JP3190162B2 - Curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable resin composition. More specifically, the present invention relates to a curable resin composition capable of imparting coating properties such as excellent blocking resistance and thixotropy to interior and exterior of buildings, automobiles, and home electric appliances that require weather resistance and durability.

[0002]

2. Description of the Related Art Conventionally, as a paint for interior and exterior of buildings, automobiles, home electric appliances, etc., it is necessary to form a coating film exhibiting excellent weather resistance, stain resistance, and adhesion to inorganic base materials. Because of their ability, those mainly comprising a solution-type acrylic copolymer containing a hydrolyzable silyl group are widely used.

[0003] However, the coating film formed from the coating material has a drawback that the coating film is inferior in blocking resistance such that marks are left when the coating films are superimposed immediately after formation. Also, when trying to form a thick coating film using the paint, sagging occurs, poor workability, in order to prevent such sagging,
When a large amount of a thixotropic agent is incorporated into a coating, there is a problem that the gloss and weather resistance of the formed coating film are reduced.

[0004]

Therefore, the present inventor has proposed:
As a result of intensive studies in view of the above prior art, it contains fine particles of an emulsion polymer containing a specific hydrolyzable silyl group and a solution-type acrylic copolymer containing a specific hydrolyzable silyl group. The present inventors have finally found from the resin composition that it is possible to form a coating film having excellent gloss and weather resistance, as well as significantly improved blocking resistance and thixotropy, and completed the present invention.

[0005]

That is, the present invention provides a compound represented by the general formula (I):

[0006]

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Wherein R ¹ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, X ¹ is a halogen atom, an alkoxy group, a hydroxy group, an acyloxy group, An aminooxy group, a phenoxy group, a thioalkoxy group or an amino group, a represents an integer of 0 to 2 (however, when R ¹ and X ¹ each are 2 or more, they are the same or different); Fine particles (A) of an emulsion polymer containing a hydrolyzable silyl group represented by the formula (A), containing at least one hydrolyzable silyl group represented by the general formula (I) obtained by a solution polymerization method in one molecule. The present invention relates to a curable resin composition containing an acrylic copolymer (B) and a curing catalyst (C).

[0008]

The curable resin composition of the present invention has the general formula (I) as described above:

[0009]

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(Wherein, R ¹ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, X ¹ is a halogen atom, an alkoxy group, a hydroxy group, an acyloxy group, An aminooxy group, a phenoxy group, a thioalkoxy group or an amino group, a represents an integer of 0 to 2 (however, when R ¹ and X ¹ each are 2 or more, they are the same or different); Fine particles (A) of an emulsion polymer containing a hydrolyzable silyl group represented by the formula (A), containing at least one hydrolyzable silyl group represented by the general formula (I) obtained by a solution polymerization method in one molecule. It contains an acrylic copolymer (B) and a curing catalyst (C).

The coating film formed by using the curable resin composition of the present invention exhibits excellent blocking resistance and thixotropy, and in the resin composition, the fine particles (A) and the acrylic copolymer ( By forming a crosslinked structure with B), it has good gloss and weather resistance.

The emulsion polymer containing a hydrolyzable silyl group represented by the general formula (I) for obtaining the fine particles (A) used in the present invention (hereinafter referred to as emulsion polymer (A)) includes: There is no particular limitation, and examples thereof include emulsions containing a hydrolyzable silyl group represented by the general formula (I), such as an epoxy resin, a polyester resin, a polyether resin, an acrylic resin, and a fluororesin. Among these, an emulsion of an acrylic resin is preferred from the viewpoint that a coating film formed using the obtained curable resin composition has excellent weather resistance and chemical resistance and has a wide range of resin designs.

The method for preparing the emulsion polymer (A) is not particularly limited. For example, a vinyl monomer containing a hydrolyzable silyl group represented by the general formula (I) (hereinafter referred to as monomer (A)) A-1)) and other vinyl monomers copolymerizable therewith (hereinafter referred to as monomer (A-
The method 2)) is preferred from the viewpoint that the emulsion polymer (A) can be easily obtained.

In the general formula (I), the aryl group represented by R ¹ is preferably, for example, one having 6 to 10 carbon atoms, and the aralkyl group is, for example, one having 7 to 15 carbon atoms. preferable.

Specific examples of the monomer (A-1) include, for example,

[0016]

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General formula (II) such as:

[0018]

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[0019] (wherein, R ¹ and a are as defined above, R ²
Represents a hydrogen atom or a methyl group, and X ² represents a halogen atom).

[0020]

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General formula (III) such as:

[0022]

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Wherein R ¹ , R ² , X ² and a are the same as above, and n is an integer of 1 to 12;

[0024]

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General formula (IV) such as:

[0026]

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Wherein R ¹ , R ² and a are the same as above, and R ³ is an alkyl group having 1 to 16 carbon atoms;

[0028]

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General formula (V) such as:

[0030]

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(Wherein R ¹ , R ² , R ³ , a and n are the same as those described above);

[0032]

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General formula (VI) such as:

[0034]

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Wherein R ¹ , R ² , R ³ , a and n are as defined above;

[0036]

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Formula (VII) such as:

[0038]

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(Wherein R ¹ , R ² , R ³ , a and n are the same as those described above);

[0040]

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General formula (VIII) such as:

[0042]

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(Wherein R ¹ , R ² , R ³ and a are the same as defined above);

[0044]

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General formula (IX) such as:

[0046]

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(Wherein R ¹ , R ² , R ³ , a and n are the same as those described above);

[0048]

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General formula (X) such as:

[0050]

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(Wherein R ¹ , R ² , R ³ , a and n are the same as above, and R ⁴ is —CH ₂ O— or —CH ₂ OCO
A compound represented by-);

[0052]

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General formula (XI) such as:

[0054]

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Wherein R ¹ , R ² , R ³ , a and n are the same as above, and p represents an integer of 1 to 12, and the like. These can be used in combination. Among these, alkoxysilyl group-containing vinyl monomers are preferred in view of easiness of handling, cost, and generation of reaction by-products.

The monomer (A-2) is not particularly restricted but includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate and t-butyl. (Meth) acrylate monomers such as (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate; trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, and perfluorocyclohexyl (meth) acrylate , 2,2,3,3-tetrafluoropropyl methacrylate, β- (perfluorooctyl) ethyl (meth)
Fluorine-containing vinyl monomers such as acrylates; aromatic hydrocarbon-based vinyl monomers such as styrene, α-methylstyrene, chlorostyrene, 4-hydroxystyrene, and vinyltoluene; acrylic acid, methacrylic acid, maleic acid, and anhydride Α, β-ethylenically unsaturated carboxylic acids such as maleic acid, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid, citraconic acid; polymerizable carbon-carbon double bonds such as styrenesulfonic acid and vinylsulfonic acid; Acids or salts thereof such as alkali metal salts, ammonium salts and amine salts; acid anhydrides such as maleic anhydride and half esters thereof with alcohols having a linear or branched chain having 1 to 20 carbon atoms; dimethyl Aminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, die (Meth) acrylates having an amino group such as aminoaminoethyl (meth) acrylate; (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, N-methylacrylamide, Acryloyl morpholine or hydrochloric acid or acetate thereof; vinyl acetate, vinyl propionate, vinyl ester such as diallyl phthalate or allyl compound;
Vinyl monomers containing a nitrile group such as (meth) acrylonitrile; vinyl monomers containing an epoxy group such as glycidyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 -Hydroxyethyl vinyl ether, N
-Methylol (meth) acrylamide, hydroxystyrene, Alonix M-5700 (Toa Gosei Chemical Industry Co., Ltd.)
PlaccelFA-1, PlaccelFA-3, PlaccelFA-4, Pla
ccelFM-1, PlaccelFM-4 (all manufactured by Daicel Chemical Industries, Ltd.), HE-10, HE-20, HP-10, H
P-20 (Nippon Shokubai Co., Ltd.), Blemmer PP
Series, Blemmer PE series, Blemmer PEP
Series, Blemmer AP-400, Blemmer AE-350,
Blemmer NKH-5050, Blemmer GLM (both manufactured by NOF Corporation), hydroxyl-containing vinyl monomers such as hydroxyl-containing vinyl-modified hydroxyalkyl vinyl monomers; hydroxyalkyl esters of (meth) acrylic acid, etc. Phosphate ester group-containing vinyl compounds such as condensation products of hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids and phosphoric acid or phosphoric esters, or (meth) acrylates containing urethane or siloxane bonds Vinyl compounds such as vinyl pyridine, aminoethyl vinyl ether, etc .; itaconic acid diamide, crotonamide,
Amide group-containing vinyl compounds such as maleic acid diamide, fumaric acid diamide, and N-vinylpyrrolidone; AS-6, A, which are macromonomers manufactured by Toa Gosei Chemical Industry Co., Ltd.
Compounds such as N-6, AA-6, AB-6, AK-5,
2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride,
Vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide, N-
Other vinyl monomers such as vinyl imidazole and vinyl sulfonic acid; LA87 and LA manufactured by Asahi Denka Kogyo KK
82, a polymerizable light stabilizer such as LA22, and a polymerizable ultraviolet absorber.

The type of the monomer (A-2) may be selected according to the desired physical properties of the obtained curable resin composition. For example, in order to impart water repellency to a coating film formed using the obtained resin composition and to improve water resistance and durability, a fluorine-containing vinyl monomer or a siloxane-containing vinyl monomer is used. It is preferable to use a hydroxyl group-containing vinyl monomer and a hydrophilic monomer such as polypropylene glycol methacrylate or polyethylene glycol monomethacrylate in order to improve the stability of the obtained resin composition. When an acidic vinyl monomer is used, the curability of the formed coating film is improved.

Further, as the monomer (A-2), for example, a monomer having two or more polymerizable unsaturated double bonds such as polyethylene glycol dimethacrylate, ethylene glycol diacrylate, triallyl cyanurate and the like can be used. Alternatively, the resulting polymer may have a crosslinked structure.

The monomer (A-1) and the monomer (A-
The compounding amount of the monomer (A-1) is 0.5 to 30 with respect to 100 parts (parts by weight, hereinafter the same) of the total amount of both.
Parts, especially 2 to 20 parts, that is, the monomer (A-2)
Is preferably adjusted so as to be 70 to 99.5 parts, especially 80 to 98 parts. When the amount of the monomer (A-1) is less than 0.5 part, water resistance and weather resistance of a coating film formed using the obtained resin composition tend to be poor, and more than 30 parts. In such a case, the stability of the resin composition tends to decrease.

The monomer (A-1) and the monomer (A-
The emulsion polymer (A) can be obtained by emulsion polymerization of 2).

The emulsion polymerization method is not particularly limited, and may be appropriately selected from various emulsion polymerization methods such as a batch polymerization method, a monomer drop polymerization method, and an emulsion monomer drop polymerization method. In the invention, a monomer dropping polymerization method and an emulsion monomer dropping polymerization method are particularly preferable for ensuring the stability of the emulsion during production. In order to further improve the stability of the emulsion, an emulsifier may be used.

The emulsifier is not particularly limited as long as it is used for ordinary emulsion polymerization, and examples thereof include ionic and nonionic surfactants.

Examples of the ionic surfactant include sulfonates such as sodium lauryl sulfonate, sodium dodecylbenzene sulfonate and sodium isooctylbenzene sulfonate; Newcol-723SF, Newcol
-707SN, Newcol-707SF, Newcol-740SF, Newcol-560SN
Representative examples include anionic emulsifiers containing a (poly) oxyethylene group such as (manufactured by Nippon Emulsifier Co., Ltd.); ammonium salts such as imidaline laurate and ammonium hydroxide. Examples of the nonionic surfactant include polyethylene glycol nonyl phenyl ether; polyoxyethylenes such as polyoxyethylene nonyl phenyl ether and polyoxyethylene lauryl ether; L-77, L-72
Nonionic emulsifiers containing silicone such as 0, L-5410, L-7602, and L-7607 (all manufactured by Union Carbide Co., Ltd.) are exemplified.

As the emulsifier, a reactive emulsifier having a polymerizable double bond in one molecule can be used. In particular, when a reactive emulsifier having a polyoxyethylene group in the molecule is used, the water resistance is improved. Specific examples of such an emulsifier include, for example, Adecaria Soap NE-
10, NE-20, NE-30, NE-40, SE-1
0N (all manufactured by Asahi Denka Kogyo Co., Ltd.), Antox-MS
-60 (manufactured by Nippon Emulsifier Co., Ltd.), Aqualon RN-2
0, RN-30, RN-50, HS-10, HS-2
And HS-1025 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

The amount of the emulsifier to be used is preferably 10 parts or less, more preferably 0.5 to 8 parts, based on 100 parts of the total of the monomers (A-1) and (A-2). If the amount of the emulsifier exceeds 10 parts, the water resistance of a coating film formed using the obtained resin composition tends to decrease.

In order to further improve the water resistance of the coating film, instead of using such an emulsifier, a hydrolyzable silyl group represented by the above general formula (I) is introduced into a water-soluble resin to form an emulsion. Is also good.

The monomer (A-1) and the monomer (A-
In order to carry out the polymerization with 2) more stably, a redox catalyst can be used as a polymerization initiator. In addition, in order to maintain the stability of the mixed solution during the polymerization and to stably perform the polymerization, the temperature is preferably 70 ° C. or lower, particularly preferably 40 to 65 ° C., for stabilizing the hydrolyzable silyl group. To
It is preferable to adjust the pH to 5 to 8, especially to 6 to 7.

Examples of the redox catalyst include a combination of potassium or ammonium persulfate and sodium acid sulfite or Rongalite, a combination of hydrogen peroxide and ascorbic acid, t-butyl hydroperoxide, benzoyl peroxide, cumene hydrochloride. Examples include a combination of an organic peroxide such as peroxide with sodium acid sulfite, Rongalit, or the like. In particular, a combination of an organic peroxide and a reducing agent is preferable because polymerization can be stably performed.

The amount of the polymerization initiator to be used is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, based on 100 parts of the total amount of the monomers (A-1) and (A-2). . If the amount of such a polymerization initiator is less than 0.01 part, the polymerization may be difficult to proceed, if it exceeds 10 parts, the molecular weight of the polymer to be produced is reduced, the obtained resin The durability of the coating film formed using the composition tends to decrease.

In order to stably impart the catalytic activity of the polymerization initiator, a compound containing a divalent iron ion such as iron sulfate and a chelating agent such as disodium ethylenediaminetetraacetate may be used. The amount of the chelating agent used is
0.0001 to 1 part, preferably 0.001 to 0.1 part, per 100 parts of the total amount of the monomer (A-1) and the monomer (A-2).
Preferably it is 5 parts.

The emulsion polymer (A) thus obtained is spray-dried, for example, at about 50 to 200 ° C., or is subjected to salting out and coagulation, followed by filtration and washing, followed by drying to obtain fine particles (A). You can get.

The average particle diameter of the fine particles (A) is from 0.01 to
It is preferably 1 μm, especially preferably 0.02 to 0.4 μm. When the average particle size is less than 0.01 μm, the effect of improving the anti-blocking property of a coating film formed using the obtained resin composition tends to decrease.
If it exceeds μm, the surface gloss of the coating film tends to decrease.

The acrylic copolymer (B) containing at least one hydrolyzable silyl group represented by the above general formula (I) in one molecule obtained by the solution polymerization method used in the present invention (hereinafter referred to as “B”) Acrylic copolymer (B))
Is not particularly limited, and includes, for example, a vinyl monomer containing a hydrolyzable silyl group represented by the general formula (I) (hereinafter, referred to as a monomer (B-1)) and other copolymerizable monomers. Vinyl monomer (hereinafter referred to as monomer (B-
2)) is preferably used in view of easy preparation.

In the general formula (I), the aryl group represented by R ¹ is preferably, for example, one having 6 to 10 carbon atoms, and the aralkyl group is, for example, one having 7 to 15 carbon atoms. preferable.

Specific examples of the monomer (B-1) include, for example, those exemplified as the specific examples of the monomer (A-1).
A mixture of more than one species can be used. Among these, alkoxysilyl group-containing vinyl monomers are preferred in view of easiness of handling, cost, and generation of reaction by-products.

The monomer (B-2) is not particularly limited and includes, for example, those exemplified as the monomer (A-2). These may be used alone or as a mixture of two or more. Can be.

In the present invention, as the monomer (B-2), the weather resistance, chemical resistance, solvent resistance, etc. of the coating film formed using the obtained resin composition are improved. It is preferable to select various monomers so that the ester of (meth) acrylic acid is contained at 50% by weight.

The monomer (B-1) and the monomer (B-
The compounding amount of 2) is such that the mixing amount of the monomer (B-1) is 0.5 to 70 parts, preferably 2 to 50 parts, based on 100 parts of the total amount of both.
Parts, that is, the amount of the monomer (B-2) is from 30 to 99.5.
Parts, preferably 50 to 98 parts. When the amount of the monomer (B-1) is less than 0.5 part, the weather resistance and the solvent resistance of the coating film formed using the obtained resin composition tend to be inferior.
If it exceeds the part, the coating film tends to be brittle.

The monomer (B-1) and the monomer (B-
Acrylic copolymer (B) can be obtained by subjecting 2) to solution polymerization.

The solution polymerization method is not particularly limited, and examples thereof include JP-A-54-36395 and JP-A-57-36.
No. 109, Japanese Patent Application Laid-Open No. 58-157810, etc. can be employed. In the present invention, the solution weight using an azo radical polymerization initiator such as azobisisobutyronitrile is particularly preferred. Legalization is preferred in terms of easy handling.

The solvent used in the solution polymerization is not particularly limited as long as it is non-reactive, and examples thereof include hydrocarbons such as toluene, xylene, n-hexane and cyclohexane; ethyl acetate, butyl acetate and the like. Acetic acid esters; alcohols such as methanol, ethanol, isopropanol and n-butanol; ethers such as ethyl cellosolve, butyl cellosolve and cellosolve acetate; methyl ethyl ketone, ethyl acetoacetate;
Examples include ketones such as acetylacetone, diacetone alcohol, methyl isobutyl ketone, and acetone.

In the solution polymerization, if necessary, for example, n-dodecylmercaptan, t-dodecylmercaptan, n-butylmercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, (CH ₃ O) ₃ Si—S—S—Si (O
CH ₃ ) ₃ , (CH ₃ O) ₃ Si—S ₈ —Si (OCH
₃ ) The molecular weight of the acrylic copolymer (B) obtained can be adjusted by using a chain transfer agent such as ₃ alone or in combination of two or more. In particular, if a chain transfer agent having a hydrolyzable silyl group such as γ-mercaptopropyltrimethoxysilane in a molecule is added to a mixed solution of monomers and then further added continuously, the molecular weight is adjusted and the acrylic copolymer is added. It is useful because a hydrolyzable silyl property can be introduced into the terminal of the polymer (B). The amount of the chain transfer agent used is
The amount is preferably 0.1 to 5 parts, more preferably 0.5 to 2 parts, based on 100 parts of the total amount of the monomer (B-1) and the monomer (B-2).

The acrylic copolymer (B) thus obtained contains at least one hydrolyzable silyl group represented by the above general formula (I) in one molecule thereof, and the obtained resin composition It improves the durability, weather resistance, chemical resistance, and the like of the coating film formed by using.

The number average molecular weight of the acrylic copolymer (B) is such that the formed coating film has excellent durability, weather resistance, chemical resistance, etc. and excellent workability. 2000 to 30000, preferably 4000 to 25000, and the resin solid content concentration is excellent in terms of workability and storage stability of the obtained resin composition.
It is preferably adjusted to be 30 to 70% by weight, especially 40 to 60% by weight.

Specific examples of the curing catalyst (C) used in the present invention include, for example, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate,
Organotin compounds such as dioctyltin dimaleate, dioctyltin maleate polymer, tin octylate;
Phosphoric acid or phosphoric acid esters such as phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, didecyl phosphate; hexylamine, dihexylamine -2-
Amines such as ethylhexylamine, N, N-dimethyldodecylamine and dodecylamine; mixtures or reactants of these amines with acidic phosphate esters; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriamine Ethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, formula:

[0086]

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Reactive silane compounds such as compounds represented by the following formulas: propylene oxide, butylene oxide, cyclohexene oxide, glycidyl (meth) acrylate, glycidol, (meth) acrylic glycidyl ether, Cardura E, Epicoat 828, Epicoat 1
Addition products of an epoxy compound such as 001 (both manufactured by Yuka Shell Epoxy Co., Ltd.) and phosphoric acid and / or monoacid phosphate; isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (Dioctyl pyrophosphate) Organic titanate compounds such as oxyacetate titanate; Tris (ethylacetoacetate)
Organic aluminum compounds such as aluminum, tris (acetylacetonato) aluminum; organic zirconium compounds such as tetrabutyl zirconate, tetrakis (acetylacetonato) zirconium, tetraisobutylzirconate, butoxytris (acetylacetonato) zirconium; maleic acid, Saturated or unsaturated polycarboxylic acids such as adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, phthalic acid, trimellitic acid and pyromellitic acid and their acid anhydrides; paratoluenesulfonic acid, etc. And acidic compounds such as sodium hydroxide and potassium hydroxide. These can be used alone or in combination of two or more.

Among the curing catalysts (C), organotin compounds, acidic phosphates, mixtures or reactants of acidic phosphates and amines, reactive silane compounds, organic titanate compounds, organic aluminum compounds, organic zirconium compounds Compounds, saturated or unsaturated polycarboxylic acids and acid anhydrides of the polycarboxylic acids are preferred from the viewpoint of high curing activity.

The curable resin composition of the present invention is obtained by stirring and mixing the fine particles (A), the acrylic copolymer (B) and the curing catalyst (C) so as to have a uniform composition using a homogenizer or the like. You can get things.

The mixing ratio of the fine particles (A), the acrylic copolymer (B) and the curing catalyst (C) is slightly different depending on the use of the obtained curable resin composition. 0.1 to 300 parts per 100 parts of the resin solid content of the acrylic copolymer (B), preferably 0.2
Preferably, it is up to 200 parts. When the amount of the fine particles (A) is less than 0.1 part, the fine particles (A)
When the amount exceeds 300 parts, the viscosity of the resin composition increases, the workability and the surface of the coating film formed using the resin composition tend to be insufficient. Appearance such as gloss tends to decrease.

The curing catalyst (C) is usually added in an amount of 0.1 to 100 parts of the resin solid content of the acrylic copolymer (B).
-20 parts, preferably 0.1-10 parts.
When the amount of the curing catalyst is less than 0.1 part, the curability of the obtained resin composition tends to decrease, and when the amount exceeds 20 parts, the resin composition is used. There is a tendency that the appearance, such as the surface gloss, of the formed coating film is reduced.

As described above, the curable resin composition of the present invention contains the fine particles (A), the acrylic copolymer (B) and the curing catalyst (C). , Usually used in paints, for example, titanium oxide, ultramarine, navy blue, zinc white, red iron oxide, graphite, lead white, carbon black, transparent iron oxide, inorganic pigments such as aluminum powder,
Pigments such as organic pigments such as azo pigments, triphenylmethane pigments, quinoline pigments, anthraquinone pigments, and phthalocyanine pigments; additives such as diluents, ultraviolet absorbers, light stabilizers, anti-sagging agents, and leveling agents Cellulose, nitrocellulose, cellulose acetate butyrate, etc .; epoxy resin, melamine resin, vinyl chloride resin, fluororesin, chlorinated polypropylene, chlorinated rubber, polyvinyl butyral, polysiloxane, etc .; can do.

The curable resin composition of the present invention is applied to an object to be coated by a usual method such as dipping, spraying, application using a brush or the like, and cured by baking at room temperature or at about 60 to 200 ° C. And a coating film can be obtained.

The curable resin composition of the present invention can be used, for example, for automotive interiors and exteriors, for repair on metallic bases for repair, for direct application to metals such as aluminum and stainless steel, and for ceramics such as slate, concrete and tile. It can be suitably used as a surface treatment agent, including a paint for direct application to a substrate.

Next, the curable resin composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples.

Production Examples 1-4 (Production of Fine Particles (A)) In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel, 40 parts of deionized water, 0.9 parts of sodium dodecylbenzenesulfonate were placed. Parts, 1 part of polyoxyethylene nonylphenyl ether, 0.35 part of Rongalite, 0.5 part of ammonium acetate, 0.2 part of t-butyl hydroperoxide and 20 parts of 158 parts of the mixture having the composition shown in Table 1.
Was added for initial preparation. Thereafter, the temperature was raised to 50 ° C. while introducing nitrogen gas, and after heating for 1 hour, 0.5 part of t-butyl hydroperoxide and the mixture 158 were added.
The remaining 138 parts of the mixture in this part was dropped at a constant rate over 3 hours by a dropping funnel. Thereafter, polymerization was carried out for 1 hour to obtain emulsion polymers (A) -1 to (A) -4.

The obtained emulsion polymers (A) -1 to (A)-
4 was spray-dried at an inlet temperature of 160 ° C. and an exhaust air temperature of 90 ° C. to obtain fine particles (A) -1 to (A) -4.

The obtained fine particles (A) -1 to (A)
Table 1 shows the average particle size of -4.

[0099]

[Table 1]

Production Example 5 (Production of acrylic copolymer (B)) 45.9 parts of xylene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel. After heating to 110 ° C while introducing gas, γ
-A mixture of 14 parts of methacryloxypropyltrimethoxysilane, 55 parts of methyl methacrylate, 30 parts of butyl acrylate, 1 part of acrylamide, 5 parts of xylene and 1 part of 2,2'-azobisisobutyronitrile is dropped by a dropping funnel for 5 hours. The solution was dropped at a constant speed.

After completion of the dropwise addition of the mixture, 0.5 part of 2,2'-azobisisobutyronitrile and 5 parts of toluene were added dropwise at a constant speed over 1 hour, and the mixture was aged at 110 ° C. for 2 hours, cooled and cooled. Add xylene to the solution to reduce the resin solids concentration.
An acrylic copolymer (B) of 60% by weight was obtained. The obtained acrylic copolymer (B) had a number average molecular weight of 1500.
It was 0.

Examples 1 to 6 and Comparative Examples 1 and 2 24 g of the acrylic copolymer (B) obtained in Production Example 5, 24 g of titanium oxide (CR95, manufactured by Ishihara Sangyo KK), xylene
After 16 g and 20 g of glass beads were dispersed for 3 hours using a paint shaker, 36 g of the acrylic copolymer (B) was added and dispersed for another 1 hour to obtain a white enamel having a solid content of 60% by weight.

Next, this white enamel, the fine particles (A) obtained in Production Examples 1 to 4 and dioctyltin maleate as the curing catalyst (C) were blended in the proportions shown in Table 3 and 10,000 rpm using a homogenizer. For 10 minutes to obtain a resin composition.

As the physical properties of the coating film formed using the obtained resin composition, blocking resistance, thixotropy, weather resistance, gloss and film thickness were examined according to the following methods. Table 2 shows the results.

(A) Blocking Resistance The resin composition was applied on a slate plate so that the dry film thickness became 30 μm, and was forcedly dried at 80 ° C. for 30 minutes. And
At the same time as the temperature of the slate plate dropped to 23 ° C., gauze was placed on the formed coating film and a load of 250 g / cm ² was applied and left at 23 ° C. for 1 day. Thereafter, the gauze was removed, and the surface state of the coating film was visually observed, and evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: No trace of gauze is observed at all. B: Traces of gauze are partially observed. C: Traces of gauze are clearly observed throughout.

(B) Thixotropy (Sag tester sagging level) The resin composition was drawn on a glass plate with a sag tester, and the glass plate was immediately set upright to measure the sagged film thickness (μm). In addition, 125 μm is 30 μm of dry film thickness with a sag tester.
About 200 μm and more than 50 μm.

(C) Weather resistance (gloss retention) Using a sunshine weatherometer, the gloss of the surface of the coating film on the aluminum plate immediately after the application of the resin composition and the surface of the coating film on the aluminum plate after 2,000 hours have passed. Was measured, and the gloss retention (%) after 2000 hours was obtained.

(D) Gloss of the dried coating film The resin composition was flow-coated on an aluminum plate,
After standing for days, the gloss of the surface of the formed coating film was measured according to JIS
It was measured using a GMX-202 color difference meter (manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with K5400 (60 ° gloss).

(E) Film thickness of dried coating film The thickness (μm) of the coating film formed by using the resin composition on the aluminum plate was measured by Minitest 2000 (manufactured by Electro-Physique Cologne, Germany). did.

The anti-sagging agents in Table 2 are # 6900
-20X (manufactured by Kusumoto Kasei Co., Ltd.).

[0112]

[Table 2]

From the results shown in Table 2, the coating films formed using the resin compositions obtained in Examples 1 to 6 have excellent blocking resistance and thixotropy, as well as good gloss and weather resistance. It can be seen that it has properties.

[0114]

The curable resin composition of the present invention has an effect that a coating film having good gloss and weather resistance, as well as significantly improved blocking resistance and thixotropy can be formed.

Accordingly, the curable resin composition of the present invention has an effect that it can be suitably used for painting interior and exterior of buildings, automobiles, home electric appliances and the like.

Claims (4)

(57) [Claims] 1. A compound of the general formula (I): (Wherein, R ¹ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group;
¹ represents a halogen atom, an alkoxy group, a hydroxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group or an amino group, and a represents an integer of 0 to 2 (provided that R ¹ and X ¹ are each 2 or more. In such a case, these are the same or different)) and the fine particles of an emulsion polymer containing a hydrolyzable silyl group (A),
Acrylic copolymer (B) containing at least one hydrolyzable silyl group represented by the above general formula (I) per molecule obtained by a solution polymerization method (B) and a curing catalyst (C)
A curable resin composition comprising: 2. The curing method according to claim 1, wherein the emulsion polymer is an emulsion copolymer obtained by copolymerizing an alkoxysilyl group-containing vinyl monomer and another vinyl monomer copolymerizable therewith. Resin composition. 3. An acrylic copolymer (B) is a solution copolymer obtained by copolymerizing an alkoxysilyl group-containing vinyl monomer and another vinyl monomer copolymerizable therewith. Item 3. The curable resin composition according to item 1 or 2. 4. A curing catalyst (C) comprising an organotin compound, an acid phosphate, a mixture or a reaction product of an acid phosphate and an amine, a reactive silane compound, an organic titanate compound, an organic aluminum compound, an organic zirconium compound, 4. The curable resin composition according to claim 1, wherein the curable resin composition is at least one selected from a saturated or unsaturated polycarboxylic acid and an acid anhydride of a saturated or unsaturated polycarboxylic acid.