is there.

The hydroxyl group-containing monomer and the other copolymerizable monomer used at that time are the same as those used in preparing the component (A) as described above. The various compounds as listed above are particularly representative.

To prepare the compound (D) having a carboxyl group and / or a hydroxyl group bonded to carbon using various monomers as described above, a solution polymerization method or a non-aqueous dispersion method is used. Any known conventional polymerization method such as a polymerization method can be applied, but the solution radical polymerization method is the most convenient and may be particularly recommended.

On the other hand, in order to prepare the above-mentioned polyester resin as one of the components of the compound (D), it is the simplest method by a condensation reaction of an acid component and an alcohol component, which is a known and commonly used technique. Is.

Among the compounds (D) thus obtained having a carboxyl group and / or a carbon-bonded hydroxyl group, a carboxyl group-containing vinyl polymer; or a carboxyl group and a carbon atom-bonded hydroxyl group are combined. The number average molecular weight of the vinyl polymer has about 80.
Within the range of 0 to about 50,000, preferably 1,0
The range of 00 to 30,000 is suitable.

When it is less than about 800, it tends to be difficult to obtain the one having the desired performance. On the other hand, when it exceeds about 50,000 and becomes too high, the workability is inevitable. In any case, it is not preferable because it is likely to adversely affect.

The acid value of these various vinyl polymers, which are the compound (D), is about 30 to about 170 m.
The range of gKOH / g is suitable, and preferably,
The range of 50 to 150 mgKOH / g is suitable.

When the amount is less than about 30 mgKOH / g, it becomes difficult to obtain a coating film having excellent scratch resistance, and when it exceeds about 170 and becomes too high, it is inevitable. In addition, the viscosity of the coating tends to be high, the workability is deteriorated, and the appearance of the coating film and the stability of the coating are impaired.

Further, when the hydroxyl value bonded to the carbon atom is added while maintaining the above-mentioned acid value, the amount of the hydroxyl group introduced is appropriately in the range of about 5 to about 200 mgKOH / g, and preferably Is 10 to 150 mgK
The range of OH / g is suitable.

A higher value is desirable for the curability, but if the value is too high, exceeding about 200 mgKOH / g, one of the most promising effects of the present invention is the coating film, especially the acid resistance. If the amount is less than about 5 mgKOH / g, it becomes difficult to obtain the effect of improving the curability due to the introduction of the hydroxyl group. Therefore, either case is not preferable.

On the other hand, the vinyl polymer having a hydroxyl group bonded to a carbon atom used in the present invention has a number average molecular weight of about 800 to about 50,000, preferably 1,000. The range of up to 30,000 is suitable.

If it is less than about 800, it is inevitable that it is difficult to obtain a product having desired performance.
On the other hand, if it exceeds about 50,000 and becomes too high, the workability will be adversely affected.

The amount of hydroxyl group introduced is appropriately within the range of about 5 to about 200 mgKOH / g, and preferably within the range of 10 to 150 mgKOH / g. Although higher is preferable for the curability, if it exceeds about 200 mgKOH / g and becomes too high, it is one of the most promising effects of the present invention. If the amount is less than about 5 mgKOH / g, on the other hand, it becomes difficult to obtain the effect of improving the curability by introducing a hydroxyl group.

On the other hand, the component (D) component is a polyester resin having a carboxyl group, a resin having both a carboxyl group and a hydroxyl group, and a polyester resin having a hydroxyl group. The number average molecular weight is appropriately in the range of about 300 to about 50,000, preferably 1,000 to 30,000.

When it is less than about 300, it is inevitable that the desired performance such as scratch resistance is not easily exhibited. On the other hand, when it exceeds about 50,000, it becomes too high.
In any case, it will adversely affect workability and the like, which is not preferable in any case.

The amount of the carboxyl group introduced into the compound having a carboxyl group in the compound (D) is an acid value of about 30 to about 170 mgKOH / g.
The range of (solid content) is suitable, and preferably 5
The range of 0 to 150 mg KOH / g (solid content) is suitable.

When the amount is less than about 30 mgKOH / g (solid content), it becomes difficult to increase the level of curability, which is an effect of the introduction of the carboxyl group.
If it exceeds 0 mgKOH / g (solid content) and becomes too high, the viscosity of the coating composition is inevitably increased, and the workability tends to be poor.

Further, when the component (D) is a polyester resin and the hydroxyl group-containing compound or the compound having both a carboxyl group and a hydroxyl group, the hydroxyl group introduction amount is as follows: About 5 to about 15
A range of 0 mgKOH / g (solid content) is suitable, and preferably 10 to 140 mgKOH / g (solid content).

When the amount is less than about 10 mgKOH / g (solid content), the effect of increasing the level of curability by introducing a hydroxyl group becomes difficult to be recognized, while on the other hand, 150 mgKOH / g
If the amount exceeds g (solid content) and becomes too large, the viscosity of the coating composition will inevitably increase, which in turn impairs workability, which is not preferable in any case.

Next, the polysiloxane (B) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, which is one of the essential constituents of the composition of the present invention, is generally Specifically, it refers to a polysiloxane having a form having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, which is called a silanol group.

Here, a hydrolyzable group bonded to a silicon atom means a hydrogen atom, a halogen atom, an alkoxy group, a substituted alkoxy group bonded to a silicon atom,
Various groups such as an acyloxy group, a phenoxy group, a mercapto group, an amino group, an amido group, an aminooxy group, an iminooxy group or an alkenyloxy group which are hydrolyzed to form a hydroxyl group bonded to a silicon atom are formed. This is what you call it.

As only typical examples of the polysiloxane (B), only typical examples will be given.
A class of hydrolyzed condensates of silicon compounds or such silicon, which is prepared by hydrolytically condensing at least two silicon compounds having a hydrolyzable group bonded to a silicon atom in one molecule. Part of the hydrolyzed condensates of the silicon compounds, such as those prepared by partially hydrolyzing and condensing a compound.

The polysiloxane (B) is a hydrolysis-condensation product of a silicon compound having at least two silicon-bonded hydrolyzable groups in one molecule, which is prepared by the following formulation. Alternatively, a partially hydrolyzed condensate can be used.

The above-mentioned at least two in one molecule,
A silicon compound having a silicon atom-bonded hydrolyzable group, which is used when the polysiloxane (B) is prepared by hydrolysis or partial hydrolysis of the silicon compound having a silicon atom-bonded hydrolyzable group. As for, various known and commonly used compounds can be used, but of these, only typical ones will be exemplified.

[0118]

Embedded image R ⁹ _a SiR ¹⁰ _4-a [III]

(Wherein R ⁹ in the formula may be an alkyl group which may or may not have a substituent,
A monovalent organic group consisting of an aryl group, an aralkyl group or an alkenyl group, R ¹⁰ is a hydrogen atom, a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group, an amido group or an aminooxy group. , An iminooxy group or an alkenyloxy group, and a is an integer of 0, 1 or 2. )

A silicon compound represented by the formula; a partial hydrolysis-condensation product obtained by partial hydrolysis-condensation of one of these silicon compounds; or a partial hydrolysis-condensation of two or more kinds of these silicon compounds. Partial co-hydrolysis condensate;

Alternatively, each of the following structural formulas

[0122]

Embedded image (CH ₃ CH ₂ O) ₃ SiCH ₂ CH ₂ CH ₂ CH
₂ Si (OCH ₂ CH ₃ ) ₃

Or

[0124]

Embedded image (CH ₃ CH ₂ O) ₃ SiCH ₂ CH ₂ CH ₂ CH
₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃

2 in one molecule, as shown by
Examples thereof include silicon compounds having one or more hydrolyzable silyl groups.

As only specific examples of the silicon compounds represented by the above general formula, various tetraalkoxysilanes such as tetraethoxysilane, tetramethoxysilane or tetrabutoxysilane can be given. ;

Methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane or butyltrimethoxysilane. Ethoxysilane,

Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-butoxysilane, vinyltris (β-methoxyethoxy) silane or allyltrimethoxysilane,

Trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, γ- (meth) acryloyloxypropyltrimethoxysilane or γ- (meth) acryloyloxypropyltriethoxysilane. Various organotrialkoxysilanes such as

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane or dibutyldiethoxysilane,

Diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, vinylmethyldimethoxysilane, methyldimethoxysilylethyl vinyl ether, methyldimethoxysilylpropyl vinyl ether or γ- (meth). Various diorganodialkoxysilanes such as acryloyloxypropylmethyldimethoxysilane;

Tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltotichlorosilane, vinyltrichlorosilane, γ- (meth) acryloyloxypropyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, methyl Various chlorosilanes such as phenyldichlorosilane, vinylmethyldichlorosilane or γ- (meth) acryloyloxypropylmethyldichlorosilane;

Or tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane,
Various acetoxysilanes such as dimethyldiacetoxysilane or diphenyldiacetoxysilane.

Of these, tetraalkoxysilanes, organotrialkoxysilanes, diorganodialkoxysilanes, and the like may be cited as only typical examples of the silicon compound, and the like. These are partially hydrolyzed condensates or their partially cohydrolyzed condensates.

Furthermore, when a tetrafunctional silicon compound represented by tetraethoxysilane is used as the silicon compound, it is also used for preventing gelation during the condensation reaction and for the resin solution obtained. In order to improve the storage stability, it is desirable to use a bifunctional or trifunctional silicon compound together.

When preparing the polysiloxane (B), in addition to the various silicon compounds described above,
In the form of having one hydrolyzable group bonded to a silicon atom in one molecule, such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane or triphenylethoxysilane. , So-called 1
A functional silicon compound can also be used together.

By hydrolytically condensing or partially hydrolyzing and condensing various silicon compounds as described above, a hydrolytic condensate or a partial hydrolytic condensate used as the polysiloxane (B) can be obtained. However, in that case, a catalyst may or may not be used, and it is desirable to use a catalyst from the viewpoint of facilitating the progress of each condensation reaction.

When a catalyst is used here,
It is needless to say that any of various known and commonly used catalysts may be used, and they may be used alone or in combination of two or more kinds.

As such catalysts, only representative ones are exemplified, such as hydrochloric acid, sulfuric acid or phosphoric acid.
Various inorganic acids; various organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate or acetic acid;

Various inorganic bases such as sodium hydroxide or potassium hydroxide; various titanic acid esters such as tetraisopropyl titanate or tetrabutyl titanate; various tin carboxyls such as dibutyltin dilaurate or tin octylate. Acid salts;

Various metal carboxylates such as naphthenates or octylates of various metals such as iron, cobalt, manganese or zinc; various aluminum compounds such as aluminum trisacetylacetate;

1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,4-diazabicyclo [2.2] .2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine,
Butylamine, octylamine,

Various amine compounds such as monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole and 1,4-diethylimidazole;

Tetramethylammonium salt, tetrabutylammonium salt, trimethyl (2-hydroxypropyl) ammonium salt, cyclohexyltrimethylammonium salt, tetrakis (hydroxylmethyl) ammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt or o- Various quaternary ammonium salts such as trifluoromethylphenyltrimethylammonium salt,

Furthermore, as a typical counter anion,
Examples thereof include quaternary ammonium salts having chloride, bromide, carboxylate, hydroxide and the like.

The amount of the catalyst used is in the range of about 0.0001 to about 10% by weight, preferably 0.0005 to 3%, based on the silicon compound to be subjected to hydrolysis or partial hydrolysis. The range of 0.005 to 1% by weight is suitable, and the range of 0.0005 to 1% by weight is particularly preferable.

The amount of water used in the reaction is about 0.05 mol or more, preferably 0 mol, relative to 1 mol of the hydrolyzable group bonded to the silicon atom of the silicon compound. 0.1 mol or more is suitable, and more preferably 0.2 mol or more is suitable.

If the amount is less than about 0.05 mol, the hydrolysis rate will be remarkably slowed down, which is not preferable in practical use. However, the amount of water is 5 mol, 10 mol or silicon. There is no problem in using the compound in such an amount that the amount is too much with respect to 1 mol of the hydrolyzable group bonded to the atom.

The addition of these catalysts and water is
Needless to say, they may be added all at once, or may be added in portions, or may be added in the form of using the catalyst and water together, or may be added separately.

The reaction temperature for such a reaction is 0 ° C to 1 ° C.
About 50 ° C. is appropriate, preferably 20 ° C. to 100 ° C.
C. is suitable, and on the other hand, as the pressure of these reactions, it can be carried out under any condition of normal pressure, increased pressure or reduced pressure.

In such a reaction, an organic solvent may or may not be used, but an organic solvent is used in order to facilitate stirring and the like. Is desirable.

When an organic solvent is used, any of various known and commonly used organic solvents may be used, and they may be used alone or in combination of two or more kinds. Of course.

When the polysiloxane (B) is prepared using such an organic solvent, an organic compound of a silicon compound having a hydrolyzable group bonded to at least two silicon atoms in one molecule is prepared. The concentration in the solvent is 5
It is desirable to set the content to about wt% or more.

Only the typical commercially available products of the polysiloxane having a silanol group or a methoxy group bonded to a silicon atom, prepared in this manner, will be exemplified below. "TSR-160 or 165"
[Toshiba Silicone Co., Ltd. product name], "SH-601
8 "[trade name of Toray Dow Corning Silicone Co., Ltd.] or" GR-100, 908 or 950 "
A hydrolysis-condensation product or a partial hydrolysis-condensation product having a linear, branched (branched) or ladder (type) structure, as represented by [trade name of Showa Denko KK] Is.

Vinyl polymer (A), prepared according to the preparation method as described above, respectively.
Regarding the usage ratio of the polysiloxane (B) and the compound (D), first, the component (D) is about 5 to about 150 parts by weight (solid content) per 100 parts by weight (solid content) of the component (A).
The range of 10 to 100 parts by weight (solid content) is suitable.

The proportion of the polysiloxane (B) used is 100 parts by weight (solid content) of the vinyl polymer (A), or the total of the vinyl polymer (A) and the compound (D). About 5 to 100 parts by weight (solid content)
A range of about 150 parts by weight (solid content) is suitable,
Preferably, 10 to 100 parts by weight (solid content) is suitable.

When the amount of the polysiloxane (B) is less than about 5, the polysiloxane (B) is inevitably too small, and therefore, the high weather resistance and the long-term water repellency are maintained. However, if it exceeds about 150 parts by weight (solid content) and becomes too large,
In any case, it is not preferable because it results in a brittle cured coating film with poor practicality.

An amino resin of at least one curing agent selected from the group consisting of amino resin, polyisocyanate and blocked polyisocyanate, which is used in obtaining the curable resin composition according to the present invention; Is a compound having an N-hydroxymethylamino group and / or an N-alkoxymethylamino group, and if only representative examples of the amino resin are given,

As obtained by reacting various amino group-containing compounds such as melamine, benzoguanamine, acetoguanamine, urea or glycouril with various aldehyde compounds (or aldehyde-providing substances) such as formaldehyde or acetaldehyde. Various amino resins having alkylol groups;

Alternatively, an alkoxyalkyl group having a form obtained by reacting an amino resin having such an alkylol group with various lower alcohols such as methanol, ethanol, n-butanol or i-butanol is used. Amino resin and the like.

Further, only typical compounds having an N-hydroxymethylamino group or an N-alkoxymethylamino group will be exemplified.
Of various vinyl monomers having an N-hydroxymethylamide group or an N-alkoxymethylamide group, such as methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide or N-butoxymethyl (meth) acrylamide. Homopolymer,

Alternatively, these amide group-containing vinyl monomers can be copolymerized with the monomers, and each is a (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl. Various acrylic copolymers, vinyl ester copolymers, or fluoropolymers having an N-hydroxymethylamino group or an N-alkoxymethylamino group, which can be obtained by copolymerization with monomers and the like. Various vinyl-based copolymers such as olefin-based copolymers.

Further, if only representative examples of the above polyisocyanate compounds are given, various aromatic diisocyanates such as tolylene diisocyanate or diphenylmethane diisocyanate; meta-xylylene diisocyanate, α, α ，
various aralkyl diisocyanates, such as α ', α'-tetramethyl-meta-xylylene diisocyanate;

Hexamethylene diisocyanate, lysine diisocyanate, 1,3-bisisocyanatomethylcyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane or isophorone diisocyanate. , Various aliphatic or cycloaliphatic diisocyanates; or

Prepolymers having an isocyanate group, which can be obtained by addition reaction of various polyisocyanates such as those mentioned above with polyhydric alcohols; cyclization trimerization of various polyisocyanates such as those mentioned above Prepolymers having an isocyanurate ring, such as are obtained at most; or

The polyisocyanates having a biuret structure, which can be obtained by reacting various polyisocyanates such as those mentioned above with water, and further, 2-isocyanatoethyl (meth) acrylate. Homopolymers of vinyl monomers having various isocyanate groups, such as 3-isopropenyl-α, α-dimethylbenzyl isocyanate or (meth) acryloyl isocyanate;

Alternatively, these various isocyanate group-containing vinyl monomers and (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin copolymerizable with the monomers, respectively. As obtained by copolymerizing with vinyl-based monomers, etc., each containing an isocyanate group, such as an acrylic copolymer, a vinyl ester-based copolymer or a fluoroolefin-based copolymer, Examples include various vinyl-based copolymers.

Among these polyisocyanates, aliphatic or alicyclic diisocyanate compounds; various prepolymers derived from each of these diisocyanate compounds, especially from the viewpoint of weather resistance and the like. Alternatively, the use of an isocyanate group-containing vinyl polymer or the like is particularly desirable.

As the above-mentioned blocked polyisocyanate compounds, only typical ones will be exemplified, and various polyisocyanate compounds as mentioned above will be blocked with various blocking agents as mentioned later. Various block polyisocyanate compounds in the form obtained by squeezing,

Examples include compounds of the type in which the isocyanate group is regenerated by heat, such as compounds in the form containing various uretdione structures, which are obtained by cyclizing and dimerizing the isocyanate group.

Then, only specific examples of blocking agents used when preparing the blocked polyisocyanate (compound) are exemplified, such as methanol, ethanol, benzyl alcohol or lactate ester. Various carbinol group-containing compounds;

Various phenolic hydroxyl group-containing compounds such as phenol, salicylic acid ester or cresol; or various amides such as ε-caprolactam, 2-pyrrolidone or acetanilide;

Further, various oximes such as acetone oxime or methylethylketoxime, and further various active methylene compounds such as methyl acetoacetate, ethyl acetoacetate or acetylacetone.

Among the various curing agents as mentioned above, when the amino resin is also used, the amount thereof is the total amount of the resin solids of the vinyl polymer (A) and the polysiloxane (B). 5 parts by weight to 100 parts by weight or 100 parts by weight of the total resin solid content of the vinyl polymer (A), the polysiloxane (B) and the compound (D). (Solid content), preferably 10 to 150 parts by weight (solid content), more preferably 15 to 100 parts by weight (solid content).
It may be mixed such that the content is within the range.

The amounts of the polyisocyanate and / or the blocked isocyanate as listed above are used as the vinyl polymer (A) and the polysiloxane (B).
With respect to 100 parts by weight of the total resin solid content, or with respect to 100 parts by weight of the total resin solid content of the vinyl polymer (A), polysiloxane (B) and compound (D). , About 1 to about 200 parts by weight (solid content), preferably 5 to 150 parts by weight (solid content), more preferably 10 to 100 parts by weight (solid content). It may be mixed such that the content is within the range.

The above-mentioned curing catalyst (C) is blended in the curable resin composition according to the present invention as an essential constituent component, but only typical ones are exemplified as the curing catalyst (C). If only, tetramethylammonium fluoride, tetramethylammonium bromide, trimethylbenzylammonium hydroxide, 2-
Including hydroxypyridine, trimethylammonium methoxide, phenyltrimethylammonium chloride, phenyltrimethylammonium bromide, phenyltrimethylammonium hydroxide, phenyltrimethylammonium iodide, phenyltrimethylammonium bromide or phosphocholine chloride sodium salt,

Furthermore, stearyl ammonium bromide, tetra-n-butylammonium hydroxide, tetra-n-butylammonium phosphate,
Tetra-n-dodecyl ammonium trichloride, tetraethyl ammonium hydroxide, tetraethyl ammonium tetrafluoroborate, acetylcholine bromide, alkyldimethylbenzyl ammonium chloride, benzylcholine bromide, benzyl-n
-Butyl ammonium bromide, betaine, butyryl chloride, bis (tetra-n-butyl ammonium)
Various quaternary ammonium salts such as dichromate, trimethylvinylammonium bromide, trioctylmethylammonium acetate or tributylmethylammonium acetate;

Allyltriphenylphosphonium chloride, n-amyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride,
Bromomethyltriphenylphosphonium bromide,
2-dimethylaminoethyltriphenylphosphonium bromide, ethoxycarbonylphosphonium bromide, n-heptyltriphenylphosphonium bromide, methyltriphenylphosphonium bromide,
Various phosphonium salts, such as tetrakis (hydroxymethyl) phosphonium sulfate or tetraphenylphosphonium bromide;

Alternatively, various acid catalysts such as phosphoric acid, p-toluenesulfonic acid or dimethylsulfate; 1,8-diazabicyclo (5,4,0) undecene-7 or 1,
Various basic catalysts such as 4-diazabicyclo (2,2,2) octane; or various carbonates such as calcium carbonate.

The curing catalyst (C) is used in an amount of 100 parts by weight of the total resin solid content of the vinyl polymer (A) and polysiloxane (B), or the vinyl polymer (A). The amount of the group (or group) having the catalytic activity is about 0.0001 to about 0.2 mol based on 100 parts by weight of the total amount of the resin solids of the polysiloxane (B) and the compound (D). , Preferably 0.001
A suitable range is from 0.1 to 0.1 mol, and addition within this range is desirable.

When the amount used is less than about 0.0001 mol, the crosslinking reaction is difficult to proceed sufficiently. On the other hand, when it exceeds about 0.2 mol and too much. Inevitably, the storage stability of the thermosetting resin composition, the water resistance of the coating film, and the like are remarkably reduced, which is not preferable in any case.

It can be said that the curable resin composition according to the present invention thus obtained may further contain, if necessary, a polyepoxy compound having an alicyclic epoxy group or a glycidyl group. In particular, the use of an epoxy group-containing acrylic resin is optimal because it has good compatibility.

Further, a leveling agent or an ultraviolet absorber,
Further, it goes without saying that various known and commonly used additives such as light stabilizers, plasticizers and the like can be added.

Next, the method for forming a coating film according to the present invention, which comprises using the curable resin composition according to the present invention of various types as described above, will be described. To do.

Specifically, a novel and practical coating finishing method will be described in which the curable resin composition of the present invention is used as a clear coat to form a multilayer coating film. It is a thing.

That is, such a multilayer coating film
A crosslinkable base coat paint in the form of blending a metal pigment and / or a coloring pigment is applied on an object to be coated (base material), and then the thermosetting resin composition of the present invention is used on the base coat coated surface. A coating method by a so-called 2 coat 1 bake system (hereinafter, also referred to as 2C1B) in which the clear coat paint prepared in the above is coated and crosslinked.

[0187] Alternatively, various known clear coat paints, or a 2C1B multi-layer coating prepared as described above using a clear coat paint prepared from the thermosetting resin composition of the present invention may be used. On the film, a clear coat paint prepared by using the thermosetting resin composition of the present invention is further applied to crosslink the film.
Coating method by coat 2 bake method (hereinafter, also referred to as 3C2B);

Alternatively, on the article to be coated (base material), a crosslinkable base coat paint in the form of a mixture of a metal pigment and / or a coloring pigment is applied for cross-linking, and then on the base coat-coated surface, It refers to various coating film forming systems by a coating method such as a so-called two-coat, two-bake system in which a clear coat coating composition prepared by using the thermosetting resin composition of the present invention is coated and crosslinked. . Therefore, in the present invention, the term "multilayer coating film" refers to a coating film obtained by the above-described coating method.

In carrying out the coating film forming method or coating finishing method according to the present invention, various known and conventional solvent-based, non-aqueous dispersion-based or water-based coating materials can be used as the base coating material. Since paint can be used, it is not particularly limited.

[0190] As the curable composition which constitutes such a base coat coating material, only representative examples are given, and a composition comprising a hydroxyl group-containing resin and a melamine resin, and a hydroxyl group A composition in the form of a containing resin and a blocked polyisocyanate compound,

Furthermore, with carboxyl group-containing resins,
A composition in the form of an epoxy group-containing resin; a composition in which a hydrolyzable silyl group-containing resin is used as a base polymer component, and further, based on the curable resin composition of the present invention Or a combination system of two or more of these.

The paint for base coat refers to a paint in which at least one kind of various pigments such as an organic pigment, an inorganic pigment or a metal pigment is mixed as an essential constituent component. is there.

In addition, various known and commonly used coating methods can be applied to the above-mentioned various types of coatings, but only typical ones are specifically exemplified. For example, airless coating, air atomization coating or rotary atomization coating.

2 coat 1 bake system, 2 coat 2
In forming a multilayer coating film by a baking method or a 3 coat 2 baking method, the conditions for baking are generally at a temperature of about 100 to 180 ° C. for about 20 to 40 minutes. Time is suitable.

The curable resin composition according to the present invention thus obtained can be used for a wide range of materials regardless of iron and non-ferrous metals, and among them, it is particularly representative. Of these, only to specifically exemplify, iron, aluminum, zinc, tinplate, dull steel plate, brass, polypropylene, polycarbonate, polyphenylene sulphite, polyethylene or vinyl chloride, but in the present invention, It is by no means limited to these illustrative examples.

Therefore, also in the coating film forming method according to the present invention, it can be applied to a wide range of materials regardless of whether it is ferrous or non-ferrous metal. Specific examples are iron, aluminum, zinc, tinplate, dull steel plate, brass, polypropylene, polycarbonate, polyphenylene sulphite, polyethylene or vinyl chloride, but only in the present invention. It is by no means limited to these illustrative examples.

[0197]

EXAMPLES Next, the present invention will be explained more specifically with reference to Reference Examples, Examples and Comparative Examples, but the present invention is by no means limited to these Examples. Absent. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 [Preparation Example of Vinyl Polymer (A) Having Linear Carbonate Group in Molecule]

A four-necked flask equipped with a thermometer, a cooling tube, a stirrer and a nitrogen gas introducing tube was charged with 350 g of xylene.
Parts, 300 parts of n-butanol and 150 parts of n-butyl acetate were charged and heated to 120 ° C.

[0200]

Embedded image

(However, n in the formula means the number of repeating units, and is an arbitrary number within the range of 0.5 to 20.)

That is, that is, the structural formula [I-5] shown above.
300 of linear carbonate (L-CABO) represented by
Parts, 200 parts of methyl methacrylate, 20 parts of styrene
A mixture of 0 parts and 300 parts of n-butyl methacrylate, 200 parts of xylene, 10 parts of azobisisobutyronitrile (AIBN) and 20 parts of tert-butylperoxy-2-ethyl-hexanoate. And the mixture were added dropwise at the same temperature over 5 hours,

After the completion of dropping, the reaction was continued at the same temperature for 7 hours to allow the reaction to continue, whereby the nonvolatile content was 50.4% and the Gardner viscosity at 25 ° C. (hereinafter, abbreviated as viscosity). .) Is T-U and the number average molecular weight is 12,000 to obtain a solution of the target resin. Hereinafter, this is abbreviated as resin (A-1).

Reference Examples 2 to 4 (same as above) The same procedure as in Reference Example 1 was repeated except that the composition ratio of the raw materials charged was changed as shown in Table 1. Carbonate groups and hydroxyl groups bonded to carboxyl groups and / or carbon. A vinyl polymer (A) solution having both and was obtained. The property values of each resin are shown together in the table.

[0205]

[Table 1]

<< Footnote in Table 1 >>"PlaxelFM-1" ... Trade name of caprolactone-added hydroxyl group-containing monomer manufactured by Daicel Chemical Industries, Ltd.

[0207]

[Table 2]

Reference Example 5 [Preparation example of vinyl polymer (A) having 6-membered ring carbonate group in molecule]

In a four-necked flask equipped with a thermometer, a cooling tube, a stirrer and a nitrogen gas introducing tube, 350 g of xylene was added.
Parts, 300 parts of n-butanol and 150 parts of n-butyl acetate were charged and heated to 120 ° C.,

6-Membered Ring Carbonate 5-Ethyl-5-
300 parts of (meth) acryloyloxymethyl-1,3-dioxan-2-one, 20 of methyl methacrylate
A mixture of 0 parts, 200 parts of styrene and 300 parts of n-butylmethacrylate, 200 parts of xylene, 10 parts of AIBN and 20 parts of tert-butylperoxy-2-ethylhexanoate. , At the same temperature, added dropwise over 5 hours,

After the dropping, the reaction is continued at the same temperature for 7 hours so that the nonvolatile content is 50.1%, the viscosity is VW, and the number average molecular weight is 11%. A solution of the desired resin was obtained. Hereinafter, this is abbreviated as resin (A-5).

Reference Examples 6 to 8 (same as above) The same procedure as in Reference Example 5 was carried out except that the composition ratio of the raw materials charged was changed as shown in Table 2 to bond the cyclic carbonate group, the carboxyl group and / or the carbon. A solution of the vinyl polymer (A) having both hydroxyl groups was obtained. The property values of each resin are shown together in the table.

[0213]

[Table 3]

[0214]

[Table 4]

Reference Example 9 [Preparation Example of Vinyl Polymer (A) Having 5-Membered Ring Carbonate Group in Molecule]

In a four-necked flask equipped with a thermometer, a cooling tube, a stirrer and a nitrogen gas introducing tube, 350 g of xylene was added.
Part, 300 parts of n-butanol and 150 parts of n-butyl acetate were charged, and the temperature was raised to 120 ° C.
A mixture of 300 parts of 2,3-carbonate propyl (meth) acrylate of a membered ring carbonate, 200 parts of methyl methacrylate, 200 parts of styrene and 300 parts of n-butyl methacrylate, and 20 parts of xylene.
0 part, 10 parts of AIBN and tert-butylper
A mixture with 20 parts of oxy-2-ethyl-hexanoate was added dropwise at the same temperature over 5 hours,

After completion of the dropping, the reaction was continued at the same temperature for 7 hours so that the non-volatile content was 50.1%, the viscosity was VW, and the number average molecular weight was 12%. A solution of the desired resin was obtained. Hereinafter, this is abbreviated as resin (A-9).

Reference Examples 10 to 12 (same as above) A 5-membered ring carbonate group was prepared in the same manner as in Reference Example 9 except that the composition ratio of raw materials charged was changed as shown in Table 3.
A solution of the vinyl polymer (A) having both a carboxyl group and / or a hydroxyl group bonded to carbon was obtained. The property values of each resin are shown together in the table.

[0219]

[Table 5]

[0220]

[Table 6]

Reference Example 13 [Preparation example of compound (D) having carboxyl group and / or hydroxyl group bonded to carbon]

This example shows a preparation example of a carboxyl group- and hydroxyl group-containing polyester resin.

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser with a dehydration trap, and a nitrogen gas introduction tube,
190 parts of trimethylolpropane, 145 parts of 1,6-hexane glycol and 350 of isophthalic acid were charged, and the temperature was raised to 150 ° C.

Then, 390 parts of hexahydrophthalic acid and 0.85 part of lithium hydroxide were added, and the mixture was heated at 220 ° C.
The temperature was raised to 1, and a dehydration condensation reaction was performed at this temperature to continue the reaction until the solid content acid value reached 150.

After completion of the reaction, the reaction product was cooled and 400 parts of "Solvesso 100" (trade name of aromatic hydrocarbon solvent manufactured by Maruzen Sekiyu KK) and 120 parts of xylene were cooled. By adding and, a solution of the target resin having a nonvolatile content of 70%, an acid value of the solid content of 148, and a hydroxyl value of 10 was obtained. Hereinafter, this is abbreviated as resin (PA-13).

Reference Example 14 (same as above)

This example shows a preparation example of a vinyl polymer containing a carboxyl group.

In a four-necked flask equipped with a thermometer, a cooling tube, a stirrer and a nitrogen gas introducing tube, 350 g of xylene was added.
Parts, 300 parts of n-butanol and 150 parts of n-butyl acetate were charged and heated to 120 ° C., 200 parts of methacrylic acid and 200 parts of methyl methacrylate were charged.
Part, 200 parts of styrene and 300 parts of n-butyl methacrylate, 200 parts of n-butyl acrylate, 200 parts of xylene and 10 parts of AIBN.
Parts and a mixture with 20 parts of tert-butylperoxy-2-ethyl-hexanoate are added dropwise at the same temperature over 5 hours,

After the completion of the dropping, the reaction was continued at the same temperature for 7 hours, whereby the nonvolatile content was 49.6%, the viscosity was V, and the number average molecular weight was 11,500. A solution of the desired resin was obtained. Hereinafter, this is abbreviated as resin (PA-14).

Reference Examples 15 and 16 (same as above) A carboxyl group and / or a carboxyl group were prepared in the same manner as in Reference Example 14 except that the composition ratio of raw materials charged was changed as shown in Table 4.
Alternatively, a solution of the compound (D) having a hydroxyl group bonded to carbon was obtained. The property values of each resin are shown together in the table.

[0231]

[Table 7]

[0232]

[Table 8]

Next, a preparation example of a polysiloxane (B) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, which is used when the curable resin composition according to the present invention is obtained. I will show you.

Reference Examples 17 to 20

Reference Example 17 [Preparation Example of Polysiloxane (B) Having Hydroxyl Group Bonded to Silicon Atom and / or Hydrolyzable Group Bonded to Silicon Atom]

A reaction vessel equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with 9 parts of methyltriethoxysilane.
54 parts, 294 parts of xylene and 1 of n-butanol
26 parts were charged and the temperature was raised to 80 ° C.

Then, at the same temperature, 0.026 parts of "AP-3" (trade name of isopropyl acid phosphate manufactured by Daihachi Chemical Industry Co., Ltd.) and 294 parts of ion-exchanged water were added.
And 5 minutes, and after stirring for 4 hours at the same temperature, the hydrolysis of methyltriethoxysilane is progressing by nuclear magnetic resonance analysis ( ¹ H-NMR). It was confirmed. Then, water and by-products such as ethanol were removed by vacuum distillation to obtain a solution of the target resin having a nonvolatile content of 40.4%. Hereinafter, this is abbreviated as (B-1).

Reference Examples 18 to 20 (same as above)

In the same manner as in Reference Example 17, except that the composition ratio of the raw materials charged was changed as shown in Table 5, the compound had a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom. Various polysiloxanes (B) were obtained. The various property values for each resin are summarized below.
It is shown in the table.

[0240]

[Table 9]

<< Footnote in Table 5 >> Each numerical value showing the usage ratio of raw materials is assumed to be the number of parts by weight.

“MTES” ……… Abbreviation of methyltriethoxysilane “FTES” ……… Abbreviation of phenyltriethoxysilane

Example 1 Carbonate group-containing vinyl polymer (A) obtained in Reference Example 1, 5-membered ring carbonate group-containing vinyl polymer (A) obtained in Reference Example 9, and Reference Example 15 The compound (D) having both a carboxyl group and / or a carbon-bonded hydroxyl group obtained in 1. and the silicon atom-bonded hydroxyl group and / or a silicon atom-bonded hydrolyzable group obtained in Reference Example 17. A polysiloxane (B) having: and trioctylmethylammonium acetate, which is one of the curing catalysts (C),

"Tinuvin 900" (trade name of UV absorber manufactured by Ciba-Geigy, Switzerland) and "Tinuvin 1"
23 "(trade name of light stabilizer manufactured by Ciba-Geigy, Switzerland) and" P-L050 "(Wacker, Germany)
P manufactured by Silicones Corporation
aint additive's product name),

A thermosetting resin composition prepared according to the following blending composition ratio and by blending by a usual paint preparation method was used as a diluent solvent at 25 ° C. in Ford Cup No. A clear paint was obtained by diluting so that the viscosity according to 4 was 23 seconds and adjusting it. Hereinafter, this paint is abbreviated as (CC-1). In addition, the number showing the weight is
Hereinafter, all solid weights are used unless otherwise specified.

Resin (A-1) 41 Resin (A-9) 515 Resin (PA-15) 344 Resin (B-1) 100 Catalyst (trioctylmethylammonium acetate) 50 “Tinuvin 900” 20 “Tinuvin 123” 15

“P-L050” 100 ppm

Examples 2 to 18 and Comparative Examples 1 to 18 Carbonate group-containing vinyl polymers obtained in Reference Examples 1 to 12 and carboxyl groups and / or carbon atoms obtained in Reference Examples 13 to 16 A carboxyl group-containing polyester resin of a compound having a hydroxyl group bonded to, a carboxyl group-containing acrylic resin, and Reference Examples 17 to
The polysiloxane having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, which is obtained in 20, and optionally other components may also be used in Table 6 and A clear coating material was obtained in the same manner as in Example 1 except that the composition ratio was changed as shown in Table 7.

[0249]

[Table 10]

<< Footnotes in Table 6 >> TOMA ......... abbreviation of trioctylmethylammonium acetate

[0251]

[Table 11]

<< Footnote in Table 6 >> L-117 ... "Super Beckamine L-117-60" [trade name of melamine resin manufactured by Dainippon Ink and Chemicals, Inc.] abbreviation

[0253]

[Table 12]

<< Footnote of Table 6 >> 980K ... "Barnock DB-980K-75"
Abbreviation of [trade name of block polyisocyanate compound manufactured by Dainippon Ink and Chemicals, Inc.]

[0255]

[Table 13]

[0256]

[Table 14]

[0257]

[Table 15]

[0258]

[Table 16]

[0259]

[Table 17]

[0260]

[Table 18]

[0261]

[Table 19]

[0262]

[Table 20]

[0263]

[Table 21]

[0264]

[Table 22]

[0265]

[Table 23]

Then, the thermosetting resin compositions thus obtained were each subjected to a 2 coat 1 bake method (2C1B).
Thus, the intended coating film forming method was carried out by using this clear coating material as a clear coating material when forming a laminated coating film, and by combining this clear coating material with a base coating material A as described later.

That is, first, a predetermined base paint (base paint A in this example) was applied on an object to be coated (base material), and then, in a wet state, it was listed on this base coat-coated surface. The various thermosetting resin compositions as described above are used as clear paints, and the paints are applied.
The method of forming a coating film was carried out by a so-called 2-coat 1-baking method in which baking was performed to crosslink at 0 ° C. for 20 minutes.

The cured coating film thus obtained was evaluated for various physical properties and various performances. The results are shown in the same table.

The base coating material A was "Acridic KJ-204" [Dainippon Ink and Chemicals, Inc.].
Trade name of hydroxyl group-containing acrylic resin manufactured by MHI; nonvolatile content = 5
0%] and "Super Beckamine L-117-60"
(Butyl etherified melamine resin described above; nonvolatile content = 6
0%), "Aluminum paste 7160NS" [trade name of aluminum paste manufactured by Toyo Aluminum Co., Ltd.], and "Fastgen Super Red BN".
[Product name of red pigment manufactured by Dainippon Ink and Chemicals, Inc.]
Using a so-called metallic base paint obtained by using the above, the pigment weight concentration (PWC) of aluminum of the base paint A was 13%, and the red pigment P
The WC was 15%.

Further, as the base paint B, "Beckolite GF-542" [trade name of hydroxyl group-containing polyester resin manufactured by Dainippon Ink and Chemicals, Inc .; nonvolatile content =
65%], "Super Beckamine L-117-6
0 "and carbon black, PW
I use the one that C is 5%,

Further, as the base paint C, styrene:
Methyl methacrylate: n-butyl acrylate: Methacrylic acid: 2-hydroxypropyl methacrylate = 1
Hydroxyl group-containing vinyl copolymer emulsion having a composition of 0: 40: 43: 2: 5 (weight part ratio) and having a nonvolatile content of 40%, and "Cymel C-325" [available from Mitsui Ciana Mid , Non-volatile content = 80%], and "Disparlon #
6900-20X "[trade name of thixotropic agent manufactured by Kusumoto Kasei Co., Ltd .; nonvolatile content = 20%] and" aluminum paste W.
Z7160 ”[trade name of aluminum paste manufactured by Toyo Aluminum Co., Ltd.], which is a so-called metallic base coating,

Further, as the base paint D, the resin (A-12) obtained in Reference Example 2 and trioctylmethylammonium acetate were used in the same manner as in Example 12, and further, "Aluminum paste 7160NS" was used. The so-called metallic base paint obtained by using

Application Examples 1 to 18 and Comparative Application Examples 1 to 1
18 Each of the thermosetting resin compositions obtained in Reference Examples 1 to 18 and Comparative Examples 1 to 18 was laminated by a 2C1B or 2 coat 2 bake method (hereinafter, also referred to as 2C2B). Was used as a clear coating for forming the coating composition, and the intended coating film formation method was carried out by appropriately combining each of these clear coatings with each base coating as described below.

However, in the case of the method of 2C2B among them, first, a predetermined base paint is applied on the object to be coated (base material) and baked at 140 ° C. for 20 minutes. Then, the thermosetting resin composition as described above is used as a clear paint on the crosslinked coating film, and the paint is applied.
The method of forming a coating film was carried out by a so-called two-coat two-bake system (2C2B) in which baking was performed to cross-link at 40 ° C. for 20 minutes.

[0275] A coating film forming method and a clear coating used,
The combinations with the base paint are collectively shown in Table 8 and Table 9, respectively.

[0276]

[Table 24]

<< Footnote in Table 8 >>"B" is an abbreviation for "the name of the base paint used".

The circles (∘) displayed as the base coating materials A, B, C and D mean that the corresponding base coating materials are used.

[0279]

[Table 25]

[0280]

[Table 26]

[0281]

[Table 27]

[0282]

[Table 28]

[0283]

[Table 29]

[0284]

[Table 30]

[0285]

[Table 31]

<< Footnote >> "Pattern" ......... abbreviation of "multilayer coating pattern"

"Paint name" ......... abbreviation of "name of clear paint" or "clear paint name"

"Paint A" ......... Abbreviation of "base paint A" "Paint B" ......... Abbreviation of "base paint B" "Paint C" ......... Abbreviation of "base paint C" "Paint D" ... …… Abbreviation for “base paint D”

[0289]

[Table 32]

Next, the above-mentioned 8th and 9th, respectively.
For each cured coating, which was painted and baked by the paint finishing method as shown in the table,
Tests were carried out for measuring various property values and evaluating and determining various physical properties and performances. The results are summarized as
It is shown in Tables 10 and 11.

[0291]

[Table 33]

The measurement items of various property values, the items of evaluation judgment tests of various physical properties and performances, and the points of the measurement or evaluation judgment tests thereof are as follows.

Mitsuzawa: Displayed with a specular reflectance (%) of 60 degrees.

Hardness: The hardness of the pencil was measured by using Mitsubishi Uni [Mitsubishi Pencil Co., Ltd. product] at the time when the coating film started to be scratched.

Impact resistance: A DuPont type impact test was conducted with a 1/2 inch notch and a load of 500 g.

Acid resistance: O.D. of 5% H ₂ SO ₄ aqueous solution. After dropping 2 ml, the film was dried at 80 ° C. for 30 minutes, and the change in the state of the coating film was visually determined.

Alkali resistance ............ O.V. Of 5% NaOH aqueous solution. After dropping 2 ml, the film was dried at 80 ° C. for 30 minutes, and the change in the state of the coating film was visually determined.

Scratch resistance: The gloss retention rate (%) of the coated surface after 30 reciprocations with the felt impregnated with 5% cleanser and a load of 1 kg applied displayed.

Solvent resistance: A xylene rubbing test, in which a felt impregnated with xylene was used,
The change in the state of the coating film after rubbing 0 times was visually determined.

* 1) Yellowing resistance: A white plate obtained by applying a white paint having good heat resistance on a tin plate and curing it has a compounding ratio as shown in Table 1. The color difference (Δb) between the film coated with only the so-called clear paint and cured at 140 ° C. for 20 minutes and the white plate was measured 1 hour after baking and the value was displayed.

At this time, the film thickness is 5
Hold at 0 ± 5 micrometer (μm).

Weather resistance: Shown by 20% gloss retention rate (%) after exposure for 2,500 hours with an accelerated weathering tester (DPW).

"Water repellency (1)" means "initial water repellency".
(That is, "initial water repellency") is an abbreviation for "coating water and water by using" CC-AZ type automatic contact angle measuring device "manufactured by Kyowa Interface Science Co., Ltd. The contact angle with is measured and displayed with the contact angle. "Water repellency (2)" is an abbreviation for "water repellency after accelerated weathering test", which means the contact angle between a coating film and water after exposure with DPW for 2500 hours. The measurement is performed in the same manner as in the case of the "initial water repellency", and the contact angle is displayed.

Gel fraction: Only so-called clear paint having a compounding ratio as shown in Table 1 is 1
It was cured at 40 ° C. for 20 minutes and then the cured coating film thus obtained was dipped in acetone for 24 hours to change the initial coating weight and the coating weight after immersion. The degree was measured and displayed by the change ratio (%) before and after the immersion.

* 2) Storage stability ... First, "initial viscosity"
Ford Cup No. 4, a constant value of 30 seconds was set, and then the "viscosity with time" was maintained at 50 ° C. for 1 month, and then the Ford Cup No. The viscosity after 4 is measured and the viscosity after aging is displayed, and the difference between the initial viscosity and the aging viscosity is to be seen.

[0306]

[Table 34]

[0307]

[Table 35]

[0308]

[Table 36]

[0309]

[Table 37]

[0310]

[Table 38]

[0311]

[Table 39]

[0312]

[Table 40]

<< Footnote >> "Al" ……………… Abbreviation for "alkali resistance"

“Heat resistance” ……………… “Heat resistant yellowing *
Abbreviation of 1 "

“Storage” ……………… “Storage stability *
2 ”abbreviation

[0316]

[Table 41]

[0317]

INDUSTRIAL APPLICABILITY The curable resin composition according to the present invention is excellent as a thermosetting resin composition, especially in heat yellowing, and as a one-pack type coating composition, it has storage stability. It is extremely practical and has excellent workability.

In addition, according to the coating film forming method of the present invention which is carried out using such a thermosetting resin composition, among others, heat yellowing resistance, acid resistance, weather resistance, scratch resistance and coating film appearance, etc. To provide a coating film having excellent smoothness, and particularly a coating film having excellent smoothness.

Therefore, it can be said that the coating finishing method carried out using the thermosetting resin composition for paints of the present invention opens up a new genre, especially for automobiles.

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Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08L 83/06 LRY C08L 83/06 LRY C09D 157/10 PDM C09D 157/10 PDM // C08F 290/06 MRR C08F 290/06 MRR

Claims (11)

[Claims] 1. A vinyl polymer (A) having a carbonate group, a polysiloxane (B) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, and a curing catalyst (C). ) And a curable resin composition. 2. A vinyl polymer having a carbonate group (A), a compound (D) having a carboxyl group and / or a hydroxyl group bonded to a carbon atom, and a hydroxyl group and / or a silicon atom bonded to a silicon atom. A curable resin composition comprising a polysiloxane (B) having a bonded hydrolyzable group and a curing catalyst (C). 3. The curable resin composition according to claim 1, wherein the vinyl polymer (A) also contains a carboxyl group and / or a hydroxyl group bonded to a carbon atom. 4. The curable resin composition according to claim 1, further comprising at least one curing agent selected from the group consisting of an amino resin, a polyisocyanate and a blocked polyisocyanate. The curable resin composition according to. 5. The curable resin composition according to claim 1, wherein the carbonate group is a cyclic carbonate group. 6. The curable resin composition according to claim 1, wherein the carbonate group is a 5-membered cyclic carbonate group. 7. The above-mentioned polysiloxane (B) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom is at least two hydrolyzed groups bonded to a silicon atom in one molecule. A hydrolytic condensate or a partial hydrolytic condensate of a silicon compound having a decomposable group,
The curable resin composition according to claim 1. 8. The above-mentioned polysiloxane (B) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom has an alkoxy group as the hydrolyzable group. Item 8. The curable resin composition according to Item 1, 2 or 7. 9. The above-mentioned polysiloxane (B) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom is tetraalkoxysilane, organotrialkoxysilane, or diorganodialkoxysilane. At least one alkoxysilane selected from the group consisting of a partial hydrolysis-condensation product of a tetraalkoxysilane, a partial co-hydrolysis condensation product of an organotrialkoxysilane and a partial co-hydrolysis condensation product of a diorganodialkoxysilane. The curable resin composition according to claim 1, 2, 7, or 8. 10. The curable resin composition according to claim 2, wherein the compound (D) having a carboxyl group and / or a hydroxyl group bonded to carbon is a vinyl polymer. 11. A multilayer coating film is formed by using a paint containing the curable resin composition according to any one of claims 1 to 10 as a top clear coat.
Coating film forming method.