JPH06279648A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition providing a coating film having excellent gloss and weathering resistance, extremely improved blocking resistance and thixotropic properties, comprising a specific hydrolyzable silyl- containing emulsion polymer particles arid a specific solution-like acrylic copolymer. CONSTITUTION:The objective composition comprises (A) emulsion polymer particles containing a hydrolyzable silyl of the formula (R<1> is 1-10C alkyl, aryl, etc.; X<1> is halogen, alkoxy, etc., (a) is 0-2), (B) an acrylic copolymer containing the hydrolyzable silyl of the formula obtained by solution polymerization method and (C) a curing catalyst (preferably organotin compound such as dibutyltin dilaurate). The compound A is preferably obtained by subjecting an alkoxysilyl group-containing vinyl-based monomer and another copolymerizable vinyl-based monomer to emulsion polymerization and the component B is preferably prepared by subjecting both the monomers to emulsion polymerization. gamma- Methacryloxypropyltrimethoxysilane is used as the alkoxysilyl group-containing vinyl-based monomer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a curable resin composition. More specifically, the present invention relates to a curable resin composition capable of imparting excellent blocking resistance, thixotropy, and other coating film properties to building interiors and exteriors, automobiles, home appliances, etc., which require weather resistance and durability.

[0002]

2. Description of the Related Art Conventionally, as a paint for interiors and exteriors of buildings, automobiles, household appliances, etc., it is possible to form a coating film having excellent weather resistance, stain resistance, and adhesion to an inorganic substrate. Therefore, those containing a solution type acrylic copolymer containing a hydrolyzable silyl group as a main component are widely used.

However, a coating film formed from the above-mentioned paint has a drawback that it is inferior in blocking resistance such that a trace remains when the coating films are superposed immediately after formation. Further, when trying to form a thick coating film using the above paint, sagging occurs, workability is poor, and in order to prevent such sagging,
When a large amount of a thixotropy-imparting agent is added to the coating material, there is a problem that the gloss and weather resistance of the formed coating film are reduced.

[0004]

Therefore, the inventor of the present invention
As a result of repeated intensive studies in view of the above-mentioned 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. It was finally found that a coating film having good gloss and weather resistance, as well as significantly improved blocking resistance and thixotropy, can be formed from a resin composition, and the present invention was completed.

[0005]

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

[0006]

[Chemical 2]

(In the formula, 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 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, they are the same or different). Emulsion polymer fine particles (A) containing a hydrolyzable silyl group represented by 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]

Functions and Examples The curable resin composition of the present invention has the general formula (I):

[0009]

[Chemical 3]

(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 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, they are the same or different). Emulsion polymer fine particles (A) containing a hydrolyzable silyl group represented by 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).

A 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 ( It has good gloss and weather resistance due to the formation of a crosslinked structure with B).

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 the emulsion polymer (A)) is There is no particular limitation, and examples thereof include emulsions containing a hydrolyzable silyl group represented by the general formula (I), such as epoxy resins, polyester resins, polyether resins, acrylic resins and fluororesins. Among these, an acrylic resin emulsion is preferable because the coating film formed using the obtained curable resin composition has excellent weather resistance and chemical resistance, and the range of resin design is wide.

The method for preparing the emulsion polymer (A) is not particularly limited, and for example, a vinyl monomer containing a hydrolyzable silyl group represented by the general formula (I) (hereinafter referred to as monomer ( A-1)) and other vinyl monomers copolymerizable therewith (hereinafter referred to as the monomer (A-
The method of emulsion-polymerizing (2)) is preferable 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 one having 6 to 10 carbon atoms, and the aralkyl group is one having, for example, 7 to 15 carbon atoms. preferable.

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

[0016]

[Chemical 4]

General formula (II) such as:

[0018]

[Chemical 5]

(Wherein R ¹ and a are the same as described above, R ²
Is a hydrogen atom or a methyl group, and X ² is a halogen atom).

[0020]

[Chemical 6]

General formula (III) such as:

[0022]

[Chemical 7]

A compound represented by the formula: wherein R ¹ , R ² , X ² and a are the same as defined above, and n is an integer of 1 to 12;

[0024]

[Chemical 8]

General formula (IV) such as:

[0026]

[Chemical 9]

A compound represented by the formula: wherein R ¹ , R ² and a are the same as defined above, and R ³ is an alkyl group having 1 to 16 carbon atoms;

[0028]

[Chemical 10]

General formula (V) such as:

[0030]

[Chemical 11]

A compound represented by the formula (wherein R ¹ , R ² , R ³ , a and n are the same as defined above);

[0032]

[Chemical 12]

General formula (VI) such as:

[0034]

[Chemical 13]

A compound represented by the formula: wherein R ¹ , R ² , R ³ , a and n are the same as defined above;

[0036]

[Chemical 14]

General formula (VII) such as:

[0038]

[Chemical 15]

A compound represented by the formula (wherein R ¹ , R ² , R ³ , a and n are the same as defined above);

[0040]

[Chemical 16]

General formula (VIII) such as:

[0042]

[Chemical 17]

A compound represented by the formula (wherein R ¹ , R ² , R ³ and a are the same as defined above);

[0044]

[Chemical 18]

General formula (IX) such as:

[0046]

[Chemical 19]

A compound represented by the formula (wherein R ¹ , R ² , R ³ , a and n are the same as defined above);

[0048]

[Chemical 20]

General formula (X) such as:

[0050]

[Chemical 21]

(In the formula, 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]

[Chemical formula 22]

General formula (XI) such as:

[0054]

[Chemical formula 23]

(Wherein R ¹ , R ² , R ³ , a and n are the same as defined above, p is an integer of 1 to 12) and the like. These may be used alone or in combination. The above can be mixed and used. Among these, the alkoxysilyl group-containing vinyl-based monomer is preferable from the viewpoint of easy handling, cost, and no reaction by-product.

The monomer (A-2) is not particularly limited and includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl. (Meth) acrylate-based monomers such as (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate; trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate , 2,2,3,3-tetrafluoropropyl methacrylate, β- (perfluorooctyl) ethyl (meth)
Fluorine-containing vinyl monomers such as acrylates; aromatic hydrocarbon vinyl monomers such as styrene, α-methylstyrene, chlorostyrene, 4-hydroxystyrene, vinyltoluene; acrylic acid, methacrylic acid, maleic acid, anhydrous Α, β-ethylenically unsaturated carboxylic acids such as maleic acid, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid and citraconic acid; polymerizable carbon-carbon double bonds such as styrene sulfonic acid and vinyl sulfonic acid An acid having, or a salt thereof such as an alkali metal salt, an ammonium salt or an amine salt; an acid anhydride such as maleic anhydride or a half ester of the same with an alcohol having a linear or branched chain having 1 to 20 carbon atoms; dimethyl Aminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, die (Meth) acrylate having an amino group such as ruaminoethyl (meth) acrylate; (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, N-methylacrylamide, Acryloylmorpholine, or their hydrochloric acid, acetate; vinyl acetate, vinyl propionate, diallyl phthalate and other vinyl esters and allyl compounds;
Nitrile group-containing vinyl monomers such as (meth) acrylonitrile; epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 -Hydroxyethyl vinyl ether, N
-Methylol (meth) acrylamide, hydroxystyrene, Aronix M-5700 (Toagosei 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 (above, manufactured by Nippon Shokubai Co., Ltd.), Bremmer PP
Series, Blemmer PE series, Blemmer PEP
Series, Bremmer AP-400, Bremmer AE-350,
Blemmer NKH-5050, Blemmer GLM (all manufactured by NOF CORPORATION), hydroxyl-containing vinyl-based modified hydroxyalkyl vinyl-based monomers such as hydroxyl-containing vinyl-based monomers; (meth) acrylic acid hydroxyalkyl esters, 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 acid esters, or (meth) acrylates containing urethane bond or siloxane bond Vinyl compounds; amino group-containing vinyl compounds such as vinyl pyridine and aminoethyl vinyl ether; itaconic acid diamide, crotonamide,
Amide group-containing vinyl compounds such as maleic acid diamide, fumaric acid diamide, and N-vinylpyrrolidone; AS-6 and A, which are macromonomers manufactured by Toagosei 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, LA manufactured by Asahi Denka Co., Ltd.
82, LA22 and other polymerization type light stabilizers, polymerization type ultraviolet absorbers and the like.

The type of the monomer (A-2) may be selected according to the desired physical properties of the curable resin composition obtained. For example, in order to impart water repellency to a coating film formed by using the obtained resin composition and improve water resistance and durability, a fluorine-containing vinyl-based monomer or a siloxane-containing vinyl-based monomer is used. In order to improve the stability of the obtained resin composition, it is preferable to use a hydroxyl group-containing vinyl monomer and a hydrophilic monomer such as polypropylene glycol methacrylate or polyethylene glycol monomethacrylate. Further, when the acidic vinyl-based 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 and triallyl cyanurate can be used. Alternatively, the polymer produced may have a crosslinked structure.

The monomer (A-1) and the monomer (A-
The compounding amount of 2) is such that the compounding amount of the monomer (A-1) is 0.5 to 30 with respect to the total amount of both 100 parts (parts by weight, the same applies hereinafter).
Part, especially 2 to 20 parts, namely monomer (A-2)
It is preferable to adjust the compounding amount of 70 to 99.5 parts, especially 80 to 98 parts. When the compounding amount of the monomer (A-1) is less than 0.5 part, the water resistance and weather resistance of the coating film formed using the obtained resin composition tend to be inferior, and exceeds 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) and.

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

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

Examples of the ionic surfactants 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 those manufactured by Nippon Emulsifier Co., Ltd .; ammonium salts such as imidazoline laurate and ammonium hydroxide. Examples of the nonionic surfactant include polyethylene glycol nonylphenyl ether; polyoxyethylenes such as polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl ether; L-77, L-72.
Representative examples include nonionic emulsifiers containing silicone such as 0, L-5410, L-7602, L-7607 (all manufactured by Union Carbide Co.).

As the emulsifier, a reactive emulsifier having a polymerizable double bond in one molecule can be used. Especially when a reactive emulsifier having a polyoxyethylene group in the molecule is used, the water resistance is improved. Specific examples of such emulsifiers include, for example, ADEKA REASOAP NE-
10, NE-20, NE-30, NE-40, SE-1
0N (above, Asahi Denka Kogyo KK), Antox-MS
-60 (Nippon Emulsifier Co., Ltd.), Aqualon RN-2
0, RN-30, RN-50, HS-10, HS-2
0, HS-1025 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like.

The emulsifier is preferably used in an amount of 10 parts or less, particularly 0.5 to 8 parts, per 100 parts of the total amount of the monomer (A-1) and the monomer (A-2). When the amount of such an emulsifier used exceeds 10 parts, the water resistance of the 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 general formula (I) is introduced into a water-soluble resin to prepare an emulsion. 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. Further, in order to maintain the stability of the mixed solution during the polymerization and carry out the polymerization stably, it is preferable that the temperature is 70 ° C. or lower, especially 40 to 65 ° C., in order to stabilize the hydrolyzable silyl group. To
The pH is preferably adjusted to 5-8, especially 6-7.

Examples of the redox catalysts include a combination of potassium or ammonium persulfate with sodium acid sulfite or rongalite, a combination of hydrogen peroxide and ascorbic acid, t-butyl hydroperoxide, benzoyl peroxide, cumene hydro. Examples include combinations of organic peroxides such as peroxides and acidic sodium sulfite, Rongalit, and the like. Particularly, a combination of an organic peroxide and a reducing agent is preferable from the viewpoint that stable polymerization can be carried out.

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

Further, a compound containing a divalent iron ion such as iron sulfate and a chelating agent such as disodium ethylenediaminetetraacetate may be used in order to stably impart the catalytic activity of the polymerization initiator. The amount of such chelating agent used is
0.0001 to 1 part based on 100 parts of the total amount of the monomer (A-1) and the monomer (A-2), especially 0.001 to 0.
It is preferably 5 parts.

The emulsion polymer (A) thus obtained is spray-dried at, for example, about 50 to 200 ° C., salted out and coagulated, filtered, washed with water, and then dried to obtain the fine particles (A). You can get it.

The average particle size of the fine particles (A) is 0.01 to
It is preferably 1 μm, especially 0.02 to 0.4 μm. When the average particle size is less than 0.01 μm, the effect of improving the blocking resistance of the coating film formed using the obtained resin composition tends to decrease, and 1
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 general formula (I) in one molecule obtained by the solution polymerization method used in the present invention (hereinafter referred to as Acrylic copolymer (B))
Is not particularly limited, and includes, for example, a vinyl-based monomer containing a hydrolyzable silyl group represented by the general formula (I) (hereinafter referred to as monomer (B-1)) and a copolymerizable monomer with the vinyl-based monomer. Vinyl monomer (hereinafter referred to as monomer (B-
A copolymer obtained by solution polymerization of (2)) is preferably used from the viewpoint of easy preparation.

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

Specific examples of the monomer (B-1) include those exemplified as the specific examples of the monomer (A-1), and these may be used alone or in 2
A mixture of two or more species can be used. Among these, the alkoxysilyl group-containing vinyl-based monomer is preferable from the viewpoint of easy handling, cost, and no reaction by-product.

The monomer (B-2) is not particularly limited, and examples thereof include those exemplified as the monomer (A-2). These may be used alone or in admixture of two or more. You can

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

Monomer (B-1) and monomer (B-
The blending amount of 2) is such that the blending amount of the monomer (B-1) is 0.5 to 70 parts, especially 2 to 50 parts based on 100 parts of the total amount of both.
Part, that is, the blending amount of the monomer (B-2) is 30 to 99.5
It is preferable to adjust so that it is 50 to 98 parts. When the compounding amount of the monomer (B-1) is less than 0.5 part, the weather resistance and solvent resistance of the coating film formed by using the obtained resin composition tend to be inferior.
If it exceeds the area, the coating film tends to become brittle.

The monomer (B-1) and the monomer (B-
The acrylic copolymer (B) can be obtained by solution polymerization with 2).

The solution polymerization method is not particularly limited. For example, JP-A-54-36395 and JP-A-57-36.
The methods described in Japanese Patent Application Laid-Open No. 109, JP-A-58-157810 and the like can be adopted, but in the present invention, solution polymerization using an azo radical polymerization initiator such as azobisisobutyronitrile is particularly preferable. The legal method is preferable because it is easy to handle.

The solvent used for the solution polymerization is not particularly limited as long as it is a non-reactive solvent. For example, hydrocarbons such as toluene, xylene, n-hexane and cyclohexane; ethyl acetate, butyl acetate, etc. Acetates; alcohols such as methanol, ethanol, isopropanol, n-butanol; ethers such as ethyl cellosolve, butyl cellosolve, cellosolve acetate; methyl ethyl ketone, ethyl acetoacetate,
Ketones such as acetylacetone, diacetone alcohol, methyl isobutyl ketone, and acetone are included.

In the solution polymerization, if necessary, for example, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, 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 ) By using a chain transfer agent such as ₃ alone or in combination of two or more, the molecular weight of the obtained acrylic copolymer (B) can be adjusted. In particular, if a chain transfer agent having a hydrolyzable silyl group in the molecule, such as γ-mercaptopropyltrimethoxysilane, is added to a mixed solution of monomers and then continuously added, the molecular weight is adjusted and the acrylic copolymer is simultaneously added. It is useful because a hydrolyzable silyl property can be introduced into the terminal of the polymer (B). The amount of such chain transfer agent used is
The total amount of the monomer (B-1) and the monomer (B-2) is preferably 0.1 to 5 parts, especially 0.5 to 2 parts, per 100 parts.

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

The number average molecular weight of the acrylic copolymer (B) is excellent in durability, weather resistance, chemical resistance, etc. of the formed coating film, and also in workability. It is preferably 2000 to 30000, especially 4000 to 25000, and the resin solid content concentration is excellent in workability and storage stability of the obtained resin composition,
It is preferably adjusted to 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, polymers of dioctyltin maleate, tin octylate;
Phosphoric acid or phosphoric acid ester 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, di -2-
Amines such as ethylhexylamine, N, N-dimethyldodecylamine and dodecylamine; a mixture or reaction product of these amines and an acidic phosphoric acid ester; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltri Ethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, formula:

[0086]

[Chemical formula 24]

Reactive silane compounds such as compounds represented by: propylene oxide, butylene oxide, cyclohexene oxide, glycidyl (meth) acrylate, glycidol, (meth) acrylic glycidyl ether, cardura E, Epicoat 828, Epicoat 1
Addition reaction products of an epoxy compound such as 001 (manufactured by Yuka Shell Epoxy Co., Ltd.) with phosphoric acid and / or monoacidic phosphoric acid ester; isopropyltriisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis. (Dioctyl pyrophosphate) Oxyacetate Organic titanate compounds such as titanate; Tris (ethylacetoacetate)
Organoaluminum compounds such as aluminum and tris (acetylacetonato) aluminum; Tetrabutylzirconate, tetrakis (acetylacetonato) zirconium, tetraisobutylzirconate, butoxytris (acetylacetonato) zirconium and other organic zirconium compounds; maleic acid, Saturated or unsaturated polyvalent carboxylic acids such as adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, phthalic acid, trimellitic acid, 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 admixture of two or more.

Among the above curing catalysts (C), organotin compounds, acidic phosphoric acid esters, mixtures or reactants of acidic phosphoric acid esters and amines, reactive silane compounds, organic titanate compounds, organic aluminum compounds, organic zirconium compounds. A compound, a saturated or unsaturated polycarboxylic acid and an acid anhydride of the polycarboxylic acid are preferable 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 obtain a uniform composition with, for example, a homogenizer. You can get things.

The mixing ratios of the fine particles (A), the acrylic copolymer (B) and the curing catalyst (C) are slightly different depending on the use of the obtained curable resin composition, but the mixing amount of the fine particles (A) is Ordinarily, 0.1 to 300 parts per 100 parts of resin solids of acrylic copolymer (B), especially 0.2
It is preferably about 200 parts. When the amount of the fine particles (A) is less than 0.1 part, the fine particles (A) are
The effect of using the resin tends to not be fully exerted, and when it exceeds 300 parts, the resin composition thickens, and workability and the surface of the coating film formed using the resin composition The appearance such as gloss tends to deteriorate.

The curing catalyst (C) is usually added in an amount of 0.1 with respect to 100 parts of the resin solid content of the acrylic copolymer (B).
It is preferably -20 parts, especially 0.1-10 parts.
If the compounding amount of the curing catalyst is less than 0.1 part, the curability of the obtained resin composition tends to decrease, and if it exceeds 20 parts, the resin composition is used. Appearance such as surface gloss of the coating film formed as described above tends to deteriorate.

The curable resin composition of the present invention contains the fine particles (A), the acrylic copolymer (B) and the curing catalyst (C) as described above. Inorganic pigments such as titanium oxide, ultramarine blue, navy blue, zinc white, red iron oxide, yellow lead, lead white, carbon black, transparent iron oxide, aluminum powder, etc.
Organic pigments such as azo pigments, triphenylmethane pigments, quinoline pigments, anthraquinone pigments, phthalocyanine pigments, etc .; diluents, UV absorbers, light stabilizers, anti-sagging agents, leveling agents, etc. Fibrin such as nitrocellulose, cellulose acetate butyrate; epoxy resin, melamine resin, vinyl chloride resin, fluororesin, chlorinated polypropylene, chlorinated rubber, polyvinyl butyral, polysiloxane, and other resins are blended as necessary. can do.

The curable resin composition of the present invention is applied to an object to be coated by a conventional method such as dipping, spraying, coating with a brush, etc., and baked at room temperature or at about 60 to 200 ° C. to cure. And a coating film can be obtained.

The curable resin composition of the present invention is used, for example, for interior and exterior of buildings, for automobiles such as clear on a metallic base for repair, for direct coating of metals such as aluminum and stainless steel, and ceramics such as slate, concrete and roof tiles. It can be suitably used as a surface treatment agent including a coating material for direct coating on a substrate.

Next, the curable resin composition of the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Production Examples 1 to 4 (Production of Fine Particles (A)) In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube and a dropping funnel, 40 parts of deionized water, sodium dodecylbenzenesulfonate 0.9. Parts, 1 part of polyoxyethylene nonylphenyl ether, 0.35 parts of rongalite, 0.5 parts of ammonium acetate, 0.2 parts of t-butyl hydroperoxide and 20 out of 158 parts of the mixture having the composition shown in Table 1.
Parts were added to carry out initial charging. Then, 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
The remaining 138 parts of the mixture was added dropwise at a constant rate through a dropping funnel over 3 hours. After this, post-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)
The average particle size of -4 is shown in Table 1.

[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 introducing pipe and a dropping funnel, and nitrogen was added. After introducing gas, raise the temperature to 110 ° C and
-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 for 5 hours with a dropping funnel. It was dripped at a constant speed.

After the completion of the dropping of the mixture, 0.5 parts of 2,2'-azobisisobutyronitrile and 5 parts of toluene were added dropwise at a constant rate over 1 hour, followed by aging at 110 ° C for 2 hours and then cooling to obtain a resin. Xylene was added to the solution so that the resin solids concentration
60% by weight of an acrylic copolymer (B) was obtained. The number average molecular weight of the obtained acrylic copolymer (B) is 1500.
It was 0.

Examples 1 to 6 and Comparative Examples 1 to 24 24 g of the acrylic copolymer (B) obtained in Production Example 5, 24 g of titanium oxide (CR95, manufactured by Ishihara Sangyo Co., Ltd.), 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 further dispersed for 1 hour to obtain white enamel having a solid content concentration of 60% by weight.

Next, this white enamel, the fine particles (A) obtained in Production Examples 1 to 4 and dioctyl tin maleate as a curing catalyst (C) were blended at a ratio shown in Table 3, and a homogenizer was used to obtain 10,000 rpm. The resin composition was obtained by stirring for 10 minutes.

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. The results are shown in Table 2.

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

(Evaluation Criteria) A: No trace of gauze is observed. B: A trace of gauze is partially observed. C: The trace of gauze is clearly recognized as a whole.

(B) Thixotropic property (sagg tester sag level) The resin composition was drawn on a glass plate with a sag tester, and immediately the glass plate was erected vertically to measure the sagging film thickness (μm). In addition, 125 μm with a sag tester is 30 μm of dry film thickness.
Corresponding to the degree, and above 200 μm corresponds to above 50 μm.

(C) Weather resistance (gloss retention) Gloss of the coating film surface on the aluminum plate immediately after applying the resin composition and after 2000 hours on the aluminum plate using a sunshine weatherometer Was measured and the gloss retention rate (%) after 2000 hours was determined.

(D) Gloss of dry coating film The resin composition was applied by flow coating on an aluminum plate, and 1
After leaving for a day, the gloss of the formed coating film surface can be measured by JIS
It was measured using a GMX-202 color difference meter (manufactured by Murakami Color Research Laboratory Co., Ltd.) according to K 5400 (60 ° gloss).

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

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

[0112]

[Table 2]

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

[0114]

EFFECTS OF THE INVENTION The curable resin composition of the present invention has the effect of forming a coating film having excellent gloss and weather resistance, as well as significantly improved blocking resistance and thixotropy.

Therefore, the curable resin composition of the present invention has an effect that it can be suitably used for coating interiors and exteriors of buildings, automobiles, household appliances, and the like.

Claims (4)

[Claims] 1. A compound represented by the general formula (I): (In the formula, 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 is 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 is an integer of 0 to 2 (provided that each of R ¹ and X ¹ is 2 or more. In some cases, these are the same or different)) and are fine particles (A) of an emulsion polymer containing a hydrolyzable silyl group.
Acrylic copolymer (B) and curing catalyst (C) containing at least one hydrolyzable silyl group represented by the general formula (I) obtained in a solution polymerization method in one molecule.
A curable resin composition containing: 2. The curing 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. The 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. The curing catalyst (C) is an organic tin compound, an acidic phosphoric acid ester, a mixture or reaction product of an acidic phosphoric acid ester and an amine, a reactive silane compound, an organic titanate compound, an organic aluminum compound, an organic zirconium compound, The curable resin composition according to claim 1, which is at least one selected from saturated or unsaturated polycarboxylic acids and acid anhydrides of saturated or unsaturated polycarboxylic acids.