JP2000319590A - Resin composition for paint - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for paint capable of forming a coating film excellent in finishing behavior, antifouling property and resistance to cracking of a coated film even in a clear coating film for cold drying use. SOLUTION: This resin composition for paint comprises (A) polymer particles dispersed in an organic solvent obtained by polymerizing a monomer in an organic solvent that does not substantially dissolve the polymer in the presence of a dispersion stabilizing resin having hydroxyl value, (B) a silicone condensate obtained by carrying out a partial hydrolysis and condensation of (i) a functional group including alkoxy silane compound including at least a kind of functional groups selected from a mercapto, epoxy, acryloyl, methacryloyl, vinyl, haloalkyl and amino group, (ii) a tetraalkoxysilane compound and if required (iii) other di or trialkoxysilane compound, and (C) modified polymer particles obtained by bonding the polymer particle (A) and the silicone condensate (B), stably included in an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for coatings which can form a low-contamination coating film, which is particularly useful for overcoating, and a method for producing the resin composition for coatings.

[0002]

2. Description of the Related Art Conventionally, the outer coating film of various outer panels for outdoor use, for example, automobiles, railway cars, etc., has an appearance with time due to the influence of dust, sand dust, iron powder, acid rain, etc. in the atmosphere. There is a disadvantage that it gets worse, especially for coatings that are vulnerable to acid rain,
The effect was significant. On the other hand, selection of the crosslinking system of the resin and improvement of the physical properties of the coating film have been studied, but in any case, once the contaminant adheres to the coating film surface, the dirt is difficult to remove and the coating film appearance is impaired. was there.

[0003] As a method for preventing the adhesion of contaminants to a coating film, for example, an antistatic agent for preventing electrostatic adhesion of dust or the like is added to a paint, or an antistatic agent is applied to the surface of a coating film. Accordingly, a method of lowering the surface resistivity of the coating film surface has been proposed. However, conventionally used antistatic agents have essentially poor water resistance, so that their effects have been difficult to maintain in outdoor applications.

Further, as a coating composition excellent in acid rain resistance, there has been proposed a coating composition obtained by adding a condensation reaction product of an alkyl silicate oligomer and a silane coupling agent (hydrolysis product of epoxy-functional silane) to the coating composition. (Japanese Unexamined Patent Publication No.
306328), but the coating film performance was insufficient.

In order to prevent the adhesion of contaminants by developing hydrophilicity on the surface of the coating film while maintaining the performance of the coating film, the present applicant has developed a specific organic functional group as a hydrophilicity-imparting component. A coating composition comprising a silicone compound containing an alkoxy group and an alkoxysilyl group has been developed and previously proposed (for example, JP-A-9-40907, JP-A-9-40908, JP-A-9-40998). 4091
No. 1). According to these coating compositions, hydrophilicity can be imparted to the surface, and a coating film excellent in stain resistance, acid resistance, and the like can be formed. However, since the compatibility between the base resin and the above-mentioned silicone compound in the paint is insufficient, the silicone compound is liable to locally aggregate, and especially when applied to a clear paint for use at room temperature for drying. The resulting clear coating film may become cloudy or crack, making it difficult to satisfy all of the finishing properties, stain resistance and crack resistance of the coating film. In addition, the coating film surface has a drawback that it usually takes three months or more to exhibit hydrophilicity when used outdoors, and there is a need for the development of a coating composition that exhibits hydrophilicity from an early stage.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have now found that a nonaqueous dispersion polymer particle and a specific silicone condensate are contained in a coating composition. When the modified polymer particles that are partially reacted and bonded are present, the formed coating film has dramatically improved compatibility and cracking resistance in the surface layer, and a silicone component as a hydrophilicity-imparting component has been added. It has been found that it is densely dispersed on the coating surface and expresses hydrophilicity from the beginning, and it is possible to satisfy all of the finishing properties, stain resistance and crack resistance of clear coatings for room temperature drying. Thus, the present invention has been completed.

Thus, the present invention provides (A) a hydroxyl value of 20
In the presence of a dispersion stabilizing resin having ~ 200 mg KOH / g, the monomer is polymerized in an organic liquid in which the monomer dissolves but the polymer formed from the monomer does not substantially dissolve. (B) (i) at least one type of functional group selected from a mercapto group, an epoxy group, an acryloyl group, a methacryloyl group, a vinyl group, a haloalkyl group, and an amino group. A functional group-containing alkoxysilane compound having a group, (ii) a tetraalkoxysilane compound and, if necessary, (iii) a di- or trialkoxysilane compound other than the functional group-containing alkoxysilane compound (i) is partially hydrolyzed and condensed. And (C) a modified polymer particle obtained by bonding the polymer particle (A) to the silicone condensate (B) in an organic solvent. There is provided a coating resin composition characterized by comprising been contained.

[0008] The present invention also provides the above resin composition for paints, further comprising a film-forming resin (D) soluble in an organic solvent.

Further, according to the present invention, 0.1 to 50 parts by weight of a silicone condensate (B) is mixed with 100 parts by weight of a resin solid content of polymer particles (A) dispersed in an organic liquid. The resulting mixture is heated to a temperature of 50 to 150 ° C. in an organic solvent to convert the polymer particles (A) into a silicone condensate (B).
And a method for producing the above-mentioned resin composition for a coating, characterized in that the modified polymer particles (C) are formed by partially binding the above.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The components of the coating resin composition of the present invention and the method for producing the coating resin composition will be described in more detail below.

Polymer particles (A) The polymer particles (A) in the coating resin composition of the present invention.
In an organic liquid in which a monomer dissolves but a polymer formed from the monomer does not substantially dissolve in the presence of a dispersion stabilizing resin having a hydroxyl value of 20 to 200 KOH mg / g, Polymer particles dispersed in the organic liquid obtained by polymerizing the monomer.

The dispersion stabilizing resin has a hydroxyl value of 20 to 2
00KOHmg / g, preferably 30 to 180KOHm
g / g, and examples thereof include a hydroxyl group-containing acrylic resin, a hydroxyl group-containing fluororesin, a hydroxyl group-containing polyester resin, and a hydroxyl group-containing alkyd resin.

The hydroxyl group-containing acrylic resin that can be used as the dispersion stabilizing resin has a weight average molecular weight of 1,0.
00 to 100,000, preferably 5,000 to 75,
Acrylic copolymers of 000 are preferred,
It can be produced by subjecting a monomer mixture composed of a hydroxyl group-containing monomer and another monomer copolymerizable with this monomer to solution polymerization in the presence of a radical polymerization initiator.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether
And hydroxyalkylalkenyl ethers such as ter and 2-hydroxyethyl allyl ether.

Other monomers copolymerizable with the above-mentioned hydroxyl-containing monomer include, for example, vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and α-chlorostyrene; methyl (meth) acrylate , Ethyl (meth) acrylate, n- or i-propyl (meth) acrylate, n-, i- or t-butyl (meth) acrylate, hexyl (meth) acrylate
Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth)
Acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate
And alkyl or cycloalkyl esters of acrylic acid or methacrylic acid having 1 to 24 carbon atoms, such as isobutenyl (meth) acrylate; vinyl acetate, vinyl chloride, vinyl ether, acrylonitrile, and methacrylonitrile; Further, so-called macromonomers, which are polymers of one or more of these monomers and have a polymerizable unsaturated group at one end, can also be mentioned as copolymerizable monomers. In the present specification, “(meth) acrylate” means “acrylic”.
Or methacrylate.

Solvents that can be used in the solution polymerization of the above monomer mixture include, for example, alkylbenzene derivatives such as benzene, toluene, and xylene; ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methoxybutyl acetate, and methyl acetoacetate. , Ethyl acetoacetate, methyl cellosolve acetate, cellosolve acetate, diethylene glycol monomethyl ether acetate, carbitol acetate
Acetate solvents such as dioxane; ether solvents such as dioxane, ethylene glycol diethyl ether, ethylene glycol dibutyl ether and diethylene glycol diethyl ether; methanol, ethanol, propanol
, I-propanol, (n-, i-, t-) butano-
Alcohol solvents such as toluene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and these can be used alone or as a mixture of two or more.

Examples of the radical polymerization initiator include benzoyl peroxide, di-t-butylhydroperoxide, t-butylhydroperoxide, cumylperoxide, cumenehydroperoxide, diisopropylbenzene hydroperoxide. , T-butyl par
Peroxides such as oxybenzoate, lauryl peroxide, acetyl peroxide, t-butyl peroxy-2-ethylhexanoate; α, α'-azobisisobutyronitrile, α, α'-azobis- Examples include azo compounds such as 2-methylbutyronitrile, azobisdimethylvaleronitrile, and azobiscyclohexanecarbonitrile.

In the above monomer mixture, the hydroxyl group-containing monomer is 5 to 45% by weight, especially 10 to 35% by weight, and the other monomer copolymerizable therewith is 55 to 95% by weight.
Suitably it is present in the range of weight percent.

The hydroxyl group-containing fluororesin has a weight average molecular weight of 1,000 to 100,000, preferably 5,000 to 75,000, and a fluorine atom content of 1 to 100.
A fluorine-containing copolymer in an amount of 60% by weight, preferably 10 to 30% by weight is suitable. Usually, as the hydroxyl group-containing fluororesin, for example, a fluoroolefin and a hydroxyalkylvinyl ether as main components are used. Accordingly, a fluorinated copolymer obtained by copolymerizing a monomer mixture containing other monomers such as alkyl vinyl ether may be used. The fluorinated copolymer is produced by a production method known per se, for example, a solution polymerization method, and the solution polymerization method can be carried out in the same manner as described for the acrylic copolymer.

In the above-mentioned fluorine-containing copolymer, any fluoroolefin can be used without any particular limitation. Perfluoroolefins, in particular, chlorotrifluoroolefins, tetrafluoroolefins and mixtures thereof are preferred. Examples of the hydroxyalkyl vinyl ether include a hydroxyalkyl vinyl ether having a linear or branched alkyl group having 2 to 5 carbon atoms.
Ter is preferred. Other monomers such as alkyl vinyl ethers include, for example, alkyl vinyl ethers having a cyclohexyl group or a linear or branched alkyl group having 1 to 8 carbon atoms, fatty acid vinyl esters and fatty acid iso-esters. Fatty acid alkenyl esters such as propenyl ester and the like can be used. The content of the fluoroolefin in these monomer mixtures is 10 to
40% by weight, especially 15 to 35% by weight, the content of hydroxyalkyl vinyl ether is 5 to 20% by weight, especially 7 to
17% by weight, and the content of other monomers is 85 to 85%.
A suitable range is 40% by weight, in particular 78 to 58% by weight.

Specific examples of the above fluorine-containing copolymer include:
For example, LUMIFLON LF100, LUMIFLON LF200, LUMIFLON LF300, LUMIFLON LF400, LUMIFLON LF9 of the product "LUMIFLON" series manufactured by Asahi Glass Co., Ltd.
012 etc. are mentioned as a commercial item.

As the hydroxyl group-containing polyester resin, a polyester resin having a weight average molecular weight of 1,000 to 100,000, preferably 3,000 to 65,000 is suitable, and usually, ethylene glycol, butylene glycol, Polyhydric alcohols such as 2,6-hexanediol, neopentyl glycol, trimethylolpropane, and pentaerythritol, and adipic acid, succinic acid, fumaric acid, terephthalic acid, isophthalic acid, phthalic anhydride, hexahydrophthalic anhydride, etc. It can be easily obtained by a condensation reaction with a polyvalent carboxylic acid. The reaction between the polyhydric alcohol and the polycarboxylic acid can be carried out by a method known per se, in which the hydroxyl group is mixed with the carboxyl group in excess.

In the dispersion of the polymer particles (A), the above-mentioned dispersion stabilizing resin must be dissolved, and the particles must be dispersed without being substantially dissolved. Therefore, a low-polarity solvent is advantageously used as the solvent, and the dispersion-stabilizing resin preferably has a low polarity.

The polymer particles (A) are dissolved in an organic liquid in which a monomer is dissolved but a polymer formed from the monomer is substantially insoluble in the presence of the dispersion stabilizing resin. It is obtained by polymerizing a monomer.

As the above-mentioned monomer, at least one of those described above as a hydroxyl-containing monomer constituting the hydroxyl-containing acrylic resin usable as the dispersion stabilizer and other monomers copolymerizable with the hydroxyl-containing monomer can be used. The polymer particles (A) composed of the monomer need not substantially dissolve in an organic liquid as a solvent. Preferably have high polarity. As such a monomer, for example, styrene, acrylonitrile, alkyl methacrylate having an alkyl group having 4 or less carbon atoms (especially methyl methacrylate), and the like are preferable.

In the production of the polymer particles (A), the mixing ratio of the above-mentioned dispersion stabilizing resin to the monomer is generally 5/95 to 70/30, preferably 10/95 by weight ratio of the former / the latter.
It can be in the range of 90-60 / 40.

The organic liquid, which is a solvent used in producing the dispersion of the polymer particles (A), dissolves the dispersion-stable resin and the above-mentioned monomers forming the polymer particles, but forms from the monomers. The polymer particles to be used are substantially insoluble and preferably have a small polarity, for example, aliphatic solvents having relatively low dissolving power such as VM & P naphtha, mineral spirit, solvent kerosene, aromatic naphtha and solvent naphtha. Or aromatic hydrocarbons; n-butane, n-hexane, n-heptane, n-octane, isononane, n-
Aliphatic hydrocarbons such as decane and n-dodecane; and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and cyclobutane are used. If necessary, a small amount of a polar solvent such as an ester solvent, an ether solvent, a ketone solvent, or an alcohol solvent can be used.

When the above monomers are polymerized into polymer particles, a polymerization initiator is blended and the polymerization temperature is adjusted to 40 to 150.
℃, preferably 50 to 110 ℃, the polymerization time is usually 2
It is preferable to set it to about 10 hours.

Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, caproyl peroxide, t
Organic peroxides such as -butyl peroctoate and diacetyl peroxide; azo initiators such as azobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl α, α'-azoisobutyrate; diisopropyl peroxydicarbonate And redox initiators. The concentration of the polymerization initiator is 0.01
Suitably, it is in the range of 10 to 10% by weight, more preferably 0.1 to 5% by weight.

The polymer particles have a glass transition temperature of -20 to 1 in terms of performance and stability in the polymerization reaction.
It is preferably in the range of 00 ° C, more preferably in the range of 0 to 80 ° C, and the average particle size is in the range of 50 to 500 nm, especially 90 to 400 nm. The inside of the polymer particles may be internally crosslinked.

Silicon Condensate (B) In the present invention, the silicone condensate (B) is at least one selected from a mercapto group, an epoxy group, an acryloyl group, a methacryloyl group, a vinyl group, a haloalkyl group and an amino group. Organic functional group-containing alkoxysilane compound (i) having a kind of organic functional group, tetraalkoxysilane compound (ii) and, if necessary, di- or trialkoxysilane other than the above-mentioned organic functional group-containing alkoxysilane compound (i) A partially hydrolyzed condensate of the compound is used.

The alkoxysilane compound (i) containing an organic functional group can be bonded to a silicon atom via a divalent hydrocarbon group having 1 to 10 carbon atoms even if the organic functional group is directly bonded to the silicon atom. They may be combined. As the compound, conventionally known compounds can be used, and specifically, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltributoxysilane, γ-
Mercapto groups such as mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, β-mercaptomethylphenylethyltrimethoxysilane, mercaptomethyltrimethoxysilane, 6-mercaptohexyltrimethoxysilane, and 10-mercaptodecyltrimethoxysilane Containing alkoxysilane compound; γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldi Ethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyltrimethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, 5,6- Epoxyhexyltrimethoxysilane,
Epoxy group-containing alkoxysilane compounds such as 9,10-epoxydecyltrimethoxysilane; γ- (meth) acryloyloxypropyltrimethoxysilane, γ-
(Meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropyltributoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- ( (Meth) acryloyl group-containing alkoxysilane compounds such as (meth) acryloyloxymethyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, 5-hexenyltrimethoxysilane, 9-de Vinyl group-containing alkoxysilane compounds such as senyltrimethoxysilane; γ-chloropropyltrimethoxysilane, γ
-Bromopropyltrimethoxysilane, trifluoropropyltrimethoxysilane, nonafluorohexyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltributoxysilane, γ-aminopropylmethyl Haloalkyl group-containing alkoxysilane compounds such as dimethoxysilane and γ-aminopropylmethyldiethoxysilane; N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-
γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltributoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyl Examples include amino group-containing alkoxysilane compounds such as trimethoxysilane.
It can be used in combination of more than one species.

Among these compounds, in particular, a mercapto group-containing alkoxysilane compound and an epoxy group-containing alkoxysilane compound can be suitably used because of excellent coating properties such as stain resistance and durability.

Examples of the tetraalkoxysilane compound (ii) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like, and these can be used alone or in combination of two or more. Among these, tetramethoxysilane and tetraethoxysilane can be particularly preferably used since the alkoxysilyl group is easily hydrolyzed to form a silanol group and forms a coating film having excellent stain resistance.

When the silicone condensate (B) is produced without using the compound (iii), the compounding ratio of the compounds (i) and (ii) is usually (i) / (ii)
8/1 to 1/19, preferably 2/1 to 1/19 in a molar ratio of
9, and a mixture thereof is subjected to a partial hydrolysis condensation reaction to obtain a silicone compound (B).
Can be obtained. When the amount of the compound (ii) is less than the above range, generally, the obtained silicone condensate (B)
Is reduced in hydrophilicity and inferior in stain resistance and acid resistance. On the other hand, when it is more than the above range, affinity with the polymer particles (A) becomes poor, and when reacting with the polymer particles (A), The stability of the silicone condensate (B) itself is reduced, making it difficult to obtain the modified polymer particles (C), and as a result, the finish of the coating film tends to be reduced.

The silicone condensate (B) can be produced by partially hydrolyzing and condensing a di- or trialkoxysilane compound (iii) in addition to the compounds (i) and (ii). However, by using the di- or trialkoxysilane compound (iii),
It is preferable because flexibility and flexibility can be imparted to the coating film without significantly lowering the hydrophilicity of the coating film.

Di- or trialkoxysilane compound (iii)
Examples thereof include dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane and the like, and these can be used alone or in combination of two or more.

Compounds (i), (ii) and (iii)
As a method for producing the silicone condensate (B) using the components, for example, a mixture of these three components is subjected to a partial hydrolytic condensation reaction; the partial hydrolytic condensate of the compounds (ii) and (iii) is used. Reacting compound (i); compound (i)
And the reaction of compound (ii) with the hydrolysis-condensation product of (iii).
A method of subjecting a mixture of components to a partial hydrolysis condensation reaction is preferred.

In the case of using the di- or trialkoxysilane compound (iii) in the production of the silicone compound (B), the use ratio of the above three components is usually mol%, and the compound (i) is 5 to 80%. Mol%, preferably 10 to 50 mol%, compound (ii) is 10 to 94.9 mol%, preferably 25 to 90 mol%, and compound (iii) is 0.1 to 30 mol%, preferably 1 to 25 mol%. Mol%, and the total use ratio of the compounds (ii) and (iii) is 20 to 95 mol%,
It is preferable that the content is preferably 50 to 90 mol%. The silicone compound (B) can be obtained by using the above three components in such an amount as described above and subjecting them to the partial hydrolysis condensation reaction as described above. When the use ratio of the compound (i) is less than 5 mol%, the affinity for the polymer particles (A) becomes poor, and when it exceeds 80 mol%, the hydrophilicity tends to decrease. Is 1
If the amount is less than 0 mol%, hydrophilicity is reduced, and stain resistance and acid resistance are inferior. If the amount exceeds 94.9 mol%, affinity with the base resin (A) becomes poor, and the base resin (A) and During the reaction, the stability of the silicone compound (B) itself is reduced, and it is difficult to obtain the reaction product (C). As a result, the finish of the coating film tends to be reduced. Further, when the compound (iii) is less than 0.1 mol%, the resulting coating film is not provided with flexibility and cracks are easily generated. When it exceeds 30 mol%, hydrophobicity becomes too strong and hydrophilicity becomes too high. It is liable to be insufficient and stain resistance is insufficient.

The above-mentioned silicone compound (B) preferably has an average degree of polymerization of 3 to 100, preferably 5 to 80. If the degree of polymerization is less than 3, it will not volatilize or impart sufficient hydrophilicity to the surface of the coating film, while if it exceeds 100, it will be difficult to obtain a reaction product (C) which is reacted with the base resin (A). As a result, the finish of the coating film tends to decrease.

The above-mentioned silicone compound (B) can be produced according to a method known per se, for example, in the presence of a hydrolysis catalyst, in the presence of the above-mentioned compounds (i) and (ii), or compounds (i) and (ii). ) And (iii) can be carried out by adding water and performing a partial cohydrolytic condensation reaction at room temperature to 150 ° C or lower. In the partial co-hydrolysis condensation, the degree of the partial co-hydrolysis is, for example, that the average degree of polymerization is 0 when not hydrolyzed at all,
In the case of 0% hydrolysis, the degree of polymerization is closely related to the degree of polymerization so that the degree of polymerization is too high to cause gelation, and is adjusted within the range of the average degree of polymerization described above.

As the hydrolysis / condensation catalyst to be used, various catalysts known per se can be used. For example, organic acids such as acetic acid, butyric acid, maleic acid and citric acid; and inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid. Acids; basic compounds such as triethylamine; organic metal salts such as tetrabutyl titanate and dibutyltin dilaurate; KF, NH ₄ F
And the like, and these may be used alone or in combination of two or more. Of these, fluorine-containing compounds are excellent in the function of accelerating condensation of silanol groups having high reaction activity, and thus are suitable for synthesizing compounds containing only a small amount of silanol groups. This is particularly preferable because the property is improved. Usually, the amount of the catalyst used is suitably in the range of 0.0001 to 1 mol%.

In conducting the above partial cohydrolysis condensation reaction, an organic solvent may be used, if necessary. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol and t-butanol; ketones such as acetone and methyl isobutyl ketone; ethers such as dibutyl ether and the like. And esters such as ethyl acetate; and aromatics such as toluene. Particularly, organic solvents such as methanol, ethanol and acetone are preferred.

The amount of water used in the above-mentioned partial cohydrolysis condensation reaction is determined by the desired degree of polymerization. If added in excess, the alkoxy groups are destroyed and eventually gelled, so that You need to decide. In particular, when a fluorine-containing compound is used as a catalyst, the degree of polymerization can be determined by the amount of water to be added because the fluorine-containing compound has the ability to completely promote hydrolysis and condensation, and the setting of an arbitrary molecular weight can be made. Therefore, in order to adjust the target substance having an average degree of polymerization M, it is sufficient to use (M-1) mol of water with respect to M mol of the alkoxysilane compound. In the case of other catalysts, it is necessary to slightly increase the amount.

Modified Polymer Particles (C) The modified polymer particles (C) in the composition of the present invention are obtained by mixing the hydroxyl group and the silicone condensate (B) in the polymer particles (A).
This is obtained by partially reacting an alkoxysilyl group therein.

In the production of the modified polymer particles (C), a mixture of the dispersion of the polymer particles (A) and the silicone condensate (B) is usually heated at a temperature of 50 to 150 ° C. to remove alcohol. −
Reaction can be carried out. In the dealcoholization reaction, if necessary, one or more kinds of hydrolysis-condensation catalysts that can be used in the production of the silicone compound (B) may be used.

In the production of the modified polymer particles (C), the compounding ratio of the silicone condensate (B) is determined based on the point of the stain resistance, water resistance, acid resistance and alkali resistance of the coating film. 0.1 to 50 per 100 parts by weight of the solid content of the particles (A)
It is preferred that the amount be within the range of 1 part by weight, preferably 1 to 20 parts by weight.

In the present invention, the modified polymer particles (C) produced as described above are mixed with the polymer particles (A) in a separate container.
And the silicone condensate (B), but preferably, the silicone condensate (B) is used in an amount of 0.1 to 100 parts by weight of the resin solid content of the polymer particles (A). It is desirable that the mixture containing 50 parts by weight of the mixture is usually heated at a temperature of 50 to 150 ° C. and subjected to a de-alcohol reaction to produce the modified polymer particles (C) partially. . In this case, 1 to 50% by weight, preferably 1 to 30% by weight, of the solid content of the silicone condensate (B) to be blended is consumed for the production of the modified polymer particles (C). It is desirable from the viewpoint of the effect of improving the compatibility and compatibility, the stain resistance of the coating film, the finish, the water resistance and the like.

The resin composition for a coating composition of the present invention is a resin component of the coating composition and may be composed of the polymer particles (A), the silicone condensate (B) and the modified polymer particles (C). Preferably, the composition may further contain the following film-forming resin (D) and a crosslinking agent (E) which are soluble in an organic solvent, if necessary.

The film-forming resin (D) is a resin capable of forming a film, other than the components (A), (B) and (C) and the crosslinking agent (E) described below. Examples of (D) include a hydroxyl group-containing organic resin that can be dissolved in an organic solvent, and a reaction product obtained by reacting the hydroxyl group-containing organic resin with the silicone condensate (B) and partially bonding them. . By containing the film-forming resin (D), it is possible to increase the degree of freedom with respect to the required film performance and to improve the finish of the film.

The hydroxyl-containing organic resin usable as the film-forming resin (D) includes a hydroxyl value of 20 to 200.
mgKOH / g, preferably 30-180 mgKOH /
g and a weight average molecular weight of 1,000 to 100,00
Organic resins in the range of 0, preferably in the range of 5,000 to 75,000 can be suitably used, and can be used, for example, as a dispersion stabilizing resin used in the polymerization of the polymer particles (A). Can be listed as suitable ones. Examples of the resin type of the hydroxyl group-containing organic resin include an acrylic resin, a fluorine resin, a polyester resin, and an alkyd resin. Among them, an acrylic resin and a fluorine-containing copolymer having a fluorine atom content of 1 to 60% by weight are exemplified. Is preferred. These can be used alone or in combination of two or more.

The reaction product which can be used as the film-forming resin (D) is obtained by mixing the hydroxyl-containing organic resin and the silicone condensate (B) with 100 parts by weight of a resin solid content of the hydroxyl-containing organic resin. Of a silicone condensate (B) in an amount of 0.1 to 50 parts by weight, preferably 1 to 35 parts by weight, usually in an organic solvent in an amount of 50 to 15 parts by weight.
It can be obtained by heating at a temperature of 0 ° C. and causing a dealcohol reaction to partially bond the hydroxyl group-containing organic resin and the silicone condensate (B). At this time, 1 to 50% by weight, preferably 1 to 30% by weight of the solid content of the silicone condensate (B) to be blended constitutes a combined product of the hydroxyl group-containing organic resin and the silicone condensate (B). Consumption is desirable from the viewpoints of production stability, improved compatibility, stain resistance of the coating film, finish, water resistance and the like.

When the coating resin composition of the present invention contains a film-forming resin (D), the compounding amount of the film-forming resin (D) is determined according to the above components (A), (B) and (C). ) And (D), the solid content is usually 98% by weight or less, preferably 10 to 80% by weight.

Examples of the crosslinking agent (E) include polyisocyanate compounds, blocked polyisocyanate compounds, and amino resins such as melamine resins. These can be used alone or in combination of two or more.

As the above polyisocyanate compound,
For example, aliphatic diisocyanates such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4 (or 2,6) -diisocyanate, 4,4'-methylenebis ( Cycloaliphatic diisocyanates such as cyclohexyl isocyanate) and 1,3- (isocyanatomethyl) cyclohexane; aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate; lysine triisocyanate and the like Organic polyisocyanate itself such as tri- or higher polyisocyanate, or each of these organic polyisocyanates and polyhydric alcohol Adducts of low molecular weight polyester resin or water, etc., or cyclic polymer of the organic diisocyanate comrades such described above (e.g., isocyanurates), and the like biuret type adducts. Of these, isocyanurate of hexamethylene diisocyanate is preferred. These can be used alone or in combination of two or more.

When the coating composition using the coating resin composition of the present invention is to be a low-temperature curing coating at room temperature to about 100 ° C. or lower, it is preferable to use the above polyisocyanate compound as a crosslinking agent. However, in the case of baking conditions exceeding 100 ° C., a blocked polyisocyanate compound or an amino resin can be suitably used in addition to the polyisocyanate compound.

The blocked polyisocyanate compound is obtained by blocking the isocyanate group of the polyisocyanate with a blocking agent. Examples of the blocking agent include phenols such as phenol, cresol and xylenol; ε-caprolactam; δ
Lactams such as valerolactam, γ-butyrolactam, β-propiolactam; methanol, ethanol, n
-Or i-propyl alcohol, n-, i- or t-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Alcohols such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether and benzyl alcohol; formamidoxime, acetoaldoxime, acetoxime,
Oximes such as methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, and cyclohexane oxime; blocking agents such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, and acetylacetone are preferably used. it can. The isocyanate group of the polyisocyanate can be easily blocked by mixing the polyisocyanate with the blocking agent.

Examples of the melamine resin usable as the crosslinking agent (E) include a methylolated melamine resin obtained by reacting melamine with an aldehyde. Examples of the aldehyde include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde. Further, those obtained by etherifying the methylolated melamine resin with one or more alcohols can also be used. Examples of the alcohol used for the etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, Monohydric alcohols such as isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol and 2-ethylhexanol are exemplified. Among these, a melamine resin obtained by etherifying at least a part of the methylol group of the methylolated melamine resin with a monohydric alcohol having 1 to 4 carbon atoms is preferable.

When the crosslinking agent (E) is blended in the coating resin composition, when the crosslinking agent is a polyisocyanate compound or a blocked polyisocyanate compound, the amount of the crosslinking agent is free or blocked. The isocyanate group (NCO) is usually 0.2 to 2.0, preferably 0.5 to 1 at an equivalent ratio of NCO / OH to the hydroxyl group (OH) in the resin composition for coating. It is appropriate to set it within the range of 0.5.

When the crosslinking agent is a polyisocyanate, the reaction between the resin composition for coating and the polyisocyanate compound occurs when the resin composition is mixed with the polyisocyanate compound. It is preferable to use a liquid type paint and to mix both at the time of use.

When the cross-linking agent is an amino resin such as a melamine resin, the mixing ratio of the resin composition for coating and the amino resin is such that the former / the latter is 90/10 in terms of solid content weight ratio.
Suitably, it is in the range of ６０60/40, especially 80 / 20-70 / 30.

The resin composition for a coating material of the present invention comprises the above-mentioned polymer particles (A), silicone condensate (B) and modified polymer particles (C) as essential components. D) and a crosslinking agent (E), and the resin composition for coating of the present invention can be dissolved or dispersed in an organic solvent and used as a coating composition.

The coating composition containing the coating resin composition of the present invention as a resin component contains an organic solvent, and if necessary, in addition to the resin component and the organic solvent, a pigment, a curing catalyst, and the like. And additives such as an ultraviolet absorber, an antioxidant, a coating surface adjusting agent, a fluidity adjusting agent, and a wax.

The above coating composition can be used not only as a clear top coating, but also as a colored top coating by incorporating a coloring pigment or the like.

The above coating composition can be applied to a substrate and dried at room temperature or by heating to form a coating film. Examples of the base material include inorganic base materials such as slates and concretes; iron, aluminum, zinc, stainless steel, and the like.
And metal substrates such as those obtained by surface-treating them with chromic acid, zinc phosphate and the like; and plastic substrates such as polyvinyl chloride, polyethylene terephthalate, and polyethylene. Substrates coated with a primer, an intermediate coating, a top coating or the like can be used as necessary.

The coating of the above coating composition can be carried out by means known per se, such as, for example, spray coating, brush coating, roller coating and dip coating. The coating amount is usually 1 to 100 μm in dry film thickness, preferably 10 to 60 μm.
It is desirable to be within the range of μm.

The coating film formed by the coating composition is as follows:
When exposed outdoors, the water contact angle decreases early (within one month) due to the action of rain, etc., but the surface of the coating film before exposure is treated with acid (2.5% by weight sulfuric acid in 20 ° C for 24 hours). After immersion, the attached acid is washed with water and dried), and the final contact angle of water of the exposed coating film can be estimated by measuring the water contact angle.

[0068]

The present invention will now be described more specifically with reference to examples. In the description, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

Production Preparation Example 1 of Hydroxyl-Containing Acrylic Resin A reactor equipped with a stirrer, a thermometer, a thermostat, a reflux condenser and a dropping pump was charged with 30 parts of isobutyl acetate and 50 parts of toluene. After heating to reflux temperature with stirring, 10 parts of styrene, 30 parts of isobutyl methacrylate, 10 parts of t-butyl methacrylate
Parts, cyclohexyl methacrylate 10 parts, 2-ethylhexyl methacrylate 14 parts, methacrylic acid 1 part, 2 parts
A mixture of 25 parts of -hydroxyethyl methacrylate and 6 parts of t-butylperoxy 2-ethylhexanoate as a polymerization initiator was added dropwise at a constant rate over 3 hours at the same temperature. After completion of the dropwise addition, the mixture was kept at the same temperature for 2 hours and stirring was continued.
0.02 parts of -butylpyrocatechol and 0.1 parts of N, N-dimethylethanolamine were added and reacted to introduce a polymerizable double bond having a nonvolatile content of 55% and a viscosity of G (Gardner foam viscosity, 25 ° C.). Thus, a hydroxyl group-containing acrylic resin A solution was obtained. The obtained resin (solid content) has a hydroxyl value of 108
It was mgKOH / g and the weight average molecular weight was 6,000 (see Table 1 below).

Preparation Example 2 A reactor equipped with a stirrer, a thermometer, a thermostat, a reflux condenser, and a dropping pump was charged with 30 parts of isobutyl acetate and 50 parts of toluene, heated in a nitrogen stream, and stirred. After raising the temperature to the reflux temperature, 10 parts of styrene, 20 parts of n-butyl methacrylate, 34 parts of isobutyl methacrylate
Part, n-butyl acrylate 5 parts, 2-ethylhexyl methacrylate 15 parts, methacrylic acid 1 part, 2-hydroxyethyl methacrylate 15 parts, and 2,2'-azobisisobutyi as a polymerization initiator A mixture of lonitrile (2 parts) was added dropwise at the same temperature at a constant rate over 3 hours. After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, and then 0.8 parts of glycidyl methacrylate, 0.02 parts of 4-t-butylpyrocatechol and 0.1 part of N, N-dimethylethanolamine were added. At least, non-volatile content 55%, viscosity L
A hydroxyl group-containing acrylic resin B solution having a polymerizable double bond (Gardner foam viscosity, 25 ° C.) was obtained. The obtained resin (solid content) had a hydroxyl value of 65 mgKOH / g and a weight average molecular weight of 16,000 (see Table 1 below).

Preparation Example 3 The same operation as in Preparation Example 2 was carried out except that the same reactor and raw materials as in Preparation Example 2 were used, and the amounts of the mixed solution to be dropped and the post-addition raw materials were changed as shown in Table 1 below. And the nonvolatile content 5
A hydroxyl group-containing acrylic resin C solution having a polymerizable double bond of 0% and viscosity XY (Gardner foam viscosity, 25 ° C.) was obtained. The obtained resin (solid content) has a hydroxyl value of 17 mgK.
OH / g and weight average molecular weight was 45,000.

[0072]

[Table 1] Production Example 1 of Polymer Particle Dispersion (A) In a reactor equipped with a stirrer, a thermometer, a thermostat, a reflux condenser, and a dropping pump, 93 parts of heptane and a hydroxyl group as a dispersion-stabilized resin solution were contained. Acrylic resin A solution 9
8 parts, heated in a nitrogen stream, heated to reflux temperature with stirring, then 13 parts of styrene, methyl methacrylate 2
A mixture of 8 parts, 34 parts of acrylonitrile, 25 parts of 2-hydroxyethyl acrylate and 2 parts of 2,2'-azobisisobutyronitrile as a polymerization initiator was dropped at a constant rate over 3 hours. After the completion of the dropwise addition, stirring was continued at the same temperature for 2 hours to obtain a polymer particle dispersion liquid (A-1) having a nonvolatile content of 53% and a viscosity A (Gardner foam viscosity, 25 ° C.). This polymer particle dispersion is milky white, and the particle size of the polymer particles by an electron microscope is 0.15 to 0.20 μm.
Met. The viscosity of this polymer particle dispersion is A (Gardner foam viscosity, 25 ° C.), and the blending weight ratio of the dropping monomer / dispersion stabilizing resin for polymer particle production is 65/3.
5 and storage for 3 months at room temperature showed no change and good storage stability (see Table 2 below).

Production Examples 2 to 5 The same procedures as in Production Example 1 were repeated except that the types and amounts of the heptane, the dispersion-stable resin solution, and the mixture to be dropped were as shown in Table 2 below, and the production of each polymer was repeated. A particle dispersion was obtained.

[0074]

[Table 2] (Note) in Table 2 has the following meaning. (Note 1) Lumiflon LF200: manufactured by Asahi Glass Co., Ltd.

The hydroxyl value of the polymer solution and the resin solid is about 5
0 mg KOH / g.

Production of Silicone Condensate (B) Production Example 6 1000 m equipped with thermometer, nitrogen inlet tube and dropping funnel
In a 1 l reaction vessel, 47.3 g (0.20 mol) of γ-glycidoxypropyltrimethoxysilane, 114.0 g (0.75 mol) of tetramethoxysilane, 6.8 g (0.05 mol) of methyltrimethoxysilane, and methanol −
160 g (5 mol) and potassium fluoride 0.06 g
(0.001 mol) and water at room temperature with stirring.
1 g (0.95 mol) was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, and further heated and stirred under reflux of methanol for 2 hours. Thereafter, the solvent and water were removed by evaporating the low boiling point components under reduced pressure, and the residue was filtered to obtain 113 g of a colorless transparent liquid silicone condensate (B-1). As a result of GPC measurement of this silicone condensate (B-1), the average degree of polymerization was 20.5 (set degree of polymerization = 20), which was almost as set. When the epoxy equivalent was measured by an epoxy ring opening method using hydrochloric acid, it was 625 g / mol (set value: 622 g / mol), and it was confirmed that a predetermined amount of epoxy groups had been introduced. When the amount of the alkoxyl group was determined by the alkali cracking method, 45.5%
(Theoretical 46.1%). From the results of the ¹ H-NMR measurement, the structure of the obtained silicone condensate (B-1) was a structure represented by the following average composition formula (see Table 3 below).

[0077]

Embedded image Production Examples 7 to 9 The same as Production Example 6 except that the composition of the organic functional group-containing alkoxysilane, alkyl trialkoxysilane, tetraalkoxysilane and the catalyst used in Production Example 6 was as shown in Table 3 below. The operation was performed to obtain silicone condensates (B-2) to (B-4). The amounts in Table 3 are expressed in molar units.

[0078]

[Table 3] Production Example 1 of Modified Polymer Particle-Containing Resin Composition Example 1 In a reaction vessel equipped with a thermometer, a stirrer, a thermostat and a reflux condenser, a dispersion of polymer particles having a nonvolatile content of 53% obtained in Production Example 1 ( A-1) 189 parts were charged, and 20 parts of the silicone condensate (B-1) obtained in Production Example 6 was added with stirring, the temperature was raised to 100 ° C. over about 30 minutes, and the temperature was maintained for 5 hours. The polymer condensate (B-
A resin composition liquid containing the modified polymer particles bonded to 1) was obtained. In this resin composition liquid, 20.5% of the added silicone condensate (B-1) was consumed for producing modified polymer particles (see Table 4 below).

The consumption rate of this silicone condensate was calculated as follows. First, a polyisocyanate compound (“Corone-
A mixture of EH "(trade name, manufactured by Nippon Polyurethane Co., Ltd.) and an isocyanate group equivalent to the hydroxyl group amount of the resin composition was added to a tin plate having a dry film thickness of about 40.
μm and cured in a desiccator at a humidity of 25% or less at room temperature for 7 days, and then the cured film was extracted with acetone for 6 hours under reflux to obtain a cured film which was not extracted. The residual ratio (G1)% was determined. Before the above reaction, a mixture of the polymer particle dispersion (A-1) and the silicone condensate (B-1) was mixed with "colonate EH" to prepare the polymer particle dispersion (A-1). In the same manner as described above, the isocyanate group was blended in an amount equivalent to the amount of the hydroxyl group in the solid, and applied, cured, and then extracted with acetone.
The residual ratio (G2)% of the cured film that was not extracted was determined.
The polyisocyanate compound reacts with hydroxyl groups based on the polymer particles, but does not substantially react with the silicone condensate. The consumption rate was calculated by the following equation.

Consumption rate (%) = ｛(G1-G2) / (10
0-G2)｝ × 100 Examples 2 to 5 and Comparative Examples 1 to 4 In Example 1, each resin composition liquid was obtained in the same manner as in Example 1 except that the formulation and reaction conditions shown in Table 4 below were used. Was. In Examples 2 to 5 and Comparative Examples 1 to 3, modified resin particle-containing resin composition liquids were obtained, and in Comparative Example 4, modified resin composition liquids were obtained. Table 4 shows the properties of the obtained resin composition liquids.

[0081]

[Table 4] Examples 6 to 13 and Comparative Examples 5 to 11 of the coating composition Each of the resin composition liquids obtained in Examples 1 to 5 and Comparative Examples 1 to 4, “Acridic A-801” (Dainippon Ink Chemical A hydroxyl group-containing acrylic resin solution having a solid content of 50%, manufactured by Kogyo Co., Ltd., and a hydroxyl value of 100 mgKOH /
g) and a polyisocyanate compound ("Coronate E").
H "(trade name, manufactured by Nippon Polyurethane Co., Ltd.) in a composition shown in Table 5 below, followed by stirring.
Each coating composition was prepared by adjusting the viscosity for 3 to 14 seconds (Ford Cup # 4/25 ° C). Each of the obtained coating compositions was subjected to the following coating film performance test.

Coating performance test Aminoacrylic resin clear paint is applied on the electrodeposited mild steel sheet, and the coated surface baked at 140 ° C. for 20 minutes is polished with a fine polishing compound. A paint (acrylic urethane resin) is spray-painted so as to have a dry film thickness of about 17 μm.
After setting the coating composition for about 5 minutes, each of the above coating compositions was spray-coated so that the dry film thickness was about 40 μm, and the coating composition was allowed to dry at room temperature for 7 days to prepare each test coated plate. Each test coated plate obtained was tested according to the following test method. The test results are shown in Table 5 below.

Test Method (* 1) Smoothness of Painted Surface: The condition of the painted surface was visually observed and judged according to the following evaluation criteria.

○: Yuzu skin, good smoothness without unevenness, Δ
X indicates that the smoothness is slightly inferior, and x indicates that the skin is smooth, and unevenness is observed and the smoothness is inferior.

(* 2) Coating surface gloss: JIS K5400
Specular reflectance was measured at a reflection angle of 60 degrees according to 7.6 (1990).

(* 3) Acid resistance: 0.5% of 40% sulfuric acid aqueous solution
ml was dropped on the coated surface and heated at 70 ° C. for 20 minutes.
After washing with water, the state of the coated surface was evaluated.は indicates no abnormality at all, ツ indicates slight gloss and swelling are observed, and X indicates significant gloss and swelling are observed.

(* 4) Initial water contact angle: A water drop of 0.03 cc of deionized water was dropped on the surface of the coating film of the initial test coated plate, and after 3 minutes in a room at 20 ° C., manufactured by Kyowa Chemical Co., Ltd. The measurement was performed using a contact angler-DCAA type.

(* 5) Water contact angle after acid treatment: The test coated plate was immersed in 2.5% sulfuric acid at 20 ° C. for 24 hours, and then the attached sulfuric acid was washed with water and dried. A drop of 0.03 cc of deionized water was dropped on the surface of the coating film using a Contact Angler DCAA type manufactured by Co., Ltd., and the measurement was performed 3 minutes after dropping in a room at 20 ° C.

(* 6) Accelerated weathering test: A QUV accelerated backpack test using an accelerated weathering tester manufactured by Q Panel.
The test conditions were (ultraviolet irradiation 16 hours / panel temperature 60 ° C.
(Water condensation 8 hours / panel temperature 50 ° C.) as one cycle, and the coating film was evaluated after 1512 hours (63 cycles). ○ indicates that no crack was observed in the coating film, and X indicates that crack was observed in the coating film.

(* 7) Outdoor exposure test: At Kansai Paint Co., Ltd.'s Tokyo Plant located in Minamirokugo, Ota-ku, Tokyo, a test painted plate was installed at an angle of 30 ° on the south side. Each of the test coated plates exposed for one month and three months was evaluated for the stain on the coated surface and the water contact angle without adjusting the coated surface such as washing with water.

Stain on coated surface: The degree of stain on the coated surface with respect to the initial coated plate was evaluated according to the following criteria. ◎ indicates that almost no stain is recognized, ○ indicates that slight stain is recognized, Δ indicates that considerable stain is recognized, and X indicates that significant stain is observed.

Water contact angle: The exposed test coated plate was acid-treated,
The measurement was performed in the same manner as in the above (* 4) without washing with water.

[0093]

[Table 5]

[0094]

According to the present invention, a modified polymer particle obtained by reacting a polymer particle with a part of a specific silicone condensate is present in a resin composition for coating. A coating film formed from a coating material containing the coating resin composition as a resin component has dramatically improved compatibility and crack resistance in the surface layer, and the silicone component, which is a hydrophilicity-imparting component, is not coated on the coating film surface. It is finely dispersed so that the finish, stain resistance, and crack resistance can all be satisfied. The paint containing the resin composition for a paint of the present invention as a resin component can be applied to any of a baking type paint and a normal dry type paint, and is particularly useful in a normal dry type clear application.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 CD091 CG141 CG142 CH122 DG262 DL022 DL031 DL032 DL052 DL072 DL082 DL092 EA011 EA012 GA03 JC31 JC32 JC34 JC35 JC36 KA03 MA02 MA07 MA10 MA14 NA05 PA07

Claims (10)

[Claims] (A) a hydroxyl value of 20 to 200 mg KOH
/ G in the presence of a dispersion-stabilizing resin, the monomer is dissolved, but the polymer formed from the monomer is substantially insoluble in an organic liquid by polymerizing the monomer. (B) (i) at least one functional group selected from a mercapto group, an epoxy group, an acryloyl group, a methacryloyl group, a vinyl group, a haloalkyl group and an amino group; A functional group-containing alkoxysilane compound having (ii) a tetraalkoxysilane compound and, if necessary, (iii) a di- or trialkoxysilane compound other than the functional group-containing alkoxysilane compound (i) is partially hydrolyzed and condensed. A silicone condensate, and (C) the polymer particles (A) are mixed with the silicone condensate (B).
A resin composition for coatings, characterized in that modified polymer particles formed by bonding to an organic solvent are stably contained in an organic solvent. 2. The resin composition according to claim 1, wherein the dispersion stabilizing resin is an acrylic copolymer or a fluorinated copolymer having a weight average molecular weight of 1,000 to 100,000. 3. The coating resin composition according to claim 1, wherein the silicone condensate (B) has an average degree of polymerization of 3 to 100. 4. The method according to claim 1, further comprising a film-forming resin (D) soluble in an organic solvent.
The coating resin composition according to any one of the above. 5. The film-forming resin (D) is a hydroxyl-containing organic resin having a weight average molecular weight in the range of 1,000 to 100,000 and a hydroxyl value in the range of 20 to 200 mgKOH / g. The resin composition for a coating according to claim 4. 6. A film-forming resin (D) having a weight-average molecular weight of 1,000, selected from an acrylic copolymer and a fluorine-containing copolymer having a fluorine atom content of 1 to 60% by weight.
0 to 100,000 and a hydroxyl value of 20
A reaction in which a hydroxyl group-containing organic resin within a range of from about 200 mgKOH / g is reacted with the silicone condensate (B), and the hydroxyl group-containing organic resin is partially bonded to the silicone condensate (B). The composition of claim 4, which is a product. 7. The coating resin composition according to claim 1, further comprising a crosslinking agent (E). 8. The crosslinking agent (E) is a polyisocyanate compound, and the polyisocyanate compound is used in an amount of 0.2 to 2.0 in terms of an equivalent ratio of NCO / OH to hydroxyl groups (OH) in the resin composition for coating. The coating resin composition according to any one of claims 1 to 6, wherein the resin composition is contained in such a ratio as to fall within the range. 9. A mixture obtained by mixing 0.1 to 50 parts by weight of a silicone condensate (B) with 100 parts by weight of a resin solid content of polymer particles (A) dispersed in an organic liquid. Heating in an organic solvent to a temperature of 50-150 ° C.,
The polymer particle (A) is partially bonded to the silicone condensate (B) to form a modified polymer particle (C), according to any one of claims 1 to 3, wherein A method for producing a resin composition for a paint. 10. The silicone condensate (B) in a mixture of the polymer particles (A) and the silicone condensate (B).
10. The method according to claim 9, wherein the reaction is performed so that about 50% by weight constitutes the modified polymer particles (C).