JP2002188058A - Water-based coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-based coating composition capable of forming a coating film excellent in hydrophilic property of surface and stain resistance. SOLUTION: This water-based coating composition comprises (A) a synthetic resin emulsion, (B) a modified silicone compound and (C) an organic solvent. The modified silicone compound B is one or more kinds of silicone compounds selected from silicone compounds or the like represented by general formula I: (R1O)4-aSiR2a (I) (R1 is a 1-10C alkyl group, a 6-10C aryl group or a 7-10C aralkyl group; R2 is a 1-10C alkyl group, a 6-10C aryl group, a 7-10C aralkyl group or a 1-10C alkoxy group; a is an integer of 0 to 2) and the organic solvent C has <=160 deg.C boiling point. The modified silicone compound B and the organic solvent C are respectively included in amounts of 1-100 pts.wt. and 1-60 pts.wt. based on 100 pts.wt. solid content of the synthetic resin emulsion A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the coating of various substrates such as plastics in various fields such as interior and exterior of buildings, automobiles and home electric appliances, and more particularly, to the use of various coatings requiring stain resistance. The present invention relates to a water-based coating composition used for the above.

[0002]

2. Description of the Related Art In recent years, the global environmental pollution has become a serious social problem, and attempts have been made in the field of paints to switch from solvent-based paints to water-based paints such as emulsion paints, water-soluble paints, and dispersion paints. However, the resin contained in the conventional water-based paint does not have a crosslinkable functional group in the molecule. Therefore, the resin is strongly affected by a surfactant used when the resin is produced by polymerization, and the weather resistance, water resistance, and stain resistance of the formed coating film are significantly deteriorated. Thus, the coating film had poor physical properties.

[0003] Various attempts have been proposed to remedy this drawback. For example, an aqueous paint containing a polymer emulsion having a hydrolyzable silyl group as a crosslinkable functional group (Japanese Patent Application Laid-Open No. 3-27312); and a reaction between a carbonyl group and a hydrazino group causes the resin particles contained to contain particles. A water-based paint in which crosslinking is caused (Japanese Unexamined Patent Publication No.
No. 59305). Further, there has been proposed a water-dispersed fluororesin paint in which a fluororesin exhibiting high performance with a solvent-based paint is converted to an aqueous solution (Japanese Patent Application Laid-Open No. Hei 5-25421).

[0004] Further, there is a problem that the stainability is considerably inferior to that of the solvent-based paint. In particular, in recent years, requirements for stainability have been increasing in various fields, and a level close to that of a solvent-based low-contamination type paint is required.

[0005] In recent years, paints having a function of removing contaminants adhered by rainwater by hydrophilizing the surface of the paint film after painting have been developed. When this paint is used, the hydrolyzable silicate oligomer contained in the paint is oriented on the surface of the coating film after application, and thereafter, a large number of hydroxyl groups are formed on the surface of the coating film by hydrolysis to make the coating film hydrophilic. Is achieved. Since these techniques have a problem of the stability of the silicate oligomer, they were first put to practical use as solvent-based paints, and then applied to water-based paints were studied and put into practical use (Japanese Patent Application Laid-Open No. Hei 8-259892). ,
JP-A-9-221611, JP-A-2000-448
No. 36, etc.). However, the water-based paint using the above-mentioned method has a disadvantage that the contained silicate oligomer is not effectively surface-aligned as compared with the solvent-based paint.

[0006]

An object of the present invention is to solve the above-mentioned conventional problems.
An object of the present invention is to provide an aqueous coating composition capable of forming a coating film having excellent weather resistance, water resistance, and stain resistance.
Another object of the present invention is to provide a water-based paint composition having the above-mentioned excellent performance, wherein the paint film surface after coating has a hydrophilic property and has a function of removing attached contaminants by rainwater. It is in. Still another object of the present invention is a method for producing a coated substrate using the above composition, and weather resistance, water resistance, surface hydrophilicity and stain resistance obtained by applying the composition to a substrate. It is to provide a coated substrate excellent in the above.

[0007]

The aqueous coating composition of the present invention is a composition comprising a synthetic resin emulsion (A), a modified silicone compound (B) and an organic solvent (C), wherein the modified silicone composition comprises The compound (B) is a compound represented by the general formula (I): (R ¹ O) _4-a SiR ² _a (I) (where R ¹ is each independently an alkyl group having 1 to 10 carbon atoms, An aryl group having 10 or an aralkyl group having 7 to 10 carbon atoms, and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or carbon atom. Numbers 1-1
0 is an alkoxy group, and a is an integer of 0 to 2), a modified compound in which 1 to 10 polyoxyhydrocarbon groups are bonded to a silicone compound represented by the formula (I): Is at least one selected from the group consisting of modified compounds in which 1 to 10 polyoxyhydrocarbon groups are bonded to a partially hydrolyzed condensate of (a); the organic solvent (C) is an organic solvent having a boiling point of 160 ° C. or lower. A modified silicone compound (B) of 1 to 10 parts by weight based on 100 parts by weight of a solid content of the synthetic resin emulsion (A);
0 parts by weight, and the organic solvent (C) is 1 to 60 parts by weight.
It is contained in parts by weight.

[0008] In a preferred embodiment, the synthetic resin emulsion (A) contains an acrylic resin as a main component.

In a preferred embodiment, the synthetic resin emulsion (A) is an emulsion of a silyl group-containing acrylic resin, and the silyl group-containing acrylic resin is a silyl group represented by the general formula (II): : X ¹³ _-b SiR ³ _b (II) (wherein R ³ is independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 carbon atoms)
And aralkyl groups X ¹ to X ¹ are each independently a group selected from the group consisting of a halogen atom, an alkoxy group, a hydroxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group and an amino group; Is 0
Obtained by copolymerizing a vinyl-based monomer having the following formula:

[0010] In a preferred embodiment, the synthetic resin emulsion (A) is an acrylic resin emulsion, and the acrylic resin is an acrylic resin having a urethane bond or an acrylic resin capable of cross-linking urethane.

In a preferred embodiment, the synthetic resin emulsion (A) is an acrylic resin emulsion, and the emulsion contains an acrylic resin having a carbonyl group and a compound having a hydrazino group or hydrazine. .

In a preferred embodiment, the synthetic resin emulsion (A) contains an acrylic resin having a silyl group.

In a preferred embodiment, the above formula (I)
Are silicone compounds represented by tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, and tetra-t-butoxysilane And the polyoxyhydrocarbon group is derived from an alkylene oxide.

[0014] In a preferred embodiment, the organic solvent (C) is, ^{R 4} - _{(OH) c} (where, ^{R 4} is a hydrocarbon group, and c is an integer of 1 to 3) represented by Alcohol.

In a preferred embodiment, the coating composition has a solid content of 1 in the synthetic resin emulsion (A).
The modified silicone compound (B) is contained in a proportion of 1 to 100 parts by weight and the organic solvent (C) is contained in a proportion of 1 to 60 parts by weight with respect to 00 parts by weight.

The method for producing a coated substrate of the present invention includes a step of applying the aqueous coating composition described in any one of the above to the surface of the substrate.

The present invention includes a coated substrate obtained by applying the above aqueous coating composition to the surface of the substrate.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The inventors of the present invention have conducted intensive studies to solve the above-mentioned conventional problems, and as a result, have found that a synthetic resin emulsion and a modified silicone in which a polyoxyhydrocarbon group is bonded to a silicone compound having a specific structure. The present inventors have found that an aqueous coating composition containing a compound and an organic solvent having a specific boiling point can form a coating film having excellent surface hydrophilicity and stain resistance, and have completed the present invention.

As the synthetic resin emulsion (A) contained in the aqueous coating composition of the present invention, an emulsion obtained by emulsifying various coating resins by an ordinary method, and an emulsion of a commercially available aqueous coating resin can be used. And paints using these emulsions. The resin contained in the synthetic resin emulsion (A) is not particularly limited, and examples thereof include an acrylic resin, a urethane resin, a fluororesin, a melamine resin, a silicone resin, an epoxy resin, a polyester resin, and a polyether resin. And the like. Among these, the coating film formed using the obtained coating composition has excellent weather resistance and chemical resistance, and further has a wide range of resin designs,
Acrylic resin, urethane resin, fluorine resin and the like are preferable. Further, an acrylic resin is preferred from the viewpoint of excellent stain resistance and low cost.

The above-mentioned synthetic resin emulsion (A) can be obtained by polymerizing a polymerizable monomer capable of forming the resin in any type. For example, as the polymerizable monomer capable of forming the acrylic resin, at least one of the following vinyl monomers (containing at least one acrylic monomer) is used: methyl (meth) A) alkyl or aralkyl acrylate monomers such as acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate; styrene, α-methylstyrene,
Aromatic hydrocarbon-based vinyl monomers such as chlorostyrene, 4-hydroxystyrene and vinyltoluene; α, β-ethylenically unsaturated carboxylic acids (acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, anhydride Acids having a polymerizable carbon-carbon double bond such as itaconic acid, crotonic acid, fumaric acid, citraconic acid), styrene sulfonic acid, vinyl sulfonic acid, etc. or salts thereof (alkali metal salts, ammonium salts, amine salts, etc.) ;
Acid anhydrides such as maleic anhydride, or half esters of the anhydrides with linear or branched alcohols having 1 to 20 carbon atoms; dimethylaminoethyl (meth) acrylate;
(Meth) acrylates having an amino group such as dimethylaminopropyl (meth) acrylate and diethylaminoethyl (meth) acrylate; (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N -Acrylamide derivatives such as dimethylacrylamide, N-methylacrylamide and acryloylmorpholine, or salts thereof (hydrochlorides, acetates, etc.); vinyl esters or allyl compounds such as vinyl acetate, vinyl propionate, and diallyl phthalate; (meth) acrylonitrile Vinyl monomers containing nitrile groups such as glycidyl (meth)
Epoxy group-containing vinyl monomers such as acrylates; 2
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, hydroxystyrene, Alonix 5700 (manufactured by Toa Gosei Chemical Co., Ltd.), PlacelFA-1, Pl
accelFA-4, PlacelFM-1, Pla
ccelFM-4 (all manufactured by Daicel Chemical Industries, Ltd.), HE
-10, HE-20, HP-10, HP-20 (all manufactured by Nippon Shokubai Kagaku Co., Ltd.), Blemmer PP series, Blemmer PE series, Blemmer PEP series, Blemmer AP-400, Blemmer AE-350, Blemmer NKH- 5050, Blemmer GLM (all manufactured by NOF Corporation), MA-30, MA-50, MA-10
0, MA-150, RA-1120, RA-2614,
RMA-564, RMA-568, RMA-1114,
MPG130-MA (manufactured by Nippon Emulsifier Co., Ltd.), hydroxyl-containing vinyl monomers such as hydroxyl-containing vinyl-modified hydroxyalkylvinyl monomers; α, β-ethylene such as hydroxyalkyl (meth) acrylates Unsaturated unsaturated carboxylic acid hydroxyalkyl esters; phosphate ester group-containing vinyl compounds; (meth) acrylates containing urethane bonds or siloxane bonds; AS-6, a macromonomer manufactured by Toagosei Chemical Co., Ltd.
Compounds such as AN-6, AA-6, AB-6, and AK-5; and other vinyl monomers such as vinyl methyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, and N-vinylimidazole.

The resin used in the synthetic resin emulsion (A) contained in the water-based coating composition of the present invention is preferably an acrylic resin, among which an acrylic resin having a silyl group, a fluorine-containing acrylic resin, It is preferable that the composition is an acrylic resin having a urethane bond or a urethane crosslinkable, an acrylic resin having a carbonyl group, or a composition containing an acrylic resin having a carbonyl group and a compound having a hydrazino group or hydrazine.

The acrylic resin having a silyl group is as follows:
A silyl group represented by the general formula (II): X ¹³ _-b SiR ³ _b (II) (where R ³ is each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, Or 7 carbon atoms
And aralkyl groups X ¹ to X ¹ are each independently a group selected from the group consisting of a halogen atom, an alkoxy group, a hydroxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group and an amino group; Is an integer of 0 to 2) by copolymerizing a vinyl monomer having another vinyl monomer (at least one of these monomers has an acryloyl group). Specific examples of the compound having a silyl group represented by the general formula (II) include, for example, the following compounds.

[0023]

Embedded image

[0024]

Embedded image

Among these compounds, alkoxysilyl group-containing monomers are particularly preferred in terms of stability.

These silyl group-containing vinyl monomers are
They may be used alone or in combination of two or more. These monomers are used in an amount of 1 to 50% by weight, more preferably 2 to 3% by weight of the whole acrylic resin obtained.
The copolymer is preferably copolymerized so as to have a ratio of 0% by weight. If the copolymerization amount is less than 1% by weight, the obtained resin may be poor in water resistance and weather resistance, and if it exceeds 50% by weight, the stability of the emulsion may be reduced and the storage stability may be poor.

The fluorine-containing vinyl monomer constituting the fluorine-containing acrylic resin is not particularly restricted but includes, for example, the following compounds: trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate , Perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, β- (perfluorooctyl) ethyl (meth) acrylate, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene , Pentafluoropropylene, tetrafluoropropylene, trifluoropropylene, chlorotrifluoroethylene, bromotrifluoroethylene, chlorodifluoroethylene, dichlorodifluoroethylene and the like.

These fluorine-containing vinyl monomers may be used alone or in combination of two or more. These monomers are used in an amount of 1 to 50% by weight, more preferably 2 to 30% by weight of the whole acrylic resin obtained.
It is preferred that the copolymer be copolymerized so as to have a weight percentage. If the copolymerization amount is less than 1% by weight, the water resistance and weather resistance of the obtained resin may be inferior. If it exceeds 50% by weight, the stability of the emulsion is reduced, and the effect of introducing the fluorine-containing monomer is reduced. May be done.

The acrylic resin having a urethane bond can be obtained by introducing a urethane bond into a copolymer by using an isocyanate compound and a hydroxyl group-containing monomer when preparing the acrylic resin. The urethane crosslinkable resin is a vinyl polymer containing a free isocyanate group and / or a blocked isocyanate group. Examples of the resin include an isocyanate compound and a polyether containing two or more hydroxyl groups in one molecule. resin,
Reaction products with a polyester resin, a polycarbonate resin, and the like can be given. As the above isocyanate compound,
A compound having two isocyanate groups in one molecule is used. Examples include the following compounds: tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,
Aliphatic, aromatic or alicyclic diisocyanate compounds such as 4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (2,6) -diisocyanate, isophorone diisocyanate, and trimethylhexane diisocyanate; It is also possible to use an isocyanate-containing monomer in place of the isocyanate compound having a relatively small molecular weight. Such an isocyanate-containing monomer is prepared, for example, by reacting the isocyanate compound with a hydroxyl group-containing monomer. For example, 2-isocyanatoethyl methacrylate, m-isopropenyl-α, α'-dimethylbenzyl isocyanate, an equimolar adduct of 2-hydroxyethyl methacrylate and isophorone diisocyanate, and the like are preferable.

Specific examples of the carbonyl group-containing vinyl monomer used for preparing the carbonyl group-containing acrylic resin include, for example, the following compounds: acrolein, diacetone acrylamide, formylstyrene Vinylalkyl ketones having 4 to 7 carbon atoms (such as vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone), diacetone acrylate, acetonyl acrylate, diacetone methacrylate, 2-hydroxypropyl acrylate-acetyl acetate, Butanediol-1,4-acrylate-acetyl acetate and the like. These carbonyl group-containing vinyl monomers may be used alone or in combination of two or more.
These monomers are used in an amount of 0.1 to 30% by weight, preferably 3 to 10% by weight based on the total amount of the monomers used for producing the acrylic resin.
It is preferably used in a proportion by weight.

The compound having a hydrazino group is preferably a hydrazine derivative containing at least two hydrazine residues in one molecule. For example, 2-10
Dihydrazide which is a dehydration condensate of a dicarboxylic acid having 4 to 6 carbon atoms with hydrazine (oxalic dihydrazide, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, sebacine) Acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide,
And aliphatic water-soluble dihydrazines having 2 to 4 carbon atoms (eg, ethylene-1,2-dihydrazine (H ₂ NHN—CH ₂ —CH ₂ —NHNH).
₂ ), propylene-1,3-dihydrazine, butylene-
1,4-dihydrazine, adipic dihydrazide, etc.)
Is mentioned.

The vinyl monomer constituting the resin contained in the synthetic resin emulsion (A) is selected according to the physical properties of the intended coating composition. For example, in order to improve the stability of the synthetic resin emulsion (A), (meth) acrylic acid, maleic acid, dimethylaminoethyl (meth) acrylate, (meth) acrylamide, a hydroxyl group-containing vinyl monomer, polyethylene glycol It is preferable to use a hydrophilic monomer such as methacrylate and polypropylene glycol methacrylate. In order to improve the water resistance, durability and the like of a coating film formed using the obtained resin composition, a functional group for crosslinking inside and between emulsion particles may be introduced, or a fluorine-containing vinyl-based unit may be introduced. It is preferable to use a monomer or a siloxane-containing vinyl monomer. When an acidic vinyl monomer is used,
The mechanical stability of the synthetic resin emulsion (A) is improved.

As the monomer constituting the resin, for example, a monomer having two or more polymerizable unsaturated bonds such as polyethylene glycol dimethacrylate, ethylene glycol diacrylate, triallyl cyanurate, etc. is used. It is also possible for the polymer to have a crosslinked structure.

The resin used in the synthetic resin emulsion (A) is prepared by a polymerization method used for preparing a usual resin emulsion. For example, it is prepared by appropriately selecting a means of emulsion polymerization such as batch polymerization, monomer drop polymerization, and emulsion monomer drop polymerization. In particular, monomer drop polymerization and emulsion monomer drop polymerization are suitable for securing stability during production.

As the emulsifier used for such emulsion polymerization, any of commonly used emulsifiers can be used, and examples of the emulsifier include ionic and nonionic surfactants. Representative examples of ionic surfactants include the following compounds: sulfonates such as sodium lauryl sulfonate, sodium dodecyl benzene sulfonate, sodium isooctyl benzene sulfonate; Newcol-723SF, Newco
1-707SN, Newcol-707SF, Newc
anionic emulsifiers containing a (poly) oxyethylene group such as ol-740SF and Newcol-560SN (all manufactured by Nippon Emulsifier Co., Ltd.); and ammonium salts such as imidazoline laurate and ammonium hydroxide. Examples of the nonionic surfactant include polyoxyethylenes such as polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl ether;
77, L-720, L-5410, L-7602, L-
Nonionic emulsifiers containing silicon such as 7607 (all manufactured by Union Carbide). As an emulsifier, a compound having polymerization reactivity, 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-
Water resistance can be improved by using 60, Antox-MS-2N, RMA-653, and the like (all manufactured by Nippon Emulsifier Co., Ltd.).

As the polymerization initiator, any of the usual polymerization initiators is used, but from the viewpoint of polymerization stability and the like,
It is preferable to use a redox catalyst. In particular,
For example, with potassium or ammonium persulfate,
Combination with sodium acid sulfite or Rongalite;
A combination of hydrogen peroxide and ascorbic acid; an organic peroxide such as t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, and a reducing agent such as sodium acid sulfite and Rongalite. Are used. Particularly, a combination of the above organic peroxide and a reducing agent is preferable. In order to stably obtain the catalytic activity, a compound containing a divalent iron ion such as iron sulfate and a chelating agent such as disodium ethylenediaminetetraacetate may be used in combination.

The amount of the polymerization initiator used is from 0.01 to 1 based on 100 parts by weight of the monomer used for preparing the resin.
0 parts by weight, preferably 0.05 to 5 parts by weight.

The synthetic resin emulsion (A) or a resin contained in the emulsion can be produced by a method generally used by those skilled in the art. In preparing the synthetic resin emulsion (A), the concentration of the monomer is preferably adjusted so that the solid content of the obtained emulsion is in the range of 20 to 70% by weight. When the concentration of the monomer is too high, the viscosity of the system is significantly increased, so that it is difficult to remove the heat generated by the polymerization reaction, or there may be a problem that it takes a long time to take out from the polymerization machine. . If the concentration of the monomer is too low, there is no problem in terms of the polymerization operation, but the amount of resin produced by one polymerization operation is small, which is extremely disadvantageous in terms of economy. Furthermore, when the paint is used, the solid content is 2%.
When the content is less than 0% by weight, the thickness of the coating film becomes thin,
It causes performance deterioration and is disadvantageous in terms of painting workability.

The synthetic resin emulsion (A) thus obtained is composed of ultrafine particles having an average particle size of about 0.02 to 0.7 μm, and as a result, has excellent film-forming ability. ing.

The modified silicone compound (B) contained in the aqueous coating composition of the present invention has a general formula (I): (R ¹ O) _4-a SiR ² _a (I) (where R ¹ is An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and R ² each independently represent an alkyl group having 1 to 10 carbon atoms, Aryl group, aralkyl group having 7 to 10 carbon atoms or 1 to 1 carbon atom
0 is an alkoxy group, and a is an integer of 0 to 2), a modified compound in which 1 to 10 polyoxyhydrocarbon groups are bonded to a silicone compound represented by the formula (I): Is at least one selected from the group consisting of modified compounds in which 1 to 10 polyoxyhydrocarbon groups are bonded to the partially hydrolyzed condensate.

As the silicone compound represented by the above general formula (I) (hereinafter referred to as silicone compound (I)), any of tetraalkoxysilane, trialkoxysilane and dialkoxysilane can be used. Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, and tetra-silane.
and t-butoxysilane. As trialkoxysilanes, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane ,
Examples include propyltriethoxysilane, propyltripropoxysilane, propyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, and butyltributoxysilane.
Examples of the dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethylsilane, diethyldiethoxysilane, diethyldipropoxysilane, and diethyldibutoxysilane. These can be used alone or as a mixture of two or more.

The alkoxy group of the silicone compound (I) preferably has 1 to 4 carbon atoms. If the number of carbon atoms exceeds 5, a high temperature is required in the transesterification reaction, and the high temperature may cause gelation. The hydrolysis-condensation product of the silicone compound (I) has an average degree of condensation of 1
It is preferably from 10 to 10. If the average degree of condensation exceeds 10, handling becomes inconvenient, which is not preferable.

The modified silicone compound (B) used in the present invention has a form in which 1 to 10 polyoxyhydrocarbon groups are bonded to the silicone compound (I) and / or the partially hydrolyzed condensate of the silicone compound. . As the polyoxyhydrocarbon group, a polyoxyethylene group,
There are polyoxyalkylene groups such as polyoxypropylene groups.

As the modified silicone compound (B), for example, a compound obtained by modifying the silicone compound (I) and / or the partially hydrolyzed condensate of the silicone compound with a polyoxyalkylene group-containing compound is preferably used. You. Specifically, these modified silicone compounds (B) are, for example, silicone compounds (I) and / or
Alternatively, it can be obtained by a method of reacting a partially hydrolyzed condensate of the silicone compound with a compound having a polyoxyalkylene group by transesterification, a method of performing an addition reaction using a coupling agent, or the like.

The polyoxyalkylene group-containing compound represented by the following formula _^(III): R _{5 -} represented by ^{_{(OC n H 2n) m -R}} 6 (III).

Here, R ⁵ represents a hydrogen atom, an alkyl group, an epoxy group, or an acyl group, and R ⁶ represents a hydroxyl group, an alkyl group, an alkoxyl group, an epoxy group, an acyl group, or a carboxyl group. n is an integer of 1 to 4, m is 1 to
Indicates an integer of 20.

When a compound having a polyoxyalkylene group is reacted by the above transesterification reaction, the compound having a polyoxyalkylene group needs to have at least one hydroxyl group at the molecular terminal.

Specific examples of the polyoxyalkylene group-containing compound include polyoxyethylene glycol, polyoxyethylene glycol monoalkyl ether, polyoxyethylene propylene glycol, polyoxyethylene tetramethylene glycol, polyoxyethylene glycol diglycidyl ether, Polypropylene glycol diglycidyl ether, polyoxyethylene diglycolic acid, polyoxyethylene glycol vinyl ether, polyoxyethylene glycol allyl ether, polyoxyethylene glycol diallyl ether, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid Esters and polyoxyethylene alkylamines. These compounds can be used alone or in combination of two or more.

The average molecular weight of the polyoxyalkylene group-containing compound is preferably from 150 to 2,000. When the average molecular weight is less than 150, the stability of the modified silicone compound (B) obtained by the transesterification may be poor. Conversely, when the average molecular weight exceeds 2,000, the water resistance and hardness of the cured coating film tend to decrease.

In carrying out the transesterification reaction, a transesterification catalyst can be used. As the transesterification catalyst, for example, organic tin compounds such as dibutyltin dilaurate, dibutyltin malate, dioctyltin dilaurate, dioctyltin malate; phosphoric acid or phosphoric acid ester such as phosphoric acid, monomethyl phosphate, monoethyl phosphate, monooctyl phosphate And the like; adducts of epoxy compounds (propylene oxide, butylene oxide, glycidyl methacrylate, γ-glycidoxypropyltriethoxysilane, Epikote 828, etc.) with phosphoric acid and / or acidic monophosphate esters; organic titanate compounds; organoaluminum compounds ;
Organic zirconium compounds; maleic acid, adipic acid, azelaic acid, their acid anhydrides, acids or acid anhydrides such as paratoluenesulfonic acid; hexylamine, N, N
Amines such as dimethyldodecylamine; alkaline compounds such as sodium hydroxide.

These transesterification catalysts can be used alone or in combination of two or more. The amount used is preferably from 0.0001 to 5 parts by weight based on 100 parts by weight of the silicone compound (I) and / or the partial hydrolysis condensate of the silicone compound.
When the amount of the transesterification catalyst is 0.0001 parts by weight or less, the contribution to the transesterification reaction is small, and when the amount is 5 parts by weight or more, the condensation reaction is accelerated, and the stability of the resulting modified silicone compound (B) is reduced. Tend to.

When the modified silicone compound (B) is obtained by an addition reaction with a coupling agent, the coupling agent may be the above-mentioned silicone compound (I) in one molecule.
And / or a reactive functional group that binds the partially hydrolyzed condensate of the silicone compound to the polyoxyalkylene group-containing compound; and a compound having one or more alkoxysilyl groups.

Examples of the reactive functional group include a vinyl group, an epoxy group, an amino group, an isocyanate group, and a mercapto group. This functional group may be bonded to an alkoxysilyl group via a urethane bond, a urea bond, a siloxane bond, an amide bond, or the like.

Specific examples of the coupling agent include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, N-β (aminoethyl) γ-aminopropylmethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltri Ethoxysilane and the like can be mentioned.

The modified silicone compound (B) obtained as described above may be used alone or in combination of two or more. The modified silicone compound (B) is contained in an amount of 1 to 100 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the resin solid content of the synthetic resin emulsion (A). If the amount is less than 1 part by weight, the hardness and hydrophilicity of the coating film formed by the obtained coating composition are not sufficient, and if it exceeds 100 parts by weight, the appearance of the coating film is inferior, and the formed coating film loses physical followability. This causes problems such as cracks. If it exceeds 30 parts by weight,
The effect is not so different from the case of using 30 parts by weight. Care must be taken when the amount of the modified silicone compound (B) is large, since emulsion destruction may occur.

The organic solvent (C) contained in the aqueous coating composition of the present invention has a boiling point of 160 ° C. or less, preferably 100 ° C.
Organic solvent below ℃ The organic solvent (C) is preferably an organic solvent that is soluble or partially soluble in water. As such an organic solvent, alcohols, ketones and the like are used. As alcohols, R ^4- (O
H) _c (where R ⁴ is a hydrocarbon group and c is 1-3
And a monohydric to trihydric alcohol represented by the following formula: R ⁴ includes an alkyl group having 1 to 4 carbon atoms. Examples of alcohols include methanol, ethanol, isopropanol, n-butanol, iso-
Butanol and the like. As ketones, acetone,
Methyl isobutyl ketone (MIBK) and the like.

The organic solvent (C) is used in an amount of 1 part by weight based on 100 parts by weight of the resin solid content of the synthetic resin emulsion (A).
To 60 parts by weight, preferably 3 to 30 parts by weight. If the amount is less than 1 part by weight, the hydrophilicity of the surface layer portion of the coating film formed by the obtained coating composition is insufficient, so that satisfactory low stainability cannot be provided. On the other hand, 6
If the amount is more than 0 parts by weight, the stability of the emulsion itself is impaired, so that there is a problem that the practicality is lacking. In particular, in order to provide excellent hydrophilicity, the organic solvent (C) should be 3 to 3 times.
It is preferable to contain it at a ratio of 0 parts by weight.

The aqueous coating composition of the present invention comprises the above-mentioned synthetic resin emulsion (A), modified silicone compound (B),
And, if necessary, a curing catalyst, a film-forming aid, a pigment, various additives, a solvent (a solvent contained in the synthetic resin emulsion (A) and an organic solvent (C)).
Other solvents).

Examples of the curing catalyst include the following compounds: organic tin compounds such as dibutyltin dilaurate, dibutyltin malate, dioctyltin dilaurate, dioctyltin malate, tin octylate; phosphoric acid, monomethyl phosphate, monoethyl phosphate Phosphoric acid or phosphates such as monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, didecyl phosphate; epoxy compounds (propylene oxide,
Butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidol, acrylic glycidyl ether, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, oil Cardura (E) manufactured by Shell Epoxy Co., Ltd., Epicoat 828, Epicoat 100
1) and phosphoric acid and / or acidic monophosphate ester; organic titanate compound; organic aluminum compound; organic zirconium compound; maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, Acids or acid anhydrides such as succinic acid, trimellitic acid, pyromellitic acid, these acid anhydrides, paratoluenesulfonic acid; hexylamine, di-2-ethylhexylamine, N, N-dimethyldodecylamine;
Amines such as dodecylamine; mixtures or reactants of these amines with acidic phosphate esters; and alkali compounds such as sodium hydroxide and potassium hydroxide.

The curing catalyst may be used alone.
More than one species may be used in combination. The content of the curing catalyst is not particularly limited, but is usually the modified silicone compound (B).
The content is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight based on 100 parts by weight. If the content is 0.1 parts by weight or less, the curability of the modified silicone compound (B) may be reduced, and if it exceeds 20 parts by weight, the appearance of the coating film may be poor.

As the above-mentioned film-forming aid, compounds usually used as a film-forming aid of a coating composition, such as ether alcohols and ether esters, are used. Examples thereof include ethylene glycol monobutyl ether and ethylene glycol monobutyl ether acetate. The content of the film-forming aid is appropriately selected according to the required properties of the coating composition. Usually, it is contained in a proportion of 1 to 40 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the resin solid content of the synthetic resin emulsion (A).

As the pigment (usually used for coloring), both inorganic pigments and organic pigments can be used. As inorganic pigments, there are titanium dioxide, calcium carbonate, barium carbonate, kaolin, carbon, red iron, etc., and as organic pigments, phthalocyanine blue,
And quinacridone.

Examples of the additives include a plasticizer, a dispersant, a thickener, an antifoaming agent, a preservative, an antisettling agent, a leveling agent, and an ultraviolet absorber. The coating composition of the present invention,
Further, if necessary for viscosity adjustment and the like, a solvent (solvent contained in synthetic resin emulsion (A) and organic solvent (C)
Other solvents). The content of these additives and solvents is appropriately selected according to the required properties of the coating composition.

The above synthetic resin emulsion (A), modified silicone compound (B), organic solvent (C), and if necessary, the above curing catalyst, film forming aid, pigment, various additives, solvent, etc. By dissolving or dispersing in water, an aqueous paint is obtained.

This water-based paint is applied using a general coating method such as application by a brush or a roller, or spraying. The material of the substrate to be coated may be any of metal, ceramics, concrete, mortar, wood and the like. In order to improve the adhesion of the coating composition, the surface of the substrate may be subjected to a sanding treatment or a primer treatment in advance.

When the coating composition of the present invention is applied to the surface of a substrate, hydrolysis and polycondensation of the modified silicone compound (B) contained in the composition progresses, during which the compound is coated on the surface of the coating film. It is thought that it becomes localized. After being applied to the substrate, the coating is cured usually at 10 ° C. or higher, whereby the coating is cured, and a cured film (coating) is formed on the surface of the substrate. In the present invention, the composition contains an organic solvent (C). Therefore, the cured film is formed in a short time. Since the boiling point of this solvent is 160 ° C. or less, the solvent is
Volatilizes and disappears in about a week, and does not remain in the coating film. It is considered that in the formed coating film, the polycondensate of the modified silicone compound (B) is localized on the coating film surface, so that the surface hardness increases and the surface is given hydrophilicity.

As described above, a coating film having high hydrophilicity and high surface hardness is formed in a short time. Since this coating film has a high surface hardness, it is hardly scratched and prevents contamination. At the same time, since the coating film is hydrophilic, a cleaning effect by rain or the like is exhibited, and more excellent stain resistance is obtained. In particular, the antifouling property of the coating film when the substrate coated with the coating film is subjected to natural exposure is remarkable. On the other hand, in the conventional water-based paint, a coating film having high hydrophilicity and high surface hardness is formed on the surface, and it takes a relatively long time before the hydrophilicity is developed. Therefore, the resistance performance and the hydrophilicity of the surface in the initial stage after application of the paint are poor.

As described above, by using the coating composition of the present invention, it is possible to obtain a substrate on which a coating film having excellent physical properties such as stain resistance, weather resistance, adhesion and durability is formed. .

The aqueous coating composition of the present invention is used for various uses. For example, paints for building interior and exterior; paints for automobiles as paints for metallic base or clear paint on metallic base; aluminum, stainless steel,
Paints for direct application to metal substrates in various fields of materials such as silver; slate, concrete, tile, mortar, gypsum board, asbestos slate, asbestos board, precast concrete, lightweight cellular concrete, calcium silicate board, tile, brick, etc. It is used as a paint for ceramics directly applied to a base material; as a paint for stone materials such as glass, natural marble and granite, or as an upper surface treatment agent.

[0070]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments. “Parts” and “%” in the examples and comparative examples are on a weight basis.

(Example 1) Preparation of Paint Containing Acrylic Resin 100 parts of Taipaque CR-97 (titanium dioxide pigment manufactured by Ishihara Sangyo Co., Ltd.), 15 parts of BYK-190 (dispersing agent manufactured by BYK-Chemie), and 45 parts of clear water are put into a test sand mill. Then, 400 parts of glass beads having a particle size of 1.2 to 1.5 mm (manufactured by Toshiba Corporation) are added thereto, and
For about 30 minutes. After the dispersion was completed, the glass beads were removed by filtration to obtain a mill base. Then, at 800 rpm
350 parts of AD-63 (acryl emulsion, Nippon NS Co., Ltd., 50% of non-volatile content; synthetic resin emulsion (A)), SN deformer 373 (antifoaming agent, manufactured by San Nopco Co., Ltd.) 5 copies, CS1
2 (Chisso Corporation) and 5 parts of Adecanol UH-420 (Asahi Denka Co., Ltd. thickener) were further added and stirred at 800 rpm for 30 minutes. .1) was obtained.

Separately, 100.0 parts of an ethylsilicate condensate having an average molecular weight of 750 (average molecular weight of 750), which is a condensate of tetraethoxysilane, and an average molecular weight of 20
Of polyoxyethylene glycol # 200 (manufactured by Wako Pure Chemical Industries, Ltd.). After adding 0.02 parts of dibutyltin dilaurate as a catalyst thereto, 75
The ethanol removal reaction was performed at 8 ° C. for 8 hours to obtain a modified silicone compound (B1).

The above acrylic coating liquid (No. 1) 300
Part (100% as the solid content of the synthetic resin emulsion (A))
), The modified silicone compound (B1) in the amounts shown in Tables 1 and 2 and the organic solvent (C) in the types and amounts shown in Tables 1 and 2 were added to obtain Paints 1 to 54.

2. Performance Evaluation of Paints The obtained paints 1 to 54 were subjected to an outdoor exposure test as described below as a test closest to actual use, and their performance was evaluated.

A 100 mm × 300 mm × 0.8 mm stainless steel substrate (SUS-304) to which a primer for stainless steel was previously applied was bent at 120 ° at a substantially central portion in the longitudinal direction as shown in FIGS. 1A and 1B. The coating material prepared above was applied to the outer surfaces 11 and 12 of the bent stainless steel substrate 1 by spray coating so that the dry film thickness became about 50 μm, and left at room temperature for 14 days to dry and harden. . The substrate having the obtained coating film was used as a test plate 1. One test plate for each paint
It was produced one by one.

The surface 12 of the test plate 1 is at an angle of 90 degrees with respect to the horizontal ground outdoors (in the Shiga Plant of Isamu Paint Co., Ltd. in Kusatsu, Shiga Prefecture). The test plate 1 was fixed so that the extension surface and the ground made an angle of 30 degrees.

The water contact angle on the surface 11 of the test plate 1 was measured over time. The measuring method is as follows.

Water contact angle: Kyowa Interface Science contact angle measuring instrument C
The measurement was performed using AS150. The measurement was carried out before the outdoor exposure of the test plate 1 and every 10 days after the exposure up to 30 days.

The modified silicone compound (B1) and Table 6
6 containing 15 parts of the organic solvent (C) shown in
Kinds of paints (Paint Nos. 6, 15, 24, 33, 42, 5
1 and 59), the lightness difference ΔL was measured over time for the test plate obtained. The measuring method is as follows.

Lightness difference ΔL: Color difference meter CR331 manufactured by Minolta
Was measured using an L * a * b * colorimetric system. The measurement was performed before the outdoor exposure of the test plate 1 and 1 month, 3 months, and 6 months after the exposure.

Further, the state of contamination due to rain streaks on the surface 12 of these test plates was visually evaluated with time. The criteria for the visual evaluation are as follows: 0: no contamination is observed visually 1: almost no contamination is observed visually 2: raindrops due to partial contamination can be confirmed faintly 3: almost all contamination 4: The raindrop caused by contamination can be clearly seen on the entire surface. 5: The raindrop caused by contamination can be extremely remarkably confirmed on the entire surface.

The results of measuring the water contact angles are shown in Tables 3-5.
Shown in Table 6 shows the evaluation result of the lightness difference ΔL and the evaluation result indicating the contamination due to rain streak.

(Comparative Example 1) Modification of the amount shown in Table 2 to 300 parts of the acrylic coating liquid (No. 1) obtained in Example 1 (100 parts as a solid content of the synthetic resin emulsion (A)) Paints 55 to 58 were obtained with or without the addition of the silicone compound (B1), and evaluation was performed in the same manner as in Example 1. Evaluation of the state of contamination due to rain streak
o. The test was performed on a test plate obtained using No. 58. The results are shown in Tables 3 to 6 (excluding the paint 55).

The evaluation results of the water contact angle of the paint 55 containing neither the modified silicone compound (B1) nor the organic solvent (C) were as follows. initial value:
60 degrees; after 10 days: 80 degrees; after 20 days: 78 degrees; after 30 days: 76 degrees.

(Comparative Example 2) 15 parts of the modified silicone (B1) and 300 parts of the acrylic coating liquid (No. 1) obtained in Example 1 (100 parts as the solid content of the synthetic resin emulsion (A)) Paint 59 was prepared by adding 15 parts of butyl cellosolve. With respect to the test plate obtained using this, the measurement of the lightness difference ΔL and the state of contamination due to rain streak were evaluated in the same manner as in Example 1. Table 6 shows the results.

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

[Table 3]

[0089]

[Table 4]

[0090]

[Table 5]

[0091]

[Table 6]

From the results of the above Examples and Comparative Examples, when the coating material contains the modified silicone compound (B1), the amount of the modified silicone compound (B1) was adjusted to 3, 9 and 15 parts.
The water contact angle was hardly changed even when the number of parts was increased.
However, it was found that when the organic solvent (C) was contained therein, the water contact angle was drastically reduced, and the value decreased as the amount of the organic solvent (C) increased. In the above coating composition, the best results are obtained when the amounts of the modified silicone compound (B1) and the organic solvent (C) are both 15 parts with respect to 100 parts of the solid content of the synthetic resin emulsion (A). Was. As the type of the organic solvent (C), ethanol was the best.

(Example 2) Synthetic resin emulsion (A)
Was used in the same manner as in Example 1 except that KD-10 (acrylic silicone emulsion manufactured by Nippon NS Co., Ltd., nonvolatile content: 43%) was used to obtain an acrylic coating liquid (No. 2). The above acrylic paint liquid (No.
2) 15 parts of the modified silicone compound (B1) and 15 parts of ethanol were added to 300 parts (100 parts of solid content) to obtain a paint. When this paint was evaluated in the same manner as in Example 1, the same results as in the case of using ethanol in Example 1 were obtained.

(Example 3) Synthetic resin emulsion (A)
As Nanocloth 9620 (hydrazine cross-linked acrylic emulsion manufactured by Toyo Ink Mfg. Co., Ltd., nonvolatile content 50%)
Was used in the same manner as in Example 1 to obtain an acrylic coating liquid (No. 3). 15 parts of the modified silicone compound (B1) and ethanol 15 were added to 300 parts (solid content: 100 parts) of the acrylic coating liquid (No. 3).
Parts were added to obtain a paint. When this paint was evaluated in the same manner as in Example 1, the same results as in the case of using ethanol in Example 1 were obtained.

(Example 4) Synthetic resin emulsion (A)
AD-98 (acryl polyol emulsion manufactured by Nippon NS Co., Ltd., nonvolatile content: 50%) was operated basically in the same manner as in Example 1. The above synthetic resin emulsion (A), SN Deformer 373, CS12, and Adekanol UH-420 were added, and 800 rpm was added.
, And 15 parts of Aquanate 100 (a polyisocyanate manufactured by Asahi Kasei Corporation) was further added, followed by stirring for 2 minutes to obtain an acrylic coating liquid (No. 4). 300 parts of this acrylic paint liquid (No. 4) (100 parts of solid content)
Then, 15 parts of the modified silicone compound (B1) and 15 parts of ethanol were added to obtain a paint. When this paint was evaluated in the same manner as in Example 1, the same results as in the case of using ethanol in Example 1 were obtained.

[0096]

As described above, according to the present invention, an aqueous paint capable of forming a coating film having excellent surface hydrophilicity and stain resistance, high hardness, and excellent weather resistance and water resistance. A composition is provided. When such a coating composition is applied to various substrates by the method of the present invention, a cured coating film is formed on the surface of the substrate. The coated substrate having the cured coating film thus obtained has the above-mentioned various excellent properties such as surface hydrophilicity and stain resistance. Particularly when installed outdoors, it has a function of removing adhering contaminants with rainwater, so that an excellent antifouling function is exhibited. As described above, the coating composition of the present invention and the coated substrate obtained by using the same are suitably used in many fields including interior and exterior of buildings, automobiles, home appliances, outdoor equipment, and the like.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a test plate for an outdoor exposure test used in Examples and Comparative Examples.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 143/04 C09D 143/04 183/02 183/02 183/10 183/10 (72) Inventor Kazuo Tsunoi 8-2-1 Kasayama, Kusatsu-shi, Shiga Prefecture Isamu Paint Co., Ltd., Shiga Factory (72) Inventor Hajime Okamoto 1-5-1, Otsuka, Inzai City, Chiba Prefecture Takenaka Corporation Technical Research Institute (72) Inventor Satoru Osawa 1-5-1, Otsuka, Inzai City, Chiba Prefecture, Japan Takenaka Corporation Technical Research Institute (72) Inventor Kan Hasegawa 1-5-1, Otsuka, Inzai City, Chiba Prefecture Takenaka Corporation Technical Research Institute (72) Nobuo Murakami 1-5-1, Otsuka, Inzai City, Chiba Prefecture F-term in Takenaka Corporation Technical Research Institute 4D075 CA34 DB31 DC01 DC11 DC18 EA06 EB16 EB22 EB32 EB33 E B35 EB37 EB38 EB42 EB56 4J038 CC061 CC062 CD071 CD072 CD091 CD092 CG141 CG142 CG161 CG162 CG171 CG172 CH031 CH032 CH041 CH042 CH071 CH072 CH121 CH122 CH201 CH251 CH252 CH262 CJ021 CJ012 CJ101 CJ102 CJ101 CJ001 DL031 DL032 DL101 DL102 DL151 DL152 GA02 GA06 GA09 GA15 JA19 JA33 KA04 KA06 MA08 MA10 NA03 NA04 NA05 NA06 NA27 PA18 PB07 PB09 PC02 PC03 PC04 PC08

Claims (11)

[Claims] 1. An aqueous coating composition comprising a synthetic resin emulsion (A), a modified silicone compound (B) and an organic solvent (C), wherein the modified silicone compound (B) has the general formula (I) : (R ¹ O) _4-a SiR ² _a (I) (where R ¹ is independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 to 10 carbon atoms) R ² is independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or 1 to 1 carbon atoms.
0 is an alkoxy group, and a is an integer of 0 to 2), a modified compound in which 1 to 10 polyoxyhydrocarbon groups are bonded to a silicone compound represented by the formula (I): And at least one selected from the group consisting of modified compounds in which 1 to 10 polyoxyhydrocarbon groups are bonded to the partially hydrolyzed condensate of (a), wherein the organic solvent (C) is an organic solvent having a boiling point of 160 ° C. or lower. The ratio of the modified silicone compound (B) is 1 to 100 parts by weight, and the amount of the organic solvent (C) is 1 to 60 parts by weight, based on 100 parts by weight of the solid content of the synthetic resin emulsion (A). A water-based coating composition contained in 2. The coating composition according to claim 1, wherein the synthetic resin emulsion (A) contains an acrylic resin as a main component. Wherein the synthetic resin emulsion (A) is an emulsion of an acrylic resin having a silyl group, a silyl group acrylic resin having the silyl group is represented by the general formula (II): X ¹ _{3- b} SiR ³ _b (II) (where R ³ is independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 carbon atoms)
And aralkyl groups X ¹ to X ¹ are each independently a group selected from the group consisting of a halogen atom, an alkoxy group, a hydroxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group and an amino group; Is 0
The coating composition according to claim 1, wherein the coating composition is obtained by copolymerizing a vinyl monomer having the formula (1) to (2) with another vinyl monomer. 4. The synthetic resin emulsion (A) is an acrylic resin emulsion, and the acrylic resin is an acrylic resin having a urethane bond or an acrylic resin capable of cross-linking urethane. The coating composition according to any one of the above. 5. The synthetic resin emulsion (A) is an acrylic resin emulsion, and the emulsion is
The coating composition according to any one of claims 1 to 4, comprising an acrylic resin having a carbonyl group and a compound having a hydrazino group or hydrazine. 6. The coating composition according to claim 1, wherein the synthetic resin emulsion (A) contains an acrylic resin having a silyl group. 7. The silicone compound represented by the formula (I) is tetramethoxysilane, tetraethoxysilane,
Tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-
The coating composition according to any one of claims 1 to 6, wherein the coating composition is at least one selected from the group consisting of butoxysilane and tetra-t-butoxysilane, and wherein the polyoxyhydrocarbon group is derived from an alkylene oxide. Wherein said organic solvent (C) is, ^{R 4} - (OH)
_c (where, ^{R 4} is a hydrocarbon group, and c is an integer of 1 to 3) is an alcohol represented by the claims 1-7
The coating composition according to any one of the above. 9. The modified silicone compound (B) is used in a proportion of 1 to 100 parts by weight and the organic solvent (C) is used in an amount of 1 to 60 parts by weight based on 100 parts by weight of the solid content of the synthetic resin emulsion (A). 2. The composition according to claim 1, which is contained in parts by weight.
9. The coating composition according to any one of items 1 to 8. 10. A method for producing a coated substrate, comprising a step of applying the aqueous coating composition according to claim 1 to a substrate surface. 11. A coated substrate obtained by applying the aqueous coating composition according to claim 1 to a substrate surface.