CN105086819B - Aqueous coating agent composition, film and coated articles - Google Patents

Abstract

The present invention provides a water-based coating agent composition capable of forming a coating film capable of maintaining appearance and stain resistance at a high level for a long period of time, a coating film, and a painted product. A water-based coating composition comprising a dispersion (CD) of a copolymer (C) and an inorganic oxide (D), the copolymer (C) comprising a structural unit (A) and a structural unit (B), The structural unit (A) is derived from the silane (a) with a specific structure, and the structural unit (B) is derived from the silane (b) with a specific structure; the content of the structural unit (A) in the copolymer (C) It is 32-70 mass % in conversion of a hydrolysis-condensation product, and content of the structural unit (B) in a copolymer (C) is 23-45 mass % in conversion of a hydrolysis-condensation product.

Description

Water-based coating agent composition, coating film and coated product

technical field

The invention relates to a water-based coating agent composition, a coating film and a coated product.

Background technique

The surface of outdoor structures such as building exteriors, bridges, and tanks is coated with paint, etc., but the surface of the coating film is covered by dust, soot, sand, etc. in the air; dirt components dissolved from sealing materials; Contaminated by pollutants discharged from the outlet. The contamination of such a coating film is usually light black, and remarkably impairs the appearance of buildings and outdoor structures.

As a water-based topcoat coating agent composition that suppresses the above-mentioned coating film contamination, the applicant has proposed a double-layer coating film comprising an undercoat layer and an upper coat layer disposed on the undercoat layer, and the above-mentioned undercoat layer The layer is a film formed by drying the coating film of the primer composition (I) containing polymer emulsion particles (A) in the presence of water and an emulsifier. It is obtained by the method of separately polymerizing the vinyl monomer and the hydrolyzable silicon compound; the above-mentioned top coat is a film formed by drying the coating film of the coating agent composition (II) for the top coat, and the top coat The coating agent composition (II) comprises photocatalytically active metal oxide particles (B), polymer emulsion particles (C) and colloidal silica (D), and the polymer emulsion particles (C) are obtained by using It is obtained by the method of separately polymerizing a vinyl monomer and a hydrolyzable silicon compound in the presence of water and an emulsifier (see Patent Document 1).

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2010-005595

Contents of the invention

The problem to be solved by the invention

In the technology described in Patent Document 1, a material with a high glass transition temperature is used as the undercoat layer, so even a topcoat layer formed of a topcoat coating agent composition can obtain sufficient stain resistance and weather resistance sex. In this way, the technology of Patent Document 1 is an excellent technology, but the inventors of the present invention have attempted to develop a further improved technology by making further improvements. For example, when the coating agent composition for top coating as described in Patent Document 1 is overcoated on a substrate using a material having a glass transition temperature of about -5 to 20°C, which is commonly used in building exteriors, etc., the The top coat layer formed from the top coat coating agent composition may not sufficiently follow the substrate that expands and contracts due to changes in external temperature or the like. In such a case, cracks or the like may be generated in the top coat layer, and the appearance may be deteriorated due to a decrease in gloss due to the cracks. Furthermore, dust, soot, sand, etc. may adhere to the cracked portion and become contaminated. If the aforementioned aspects of the coating film can be improved, a coating film excellent in various physical properties including appearance and stain resistance over a long period of time can be expected regardless of the substrate.

The present invention was made in view of the above circumstances, and an object of the present invention is to provide a water-based coating agent composition capable of forming a coating film capable of maintaining the appearance and stain resistance at a high level for a long period of time.

means of solving problems

As a result of intensive research, the present inventors found that the above-mentioned problems were solved by using the following water-based coating agent composition containing a dispersed copolymer (C) A body (CD) and an inorganic oxide (D), the copolymer (C) comprises a structural unit (A) and a structural unit (B), and the structural unit (A) is derived from a silane (a) having a specific structure, so The structural unit (B) is derived from a silane (b) with a specific structure, the content of the structural unit (A) in the copolymer (C) and the content of the structural unit (B) in the copolymer (C) are in a specific range .

That is, the present invention is as follows.

[1]

A water-based coating agent composition, which contains:

The dispersion (CD) of copolymer (C), this copolymer (C) comprises structural unit (A) and structural unit (B), and described structural unit (A) derives from and is represented by following general formula (1) The silane (a), the structural unit (B) is derived from the silane (b) represented by the following general formula (2); and

Inorganic oxides (D);

The content of the above-mentioned structural unit (A) in the above-mentioned copolymer (C) is 32 to 70% by mass in terms of a hydrolysis condensate,

Content of the said structural unit (B) in the said copolymer (C) is 23-45 mass % in conversion of a hydrolysis-condensation product.

(R ¹ ) ₂ -Si-(R ² ) ₂ ···(1)

( ^R1 each independently represents a hydrogen atom, an aliphatic hydrocarbon group with 1 to 16 carbon atoms, an aryl group with 6 to 10 carbon atoms, a cycloalkyl group with 5 to 6 carbon atoms, a phenyl group, a carbon atom An alkyl acrylate group with a number of 1 to 10, or an alkyl methacrylate group with a number of carbon atoms of 1 to 10, ^R2 each independently represents an alkoxy group or an acetoxy group with a number of carbon atoms of 1 to 8 , or hydroxyl.)

R ³ -Si-(R ⁴ ) ₃ ···(2)

( ^R3 represents a hydrogen atom, an aliphatic hydrocarbon group with 1 to 16 carbon atoms, an aryl group with 6 to 10 carbon atoms, a cycloalkyl group with 5 to 6 carbon atoms, a phenyl group, a phenyl group with 1 to 16 carbon atoms 10 is an alkyl acrylate group or an alkyl methacrylate group having 1 to 10 carbon atoms, R ⁴ each independently represents an alkoxy group, an acetoxy group, or a hydroxyl group having 1 to 8 carbon atoms. )

[2]

The water-based coating agent composition according to [1], wherein the dispersion (CD) of the copolymer (C) is obtained by emulsion polymerization using at least the above-mentioned silane (a) and the above-mentioned silane (b) .

[3]

The water-based coating agent composition according to [1] or [2], wherein the inorganic oxide (D) is silica.

[4]

The water-based coating agent composition according to any one of [1] to [3], wherein the composition further contains an inorganic oxide (E) having photocatalytic activity.

[5]

The water-based coating agent composition according to any one of [1] to [4], further comprising a fluorocarbon surfactant (F).

[6]

The water-based coating agent composition according to any one of [1] to [5], wherein the composition further contains a discoloring dye (G).

[7]

The water-based coating agent composition according to any one of [1] to [6], further comprising a cellulose-based thickener (H).

[8]

The water-based coating agent composition according to any one of [1] to [7], wherein the composition further contains at least one kind selected from the group consisting of an anti-algae agent and an anti-fungal agent (J). substance.

[9]

A water-based paint containing the water-based coating agent composition according to any one of [1] to [8].

[10]

A coating film obtained from the water-based paint described in [9].

[11]

A coated product comprising a substrate and the coating film according to [10], the coating film being formed on at least a part of the surface of the substrate.

[12]

The coated product according to [11], wherein the substrate is an organic substrate.

Invention effect

According to the present invention, it is possible to provide a water-based coating agent composition capable of forming a coating film capable of maintaining the appearance and stain resistance at a high level for a long period of time.

Detailed ways

This specific embodiment (hereinafter referred to as "the present embodiment") will be described below. The following present embodiment is an illustration for explaining the present invention, and is not intended to limit the present invention to the following. The present invention can be implemented with appropriate modifications within the scope of the gist. It should be noted that, as long as there is no special statement, "(meth)acrylate" refers to "acrylate" and its corresponding "methacrylate", "(meth)acrylic acid" refers to "acrylic acid" and its corresponding "methacrylic acid".

[water-based composition]

The aqueous composition of the present embodiment contains a dispersion (CD) of a copolymer (C) containing silane (a) derived from the general formula (1) and an inorganic oxide (D). Structural unit (A) and structural unit (B) derived from silane (b) represented by general formula (2). In addition, in the water-based coating agent composition, the content of the structural unit (A) in the copolymer (C) is 32 to 70% by mass in terms of hydrolytic condensate, and the content of the structural unit (B) in the copolymer (C) is It is 23-45 mass % in conversion of a hydrolysis-condensation product.

<Dispersion (CD)>

Dispersion (CD) is a dispersion of copolymer (C). The dispersion of the copolymer (C) is not particularly limited, but is preferably an aqueous dispersion from the viewpoint of an aqueous system. Examples of such aqueous dispersions include (a) components, (b) components, and, if necessary, hydrolyzable silicon compounds other than (a) and (b) components and/or vinyl monomers. Aqueous dispersion (CD) of a copolymer (C) obtained by emulsion polymerization of a body or the like.

The copolymer (C) contains 32-70 mass % of structural units (A) in terms of hydrolysis-condensation product conversion components, and the structural unit (B) in the ratio of 23-45 mass % of hydrolysis-condensation product conversion components. When the content of the structural unit (A) and the content of the structural unit (B) in the copolymer (C) are out of the above range, the weather resistance and stain resistance of the coating film will become insufficient. It should be noted that the hydrolysis condensate mentioned here refers to the conversion of reactive groups (such as alkoxy groups, etc.) of (a) component and (b) component contained in the system to silane through hydrolysis and condensation reactions. Condensates of alcohol bonds. The content (mass %) of the hydrolysis-condensation product of the structural unit (A) and the structural unit (B) can be obtained from the content of the copolymer (C) (total solid content) obtained from the heating residue of the (CD) component , (a) component, (b) the feeding amount of component, use calculation to find out. Specifically, it can be obtained by the method described in the examples described later. In addition, the content (mass %) of the structural unit (A) and the structural unit (B) in the copolymer (C) can also be directly measured by Si solid NMR.

The lower limit of the content of the structural unit (A) in the copolymer (C) is 32% by mass or more, preferably 47% by mass or more. The upper limit of the content of the structural unit (A) in the copolymer (C) is 70% by mass or less, preferably 65% by mass or less.

The lower limit of the content of the structural unit (B) in the copolymer (C) is 23% by mass or more, preferably 25% by mass or more. The upper limit of the content of the structural unit (B) in the copolymer (C) is 45% by mass or less, preferably 39% by mass or less, more preferably 35% by mass or less.

Specific examples of the silane (a) represented by the general formula (1) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyl Diethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyl Dimethoxysilane, diisobutyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldiethoxysilane Methoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethyl Oxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, dimethoxymethylbenzene silane, diphenyldiethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, etc.

Among these, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, Diphenyldimethoxysilane, dimethoxymethylphenylsilane, more preferably dimethyldimethoxysilane, dimethoxymethylphenylsilane, more preferably dimethyldimethoxysilane . These may be used alone or in combination of two or more.

Specific examples of the silane (b) represented by the general formula (2) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane , n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyl Trimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxy Silane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropyltri-n-propoxysilane, 3-(meth)acryloxypropyl Triisopropoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, etc. Among these, methyltrimethoxysilane, phenyltrimethoxysilane, and 3-(meth)acrylic acid are preferred from the viewpoints of the hydrolysis rate during polymerization, etc., and the weather resistance and stain resistance of the obtained coating film. Acyloxypropyltrimethoxysilane. These may be used alone or in combination of two or more.

The hydrolyzable silicon compound other than the components (a) and (b) used in the production of the copolymer (C) is not particularly limited, but compounds represented by the following general formula (3) and their condensates are preferably used. Wait.

SiW _x R _y ···(3)

In the formula, W represents an alkoxy group with 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group with 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group with 1 to 20 carbon atoms, At least one selected from the group consisting of enoxy (enokish) group, aminooxy group and amide group. R represents a group selected from linear or branched alkyl groups with 1 to 30 carbon atoms, cycloalkyl groups with 5 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, halogenated At least one group from the group consisting of aryl groups having 6 to 20 carbon atoms substituted by atoms. x is an integer of 1 to 4, y is an integer of 0 to 3, and the relationship of x+y=4 is satisfied. When there are two or more W, and when there are two or more R, each of W and R may be the same as or different from each other.

The silicon alkoxide of one embodiment of the hydrolyzable silicon compound represented by the general formula (3) is not particularly limited as long as it is a substance other than the (a) component and the (b) component, and examples thereof include tetramethoxysilane, Tetraalkoxysilanes such as tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane. Among tetraalkoxysilanes, tetramethoxysilane and tetraethoxysilane are preferable from the viewpoint of the hydrolysis rate during polymerization. These may be used alone or in combination of two or more.

Specific examples of vinyl monomers that can be used in the production of the copolymer (C) include (meth)acrylates, aromatic vinyl compounds, vinyl cyanide compounds, carboxyl group-containing vinyl compounds, Hydroxyl-containing vinyl compounds, glycidyl-containing vinyl compounds, vinyl compounds having secondary and/or tertiary amide groups, anionic vinyl compounds, and other functional group-containing vinyl monomers.

Specific examples of (meth)acrylates are not particularly limited, and include, for example, alkyl (meth)acrylates having an alkyl group having 1 to 50 carbon atoms, alkyl (meth)acrylates having an alkyl group having 1 to 100 carbon atoms, Vinyl (poly)oxyethylene di(meth)acrylate, etc.

Specific examples of (meth)acrylates are not particularly limited, and examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate- 2-Ethylhexyl, methylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, etc.

Specific examples of (poly)oxyethylene di(meth)acrylate are not particularly limited, and examples include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, methoxy Diethylene glycol (meth)acrylate, tetraethylene glycol di(meth)acrylate, etc.

Specific examples of the aromatic vinyl compound are not particularly limited, and examples thereof include styrene, α-methylstyrene, p-tert-butylstyrene, chlorostyrene, and vinyltoluene.

Specific examples of the vinyl cyanide compound are not particularly limited, and examples thereof include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile.

Specific examples of the carboxyl group-containing vinyl compound are not particularly limited, and examples include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, or itaconic acid, Half esters of dibasic acids such as maleic acid and fumaric acid. By using a carboxyl group-containing vinyl monomer, a carboxyl group can be introduced into the structural unit (A). In this way, the stability as an emulsion can be further improved, and it is presumed that it can have high resistance to dispersion damage from the outside (but the effects of this embodiment are not limited to these). At this time, a part or all of the carboxyl groups introduced may be neutralized with amines such as ammonia, triethylamine, and dimethylethanolamine, and bases such as NaOH and KOH. The amount of the carboxyl group-containing vinyl monomer used in the total amount of the above-mentioned vinyl monomers is preferably 0 to 10% by mass from the viewpoint of water resistance, but is not limited thereto.

Specific examples of hydroxyl-containing vinyl compounds are not particularly limited, and examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. Hydroxyalkyl of (meth)acrylic acid such as -hydroxypropyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Esters; di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fumarate, allyl alcohol or (poly)oxyethylene mono( Meth)acrylates; (poly)oxypropylene mono(meth)acrylates having 1 to 100 propylene oxide groups, and "PRAXCELL FM, FA monomers" (caprolactone addition monomers manufactured by Daicel Chemical Co., Ltd. trade names of its body), other hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids.

Specific examples of (poly)oxyethylene (meth)acrylate are not particularly limited, and examples include ethylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, (methoxyethylene glycol) ) diethylene glycol acrylate, diethylene glycol methoxy (meth)acrylate, tetraethylene glycol (meth)acrylate, tetraethylene glycol methoxy (meth)acrylate, etc.

Specific examples of (poly)oxypropylene (meth)acrylate are not particularly limited, and examples include propylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, dipropylene glycol (meth)acrylate , Dipropylene glycol methoxy (meth)acrylate, tetrapropylene glycol (meth)acrylate, tetrapropylene glycol methoxy (meth)acrylate, etc.

Specific examples of the glycidyl group-containing vinyl compound are not particularly limited, and examples thereof include glycidyl (meth)acrylate, allyl glycidyl ether, and allyl dimethyl glycidyl ether.

Specific examples of vinyl monomers having secondary and/or tertiary amide groups are not particularly limited, and examples include N-alkyl substituted (meth)acrylamides, N-alkylene substituted (methyl) acrylamide etc.

Specific examples of N-alkyl-substituted (meth)acrylamides are not particularly limited, and examples include N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N,N- Dimethyl(meth)acrylamide, N,N-diethylacrylamide, N-methyl-N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N- N-propyl (meth)acrylamide, N-methyl-N-n-propyl (meth)acrylamide, N-methyl-N-isopropyl (meth)acrylamide, N-(methyl) Acryloylpyrrolidine, N-(meth)acryloylpiperidine, N-acryloylhexahydroazepine, N-(meth)acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N, N'-methylenebis(meth)acrylamide, N-vinylacetamide, diacetone(meth)acrylamide, N-methylol(meth)acrylamide, and the like.

Specific examples of vinyl monomers other than those mentioned above include olefins such as (meth)acrylamide, ethylene, propylene, and isobutylene; dienes such as butadiene; vinyl chloride, vinylidene chloride, Halogenated olefins such as fluorinated ethylene, tetrafluoroethylene, and chlorotrifluoroethylene; vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, p-tert-butyl vinyl benzoate, pivalic acid Vinyl carboxylic acid esters such as vinyl ester, vinyl 2-ethylhexanoate, vinyl tert-carbonate, and vinyl laurate; isopropenyl carboxylic acid esters such as isopropenyl acetate and isopropenyl propionate; Vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether, and cyclohexyl vinyl ether; aromatic vinyl compounds such as styrene and vinyltoluene; allyl acetate, allyl benzoate, etc. Allyl esters; allyl ethers such as allyl ether and allyl phenyl ether; 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (Meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, perfluoromethyl (meth)acrylate, perfluoropropyl (meth)acrylate, perfluoropropyl methyl (meth)acrylate, vinylpyrrolidone, trimethylolpropane tri(meth)acrylate, allyl (meth)acrylate, etc. These substances may be used alone or in combination of two or more.

In the present embodiment, when the copolymer (C) is produced by a polymerization reaction, a chain transfer agent can be used in order to control the molecular weight of the polymerization product of the vinyl monomer used.

Specific examples of the chain transfer agent are not particularly limited, and include, for example, alkylmercaptans such as n-octylmercaptan, n-dodecylmercaptan, and t-dodecylmercaptan; benzylmercaptan, dodecylmercaptan, etc. Aromatic thiols such as alkyl benzyl mercaptans; thiocarboxylic acids such as thiomalic acid or their salts or their alkyl esters; polythiols; diisopropyl xanthate disulfide, Disulfides such as bis(methylenetrimethylolpropane) xanthate disulfide; allyl compounds such as thioethylene glycol, dimer of α-methylstyrene, etc. These substances may be used alone or in combination of two or more.

The total amount of chain transfer agents used is preferably 0.001 to 1.0% by mass relative to the total amount of the above-mentioned vinyl monomers.

The emulsifier that can be used in the production of the copolymer (C) is not particularly limited, and examples thereof include alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, poly Acidic emulsifiers such as oxyethylene alkyl aryl sulfuric acid, polyoxyethylene distyryl phenyl ether sulfonic acid, alkali metal (Li, Na, K, etc.) salts of acidic emulsifiers, ammonium salts of acidic emulsifiers, fatty acid soaps Anionic surfactants such as alkyl trimethyl ammonium bromide, alkyl pyridinium bromide, imidazolinium laurate and other quaternary ammonium salts, pyridinium salts, cationic surfactants in the form of imidazolinium salts, Non-ionic surfactants such as polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene oxypropylene block copolymer, polyoxyethylene distyryl phenyl ether; free radical Reactive emulsifiers for polymerizable double bonds, etc.

Among these emulsifiers, reactive emulsifiers (reactive emulsifiers) having a radically polymerizable double bond are preferred. By using such a reactive emulsifier, the water dispersion stability of the polymer particles is very good, and the water resistance of the obtained coating film is further improved.

The anionic emulsifier as a reactive emulsifier includes, for example, ethylenically unsaturated monomers having a sulfonic acid group, a sulfonic acid ester group, or a sulfate ester group and salts thereof, preferably having a sulfonic acid group, or A compound that is a group (ammonium sulfonate group, or alkali metal sulfonate group) of its ammonium salt or alkali metal salt. Specifically, for example, alkylallyl sulfosuccinate (for example, "ELEMINOL (trademark) JS-20" manufactured by Sanyo Chemical Industry Co., Ltd., "LATEMUL (trademark) S-120" manufactured by Kao Corporation, etc. ", "LATEMUL S-180A", "LATEMUL S-180", etc.), such as polyoxyethylene alkyl propenyl phenyl ether sulfate (for example, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron (trademark) HS -10" etc.), such as α-[1-[(allyloxy)methyl]-2-(nonylphenoxy)ethyl]-ω-polyoxyethylene sulfate (such as ADEKA Co., Ltd., "Adeka Reasoap (trademark) SE-10N", etc.), such as ammonium-α-sulfonato-ω-1-(allyloxymethyl)alkyloxypolyethylene (such as No. "Aquaron KH-1025" manufactured by Ilkyo Pharmaceutical Co., Ltd., etc.), such as styrene sulfonate (for example, "Supinoma (trademark) NaSS" manufactured by Tosoh Organic Chemicals Co., Ltd., etc.), such as α-[2-[ (allyloxy)-1-(alkyloxymethyl)ethyl]-ω-polyoxyethylene sulfate (for example, "Adeka Reasoap (trademark) SR-1025" manufactured by ADEKA Corporation, etc.) , For example, sulfate ester salts of polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (for example, "LATEMUL (trademark) PD-104" etc. manufactured by Kao Corporation) etc. are mentioned. Among these, ammonium-α-sulfonato-ω-1-(allyloxymethyl)alkyloxyethylene, α-[2-[(allyloxy)-1-(alkoxy) oxymethyl)ethyl]-ω-polyoxyethylene sulfate.

In addition, examples of nonionic emulsifiers that are reactive emulsifiers include α-[1-[(allyloxy)methyl]-2-(nonylphenoxy)ethyl]-ω- Hydroxypolyoxyethylene (for example (manufactured by ADEKA, "Adeka Reasoap NE-20", "Adeka Reasoap NE-30", "Adeka Reasoap NE-40", etc.), for example, polyoxyethylene alkyl propenyl phenyl ether (For example, "Aquaron RN-10", "Aquaron RN-20", "Aquaron RN-30", "Aquaron RN-50" manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., etc.), such as α-[2-[( Allyloxy)-1-(alkyloxymethyl)ethyl]-ω-hydroxypolyoxyethylene (for example, "Adeka Reasoap (trademark) ER-10" manufactured by ADEKA Corporation, etc.), such as poly Oxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (for example, "LATEMUL (trademark) PD-420" etc. manufactured by Kao Corporation) etc. are mentioned.

The amount of emulsifier used is relative to the raw materials of the copolymer (C) as a polymer (a) component, (b) component, hydrolyzable silicon compound other than (a) component and (b) component, and vinyl monomer 100 parts by mass of the total amount is preferably 10 parts by mass or less, more preferably 0.001 to 5 parts by mass. By making the usage-amount of an emulsifier into the said range, polymerization stability improves more, and the water resistance of a coating film becomes more favorable.

The polymerization reaction of (a) component, (b) component, the hydrolyzable silicon compound other than (a) component and (b) component, a vinyl monomer, etc. is preferably implemented in presence of a polymerization catalyst. Examples of the polymerization catalyst used include hydrogen halides such as hydrochloric acid and hydrofluoric acid; carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid and lactic acid; sulfonic acids such as sulfuric acid and p-toluenesulfonic acid; Acidic emulsifiers such as benzene sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulfuric acid, polyoxyethylene alkyl aryl sulfuric acid, polyoxyethylene distyryl phenyl ether sulfonic acid; Acidic or weakly acidic inorganic salts; acidic compounds such as phthalic acid, phosphoric acid, and nitric acid; sodium hydroxide, potassium hydroxide, sodium methoxide, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, trimethylammonium hydroxide, Butylamine, diazabicycloundecene, ethylenediamine, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)-aminopropyltrimethyl Basic compounds such as oxysilane; tin compounds such as dibutyltin octoate and dibutyltin dilaurate, etc.

Among these, acidic emulsifiers are preferable as the polymerization catalyst of the hydrolyzable silicon compound from the viewpoint of not only functioning as a polymerization catalyst but also as an emulsifier. As the acidic emulsifiers, alkylbenzenesulfonic acids having 5 to 30 carbon atoms (for example, dodecylbenzenesulfonic acid, etc.) are more preferable.

The polymerization catalyst of the vinyl monomer is not particularly limited, but a radical polymerization catalyst that initiates addition polymerization of the vinyl monomer by self-radical decomposition under the action of heat or a reducing substance or the like is preferable. It does not specifically limit as such a radical polymerization catalyst, For example, a persulfate, a peroxide, an azobis compound, etc. are mentioned. These may be water-soluble or oil-soluble.

Specific examples of the radical polymerization catalyst are not particularly limited, and examples include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, 2, 2-azobisisobutyronitrile, 2,2-azobis(2-diaminopropane) hydrochloride, 2,2-azobis(2,4-dimethylvaleronitrile), etc.

Although the compounding quantity of a radical polymerization catalyst is not specifically limited, It is preferable that it is 0.001-5.0 mass parts with respect to 100 mass parts of total vinyl monomers. It should be noted that when it is desired to accelerate the polymerization rate and to polymerize at a low temperature of 70°C or less, it is preferable to combine reducing agents such as sodium bisulfite, ferrous chloride, ascorbate, and chalk powder with free radical polymerization. Catalysts are used together.

The polymerization of the hydrolyzable silicon compound and the vinyl monomer can also be carried out separately, but it can be composited by carrying out simultaneously, so it is preferable to carry out the polymerization of the hydrolyzable silicon compound and the vinyl monomer simultaneously.

Although the number average particle diameter of the copolymer (C) which is a polymer is not specifically limited, Preferably it is 10-300 nm. By making the number average particle diameter of a copolymer (C) into the said range, the weather resistance and stain resistance of the coating film obtained tend to improve further. In addition, the particle size of the copolymer (C) is more preferably 10 to 200 nm, still more preferably 100 to 200 nm. By using the copolymer (C) of the said number average particle diameter, the weather resistance of the coating film obtained improves further. When the number average particle diameter is 10 nm or more, stain resistance becomes particularly favorable, and when the number average particle diameter is 300 nm or less, the transparency of the coating film becomes particularly favorable. It should be noted that the number average particle size mentioned here can be measured using a wet particle size analyzer.

As a suitable method for obtaining a copolymer (C) of such a particle size, there may be mentioned, for example, the so-called emulsion polymerization, in which a hydrolyzable silicon compound and a vinyl mono body aggregation. In such a mode, as a suitable example of the dispersion (CD) of the copolymer (C), for example, the dispersion (CD) of the copolymer (C) is obtained by using at least silane (a) and silane (b) ) and the dispersion obtained by emulsion polymerization.

The specific method of emulsion polymerization is not particularly limited, and for example, a method in which a hydrolyzable silicon compound and a vinyl monomer are added dropwise to a reaction vessel in the original state or in an emulsified state, all at once or in batches In the presence of a polymerization catalyst, the polymerization is preferably carried out at a reaction temperature of about 30 to 150° C. under a pressure of atmospheric pressure to 10 MPa. The reaction temperature and reaction pressure may not be the above-mentioned conditions depending on the reaction conditions and the like. The solid content obtained by emulsion polymerization is not particularly limited, but is preferably 1.0 to 50% by mass, more preferably 5.0 to 30% by mass.

For the method of producing the (CD) component as a dispersion, the following method can also be adopted: in the presence of water and an emulsifier, and if necessary in the presence of a solvent, the (a) component, (b) component, and (a) After the component and the hydrolyzable silicon compound other than the component (b) and/or the vinyl monomer are polymerized, water is further added until the polymer becomes an emulsion. However, emulsion polymerization is preferred as described above from the viewpoint of easiness in controlling the particle diameter of the copolymer (C) to be obtained.

The copolymer (C) preferably has a core/shell structure having a core and one or more shell layers. Since the physical properties (the balance of weather resistance and stain resistance, etc.) of the coating film obtained are further improved by having a core/shell structure, it is preferable to have a core/shell structure. Confirmation of the core/shell structure can be performed, for example, by morphological observation by a transmission electron microscope or by analysis by viscoelasticity measurement.

As a method for producing the copolymer (C) having a core/shell structure, for example, multistage emulsion polymerization is useful, but not limited thereto. The multi-stage emulsion polymerization referred to here refers to a method of preparing two or more reaction solutions having different compositions containing a hydrolyzable silicon compound and a vinyl monomer, and polymerizing them by dividing them into different stages. As an example of multi-stage emulsion polymerization, a method of synthesizing a copolymer (C) having a core/shell structure by two-stage emulsion polymerization will be mainly described. As an example of the two-stage emulsion polymerization, a method having a step of polymerizing a hydrolyzable silicon compound and/or a vinyl monomer in the presence of water and an emulsifier to obtain seed particles (first stage) and, in the presence of the obtained seed particles, a step of polymerizing a hydrolyzable silicon compound and/or a vinyl monomer, respectively (second stage).

The synthesis of the copolymer (C) by two-stage emulsion polymerization is carried out, for example, by a two-stage polymerization process including: a first-stage polymerization in which (a) component and (b) component are supplied and subjected to emulsion polymerization and, following the first stage, supply (b) component, (a) component, hydrolyzable silicon compound and vinyl monomer other than (b) component, and the polymerization of the second stage of further emulsion polymerization in an aqueous medium. At this time, the mass ratio ((M1)/(M2)) of the solid content mass (M1) of the first stage to the solid content mass (M2) of the second stage is not particularly limited, but is preferably 7.0/3.0 to 9.5/0.5, More preferably, it is 7.5/2.5 to 9.3/0.7.

By performing such multistage emulsion polymerization, the physical properties (the balance of weather resistance and stain resistance, etc.) of the coating film obtained are further improved, so multistage emulsion polymerization is preferable.

When performing multi-stage emulsion polymerization of three or more stages, it is sufficient to increase the number of stages of polymerization as in the two-stage polymerization.

The content of the hydrolyzable silicon compound containing (a) component and (b) component in the copolymer (C) is not particularly limited, but is preferably 75% by mass or more, more preferably 90% by mass or more in terms of hydrolyzed polycondensate. By making content of the hydrolyzable silicon compound containing (a) component and (b) component into the said range, the weather resistance of a coating film will improve more.

The content of the copolymer (C) in the water-based coating agent composition is not particularly limited, but is preferably 0.5 to 10.0% by mass, more preferably 1.0 to 5.0% by mass.

The content of the copolymer (C) in the coating film formed from the aqueous coating agent composition is preferably 10.0 to 80.0% by mass, more preferably 50.0 to 75.0% by mass. When content of a copolymer (C) is more than the said lower limit, the weather resistance of a coating film will improve more, and when it is below the said upper limit, stain resistance will improve more.

The water-based coating agent composition of this embodiment may contain the compound which has the functional group which can react with the functional group contained in the said polymer further besides a copolymer (C). Such compounds are not particularly limited, and examples thereof include (poly)isocyanate compounds, (poly)epoxide compounds, amino compounds, (poly)carboxy compounds, (poly)hydroxyl compounds, diol compounds, silanol compounds, Silyl compounds, alkoxy compounds, (meth)acrylate compounds, etc. These substances may be used alone or in combination of two or more.

<Inorganic oxide (D)>

The inorganic oxide (D) is an inorganic oxide that does not have photocatalytic activity. The non-photocatalytic activity mentioned here means that neither the oxidation reaction nor the reduction reaction occurs under light irradiation.

It does not specifically limit as (D) component, For example, silicon dioxide (silica), aluminum oxide (alumina), calcium silicate, magnesium oxide, antimony oxide, zirconium oxide, and these composite oxides etc. are mentioned. Among these, silicon dioxide, aluminum oxide, antimony oxide, and composite oxides thereof are preferable, and silicon dioxide is more preferable because there are many hydroxyl groups on the surface.

The inorganic oxide used as the component (D) is preferably present in the form of colloidal particles such as a hydrate. That is, by using the inorganic oxide colloidal particles, the copolymer (C) or other components called (E) components can be further compounded, and the stability as a water-based coating agent composition is further improved.

Silica is preferably colloidal silica. Examples of colloidal silica include colloidal silica, which is an aqueous dispersion of silica having silica as a basic unit, or a dispersion in a water-soluble solvent.

The method for producing colloidal silica is not particularly limited, and it can also be produced by, for example, a sol-gel method. When utilizing the sol-gel method for preparation, reference can be made to Werner Stober et al.; Journal of Colloid And Interface Science, vol.26, pp.62-69 (1968); Rickey D. Badley et al.; Langmuir 6,792-801 ( 1990); "Color Material Association Journal (Color Material Association Journal)", 61[9]488-493(1988), etc.

(D) The number average particle diameter of a component is not specifically limited, Preferably it is 1.0-400 nm, More preferably, it is 1.0-100 nm, More preferably, it is 1.0-30 nm. When the number average particle diameter of (D)component is 1 nm or more, the storage stability of a water-based coating agent composition improves further. By making the number average particle diameter of (D)component into 400 nm or less, the transparency of the coating film obtained will improve more. In addition, the number average particle diameter can be measured using a wet particle size analyzer.

The state of colloidal silica in the aqueous dispersion may be either acidic or basic.

A commercial item can also be used as acidic colloidal silica which uses water as a dispersion medium. Examples of such commercially available products include "Snowtex (trademark)-OXS", "Snowtex-OS", "Snowtex-O", "Snowtex-O-40", "Snowtex-OL" manufactured by Nissan Chemical Industry Co., Ltd. " and "Snowtex-OYL", "adelite (trademark) AT-20Q" manufactured by Asahi Denka Co., Ltd., "Klebosol (trademark) 20H12" and "Klebosol 30CAL25" manufactured by Clariant (Japan), etc.

Examples of basic colloidal silica include colloidal silica stabilized by adding alkali metal ions, ammonium ions, amines, and the like. These basic colloidal silica can also use a commercial item. Examples of such commercially available products include "Snowtex-XS", "Snowtex-S", "Snowtex-30", "Snowtex-50", "Snowtex-20L", "Snowtex- XL", "Snowtex-YL", "Snowtex-ZL", "Snowtex-NXS", "Snowtex-NS", "Snowtex-N", "Snowtex-N40", "Snowtex-CXS", "Snowtex-C" , "Snowtex-CM", "Snowtex-PS-S" and "SnowtexPS-M"; "adelite AT-20", "adelite AT-30", "adelite AT-20N", "adelite AT-30N", "adelite AT-20A", "adelite AT-30A", "adelite AT-40" and "adelite AT-50"; "Klebosol 30R9", "Klebosol 30R50" manufactured by Clariant (Japan) , "Klebosol 50R50", "ludox (trademark) HS-40", "ludox HS-30", "ludox LS" and "ludox SM-30" manufactured by DuPont.

A commercial item can also be used as colloidal silica which uses a water-soluble solvent as a dispersion medium. Such commercially available products include, for example, "MA-ST-M (methanol dispersion type with a particle diameter of 20 to 25 nm)" and "IPAST (isopropanol dispersion type with a particle diameter of 10 to 15 nm)" manufactured by Nissan Chemical Industries, Ltd. )", "EG-ST (ethylene glycol dispersion type with a particle size of 10-15nm)", "EG-ST-ZL (ethylene glycol dispersion type with a particle size of 10-15nm ethylene glycol monopropyl ether dispersion type)" and so on.

The aforementioned colloidal silica may be used alone or in combination of two or more. Furthermore, aluminum oxide, sodium aluminate, etc. may be contained as a small amount of component. In addition, colloidal silica may contain an inorganic base (sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc.) or an organic base (tetramethylammonium, etc.) as a stabilizer.

Although content of (D)component in a water-based coating agent composition is not specifically limited, Preferably it is 0.1-5.0 mass %, More preferably, it is 0.2-3.0 mass %. By making content of (D)component in a water-based coating agent composition into the said range, the coating film which was more excellent in weather resistance and stain resistance can be obtained.

The content of the component (D) in the coating film obtained from the water-based coating agent composition is not particularly limited, but is preferably 5.0 to 70.0% by mass, more preferably 10.0 to 50.0% by mass. When content of the (D)component in a coating film is more than the said lower limit, the stain resistance of a coating film improves more, and when it is below the said upper limit, the weather resistance of a coating film improves more.

<Inorganic oxide having photocatalytic activity (E)>

It is preferable that the water-based coating agent composition of this embodiment further contains the inorganic oxide (E) which has photocatalytic activity. Thereby, photocatalytic activity and hydrophilicity can be expressed by irradiating a coating film with light.

As an inorganic oxide (E), what is necessary is just to have photocatalytic activity, and the kind is not specifically limited. Specific examples of the component (E) are not particularly limited, and include, for example, TiO ₂ , ZnO, SrTiO ₃ , BaTiO ₃ , BaTiO ₄ , BaTi ₄ O ₉ , K ₂ NbO ₃ , Nb ₂ O ₅ , Fe ₂ O ₃ , Ta ₂ O ₅ , K ₃ Ta ₃ Si ₂ O ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , BiVO ₄ , NiO, Cu ₂ O, RuO ₂ , CeO ₂ ; Layered oxides of at least one element in the group consisting of V (for example, Japanese Patent Application Laid-Open Publication No. 62-074452, Japanese Patent Application Publication No. 02-172535, Japanese Patent Application Publication No. 07-024329, Japanese Patent Application Publication No. 08- 089799, JP-A-08-089800, JP-08-089804, JP-09-248465, JP-10-099694, JP-10-244165, etc.) .

The component (E) is preferably TiO ₂ (titanium dioxide) from the viewpoints of chemical stability, toxicity, and environmental aspects. Titanium dioxide may have any crystal structure of anatase type, rutile type, and brookite type.

The (E) component is preferably an inorganic oxide having photocatalytic activity and is a metal compound whose particle surface is modified. By performing the modification treatment, the generation amount of active oxygen species such as H ₂ O ₂ or ·OH can be reduced, and damage to the base coating film can be further suppressed. The modified substance is not particularly limited, and examples thereof include silicon oxide, aluminum, copper oxide, iron oxide, and the like. Among these, silicon oxide is preferable. It should be noted that modification with metals such as Fe, Cu, Al, and Pt, and complexes such as chloroplatinic acid can also obtain the same effect.

Regarding the method of modifying the surface of the component (E), silicon oxide will be described as an example. The method of surface modifying silicon oxide is not particularly limited, and examples thereof include a method of adding a silicon compound to a titanium dioxide slurry and precipitating a silicon hydrous oxide through steps such as neutralization treatment.

It does not specifically limit as a silicon compound, For example, water-soluble alkali metal silicate, such as sodium silicate, can be used. Among these, sodium silicate is preferable in terms of colorlessness and no coloring of the titanium dioxide sol.

The treatment amount of the hydrous oxide of silicon is preferably 3.0 to 25% by mass, more preferably 5.0 to 20% by mass based on the oxide relative to titanium dioxide. Since the increase in the amount of active oxygen species can be suppressed by making a processing amount more than the said lower limit, damage to a base coating film can be prevented. Moreover, since aggregation of titanium dioxide can be suppressed and the viscosity increase of a sol can be suppressed by making a processing amount below the said upper limit, dispersibility and transparency improve further.

The content of the component (E) in the water-based coating agent composition is not particularly limited, but is preferably 0.1 to 2.0% by mass, more preferably 0.2 to 1.0% by mass. By making content of (E) component of a water-based coating agent into the said range, the coating film which was more excellent in stain resistance and transparency can be obtained.

The content of the component (E) in the coating film obtained from the water-based coating agent composition is not particularly limited, but is preferably 3.0 to 25.0% by mass, more preferably 5.0 to 20.0% by mass. When content of the (E) component in a coating film is more than the said lower limit, the stain resistance of a coating film improves more, and when it is below the said upper limit, the transparency of a coating film improves more.

<Fluorocarbon Surfactant (F)>

The water-based coating agent composition of the present embodiment preferably further contains a fluorocarbon surfactant (F). Therefore, when coating with the water-based coating agent composition of this embodiment or using a water-based paint containing the composition, the wettability to organic substrates and the like can be further improved, and appearance problems such as repellency can be further suppressed. . Furthermore, the uniformity of a coating film also improves further. The reason for the above-mentioned effect is not certain, but it is presumed that the surface tension of the water-based coating agent composition can be lowered by containing the component (F) (however, the effect of the present embodiment is not limited to these).

Although it does not specifically limit as (F) component, Amphoteric surfactant is preferable. Examples of the amphoteric surfactant include nonionic amphoteric surfactants, anionic amphoteric surfactants, and cationic amphoteric surfactants. As a preferable specific example, the amphoteric surfactant which has a perfluoroalkyl group with 3-20 carbon atoms is mentioned, for example.

Specific examples of amphoteric surfactants having a perfluoroalkyl group having 3 to 20 carbon atoms include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl amine oxides, perfluoroalkyl amine oxides, and perfluoroalkyl sulfonates. Fluoroalkylethylene oxide adducts, perfluoroalkyl compounds having anionic groups and cationic groups, and the like. Among these, perfluoroalkyl ethylene oxide adducts and perfluoroalkyl compounds having anionic groups and cationic groups are preferable from the viewpoint of reducing the surface tension of coating materials.

As a perfluoroalkyl carboxylate, a commercial item can also be used, for example. As such a commercial item, "Surflon S-211" by AGC Seimi Chemical Co., Ltd. etc. are mentioned. As a perfluoroalkylamine oxide, a commercial item can also be used, for example. As such a commercial item, "Surflon S-241" by AGC SEIMI CHEMICAL, etc. are mentioned. As the perfluoroalkyl ethylene oxide adduct, for example, a commercially available product can also be used. As such a commercial item, "MEGAFAC F-444" by DIC Corporation, "Surflon S-242" by AGC SEIMI CHEMICAL, etc. are mentioned, for example. As a perfluoroalkyl compound which has an anionic group and a cationic group, a commercial item can also be used, for example. As such a commercial item, "Surflon S-231", "Surflon S-232", "Surflon S-233" by AGC SEIMI CHEMICAL, etc. are mentioned. These substances may be used alone or in combination of two or more.

Although content of (F)component in an aqueous coating agent composition is not specifically limited, Preferably it is 0.0001-0.50 mass %, More preferably, it is 0.01-0.10 mass %. By making content of (F)component more than the said lower limit, the uniformity of the coating film obtained will improve more. By making content of (F) component below the said upper limit, the weather resistance of the coating film obtained will improve more.

<Discoloration pigment (G)>

The water-based coating agent composition of the present embodiment preferably further contains a discoloring dye (G). This can prevent problems such as missed coating, repeated coating, and uneven coating.

As (G) component, what loses color by irradiation of sunlight and does not impair the aesthetics of a base is preferable. The time until discoloration varies depending on the season, the irradiation angle, etc., and usually the period until discoloration is confirmed visually is preferably 20 days or less, more preferably 10 days or less, and even more preferably 3 days or less.

Component (G) is not particularly limited as long as it has the property of losing color under sunlight irradiation. Preferred examples include those selected from methylene blue, crystal violet, malachite green, brilliant blue FCF, erythrosine, and carmine. , Flame Red, Rose Red, Acid Red and Fast Green FCF, etc. Among these, methylene blue is more preferable in terms of good color rendering property and fast color loss speed. These substances may be used alone or in combination of two or more.

Although content of (G)component in an aqueous coating agent composition is not specifically limited, Preferably it is 0.0002-0.01 mass %, More preferably, it is 0.001-0.007 mass %. By making content of (G)component in a water-based coating agent composition into the said range, the color development and discoloration property of a coating film will improve more. The term "color rendering" here refers to the property of developing color to such an extent that it can be visually distinguished from the color difference between the coated surface and the uncoated surface, and the color fading property refers to the property of fading to the extent that the appearance of the base material is not damaged. The nature of the degree of color.

The content of the component (G) in the coating film obtained from the aqueous coating composition is not particularly limited, but is preferably 0.01 to 0.5% by mass, more preferably 0.05 to 0.2% by mass, and still more preferably 0.1 to 0.2% by mass. When content of (G)component is more than the said lower limit, the color development property of a coating film will improve more, and when it is below the said upper limit, the discoloration property of a coating film will improve more.

<Cellulosic Thickener (H)>

The water-based coating agent composition of the present embodiment preferably further contains a cellulose-based thickener (H). Thereby, even if the solid content of a water-based coating agent composition is low, it can prevent a liquid from hanging at the time of coating. The cellulose-based thickener (H) is not particularly limited, and examples thereof include those selected from methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, and hydroxypropylmethylcellulose. One of the group consisting of elements and their modified products. Among these, one selected from the group consisting of hydroxyethyl cellulose, hydroxypropylmethyl cellulose, and modified products thereof is preferable, and hydroxyethyl cellulose and modified products thereof are more preferable. In addition, these cellulose-based thickeners may be used alone or in combination of two or more.

In addition, other thickeners may be used in combination within the range in which the effects of the present embodiment are obtained. Other thickeners are not particularly limited, and include, for example, polycarboxylic acid-based thickeners, polyacrylamide-based thickeners, acrylic-acrylamide copolymer salt-based thickeners, and polysaccharide-based thickeners other than cellulose-based thickeners. Thickeners, vinyl ether thickeners, etc.

As hydroxyethyl cellulose, a commercial item can also be used. Examples of such commercially available products include "HEC Daicel SP200", "HEC Daicel SP400", "HEC Daicel SP500", "HEC Daicel SP550", "HEC Daicel SP600", "HEC Daicel SP800" manufactured by Daicelfinechem Co., Ltd. "HEC Daicel SP850" and "HEC Daicel SP900", "Sanhec (trademark) HH", "Sanhec H", "Sanhec M" and "Sanhec G&L" manufactured by Sansho Corporation, "HECSZ-25F" manufactured by Sumitomo Seika Co., Ltd. Wait.

The weight average molecular weight of hydroxyethyl cellulose is not particularly limited, but is preferably 700,000 to 2 million, and more preferably 1 million to 1.6 million. When the weight average molecular weight is 700,000 or more, the liquid sagging of the water-based coating agent composition can be further suppressed. Transparency of the coating film obtained from an aqueous composition improves further that a weight average molecular weight is 2 million or less. The weight average molecular weight can be determined by gel permeation chromatography (GPC).

As hydroxypropylmethylcellulose, a commercial item can also be used. Examples of commercially available products include "METOLOSE 90SH-04", "METOLOSE 90SH-15", "METOLOSE 90SH-100", "METOLOSE90SH-400", "METOLOSE 90SH-4000", "METOLOSE 90SH-15000" and "METOLOSE 90SH-100000", "NEOVISCO-MC HM4000S", "NEOVISCO-MC RM4000S", "NEOVISCO-MCRM15000S", "NEOVISCO-MC RM30000S" and "NEOVISCO-MC RM50000S" manufactured by Samsang Corporation Wait.

When other thickeners are used in combination, it is preferable to use a polyvalent carboxylic acid-based thickener or a polyacrylamide-based thickener, and it is more preferable to use a polyvalent carboxylic acid-based thickener.

A commercial item can also be used as a polyhydric carboxylic acid type thickener. As a commercial item, "A-20P-X", "A-7100", "A-7185" etc. by Toagosei Co., Ltd. are mentioned, for example.

The content of the component (H) in the water-based coating agent composition is not particularly limited, but is preferably 0.04 to 0.30% by mass, more preferably 0.08 to 0.20% by mass. By making content of the (H)component in a water-based coating agent composition into the said range, the coating film more excellent in transparency and weather resistance can be obtained.

The content of the component (H) in the coating film obtained from the water-based coating agent composition is not particularly limited, but is preferably 2.0 to 15.0% by mass, more preferably 4.0 to 9.0% by mass. When content of the (H) component in a coating film is more than the said lower limit, the transparency of a coating film will improve more, and when it is below the said upper limit, the weather resistance of a coating film will improve more.

<Anti-algae agent, anti-fungal agent (J)>

It is preferable that the coating film of this embodiment further contains 1 or more types selected from the group which consists of an anti-algae agent and an antifungal agent (J). Thereby, a coating film excellent in mold resistance and/or algae resistance can be formed even in a position where light such as sunlight is difficult to irradiate (however, the effects of the present embodiment are not limited to these).

The anti-algae agent and/or anti-mold agent (J) is not particularly limited, and examples thereof include organic iodine-based compounds, alcohol-based compounds, nitrile compounds, disulfide-based compounds, thiocarbamate-based compounds, compounds containing Nitrogen compounds, etc. Among these, nitrogen-containing ring compounds are preferred. Examples of nitrogen-containing ring compounds include thiazoline-based compounds, isothiazoline-based compounds, triazine-based compounds, imidazole-based compounds, and the like. Among these, one or more compounds selected from the group consisting of isothiazoline compounds, triazine compounds, and imidazole compounds are preferred, and one or more compounds selected from the group consisting of isothiazoline compounds and triazine compounds are more preferred. more than one species. As a compound which is especially excellent in an anti-algae property, a triazine type compound etc. are mentioned, for example. As a compound excellent especially in mold resistance, a thiazoline type compound, an isothiazoline type compound, an imidazole type compound, etc. are mentioned, for example. It is of course possible to use a compound having both anti-algae and anti-fungal properties, and examples of such compounds include isothiazoline-based compounds containing chlorine atoms in their molecules. These substances may be used alone or in combination of two or more.

As a thiazoline compound, a commercial item can also be used. Examples of such commercially available products include "Millcut-180" and "Biocut-LC3" manufactured by Nippon Soda Corporation, "Amorden ALK" manufactured by Daiwa Chemical Industry Co., Ltd., and the like.

A commercial item can also be used as an isothiazoline compound. Examples of such commercially available products include "Biocut-TR120" manufactured by Nippon Soda Corporation, "PROXEL GXL" and "PROXEL BDN" manufactured by Arch Chemicals, and "KLARIX 4000" and "ROZONE 2000" manufactured by Dow Chemical. , "ROCIMA 252", "ROCIMA 200", "ROCIMA 345", "ROCIMA 350", "ROCIMA 553", "BIOBAN 551S", "Skane M-8", etc.

As a triazine compound, a commercial item can also be used. As a commercial item, "Biocut-N35", "DP-2159", and "DP-2615" manufactured by Nippon Soda Co., Ltd. are mentioned, for example. "DP-2619", "DP-2623", "Amorden NBP-8" manufactured by Daiwa Chemical Industry Co., Ltd., "Amorden NBPconc" manufactured by Sankyo Kasei Co., Ltd. "San Arga 1907", etc.

A commercial item can also be used as an imidazole compound. As a commercial item, "Biocut-N35", "Biocut-AF40", "DX-2" by Nippon Soda Corporation, "ROCIMA 363" by a Dow Chemical company, etc. are mentioned, for example.

The content of the component (J) in the water-based coating agent composition is not particularly limited, but is preferably 0.01 to 0.80% by mass, more preferably 0.05 to 0.50% by mass. By making content of (J)component in an aqueous composition into the said range, the coating film which was more excellent in transparency, weather resistance, and microbe resistance can be obtained.

The content of the component (J) in the coating film obtained from the water-based coating agent composition is not particularly limited, but is preferably 0.1 to 30.0% by mass, more preferably 1.0 to 15.0% by mass. When content of the (J) component in a coating film is more than the said lower limit, the microbial resistance of a coating film improves more, and when it is below the said upper limit, the transparency and weather resistance of a coating film improve more.

In the range in which the effects of the present embodiment can be obtained, other antibacterial agents may be further used in combination. It does not specifically limit as another antibacterial agent, For example, a silver compound, a copper compound, a zinc compound etc. are mentioned.

The solid content (solid content) in the aqueous coating agent composition is not particularly limited, but is preferably 0.5 to 10.0% by mass, more preferably 1.5 to 6.0% by mass, from the viewpoint of uniformity of the coating film. Contamination resistance improves further by making content of the solid content in a water-based coating agent composition more than the said lower limit. Transparency will further improve by making content of the solid content in a water-based coating agent composition below the said upper limit. The solid content mentioned here can be calculated|required by the method described in the Example mentioned later. In addition, depending on the application of the coating film, the film thickness of the coating film may also be required to be thin. Even in this case, by making the solid content in the water-based coating agent composition not more than the above-mentioned upper limit, it can be obtained that the film thickness is thin, but the physical properties such as weather resistance and stain resistance are also excellent. coating film. By setting the solid content in the water-based coating agent composition to be more than the above lower limit, the drying time required for forming a coating film can be shortened, and work efficiency can be further improved.

The water-based coating agent composition of this embodiment can further contain other components other than the above as needed within the range in which the effect can be obtained. Such other components are not particularly limited, and examples thereof include antifoaming agents, freeze stabilizers, matting agents, crosslinking reaction catalysts, pigments, curing catalysts, crosslinking agents, fillers, anti-skinning agents, and dispersants , wetting agent, light stabilizer, antioxidant, ultraviolet absorber, film-forming aid, rust inhibitor, plasticizer, lubricant, reducing agent, preservative, deodorant, anti-yellowing agent, antistatic agent, Charge regulator, etc. These may be used alone or in combination of two or more.

The above-mentioned water-based coating agent composition can be suitably used as a water-based paint. That is, the water-based coating material of this embodiment contains the above-mentioned water-based coating agent composition. For water-based coatings, it can further contain defoamers, freeze stabilizers, delustering agents, crosslinking reaction catalysts, pigments, curing catalysts, crosslinking agents, fillers, anti-skinning agents, dispersants, wetting agents, light stabilizers , antioxidants, UV absorbers, film-forming aids, rust inhibitors, plasticizers, lubricants, reducing agents, preservatives, anti-mold agents, anti-algae agents, deodorants, anti-yellowing agents, antistatic agents , charge regulator, etc. as other components.

The water-based paint according to the present embodiment can be applied by an appropriate method depending on the application, the material of the coating object, and the like. The coating method is not particularly limited, and examples thereof include spray coating, flow coating, roll coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing, Flexographic printing.

A coating film is obtained by applying the water-based coating material of this embodiment and then drying to remove volatile matter. At this time, heat treatment at a temperature of about 40 to 120° C., ultraviolet irradiation treatment, or the like may be further performed as necessary.

Thus, in this embodiment, the coating film containing the said water-based paint can be produced. The coating film is obtained from a water-based paint, and can also be formed on a substrate by, for example, applying the above-mentioned water-based paint to the surface of various substrates and drying it. That is, in the present embodiment, a coated product including a base material and the above-mentioned coating film formed on at least a part of the surface of the base material can also be produced.

The material of the substrate usable in this embodiment is not particularly limited as long as a coating film can be formed on the surface thereof, and may be either an organic substrate or an inorganic substrate, and an organic substrate is preferable. The material of the substrate is not particularly limited, and examples thereof include synthetic resins, natural resins, metals, ceramics, glass, stone, cement, and concrete. These substances may be used alone or in combination of two or more. In particular, in this embodiment, even an organic group composed of a material having a glass transition temperature as low as -5 to 20°C can form a coating film capable of maintaining a high level of appearance and stain resistance. material is also suitable.

The synthetic resin is not particularly limited, and examples thereof include thermoplastic resins and curable resins (thermosetting resins, photocurable resins, moisture curable resins, etc.). Specific examples of synthetic resins are not particularly limited, and include, for example, silicone resins, acrylic resins, methacrylic resins, fluororesins, alkyd resins, amino alkyd resins, vinyl resins, polyester resins, benzene Ethylene-butadiene resin, polyolefin resin, polystyrene resin, polyketone resin, polyamide resin, polycarbonate resin, polyacetal resin, polyether ether ketone resin, polyphenylene ether resin, polysulfone resin, poly Phenylsulfone resin, polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, urea resin, phenol resin, melamine resin, epoxy resin, urethane resin, silicone-acrylic resin, etc. In addition, coating films formed of acrylic resin-based paints, silicone-acrylic resin-based paints, and fluororesin-based paints used for building exteriors and the like are also included in synthetic resins.

It does not specifically limit as a natural resin, For example, a cellulose-type resin, isoprene-type resins, such as natural rubber, protein-type resins, such as casein, etc. are mentioned.

When the base material is a resin base material using the above-mentioned synthetic resin or natural resin, surface treatment such as corona discharge treatment, flame treatment, plasma treatment, etc. may be given as necessary.

The coated product of the present embodiment includes a base material and the above-mentioned coating film formed on the base material, and the coating film is useful also as a coating layer or the like. The coating film obtained by this embodiment can maintain the external appearance and anti-pollution property at a high level for a long period of time, so it can be suitably used also in an environment where it is difficult to use conventionally. From this point of view, specific examples of the coated product of this embodiment include building materials, building exteriors, building interiors, window frames, window glass, various lenses, structural parts, construction equipment such as houses, vehicles, etc. Covers and window glass for lighting, exteriors of machinery or articles, dust covers and coatings, display instruments, their covers, traffic signs, various display devices, advertising towers and other displays, roads and railways, etc. Exterior and coating of soundproof walls, bridges and guardrails, interior and coating of tunnels, insulators, solar battery covers, solar water heater heat collecting covers, etc., external parts of electronic and electrical equipment, especially transparent parts, plastic greenhouses, The exterior of greenhouses, etc.

As a method of manufacturing the coated product of this embodiment, the following method can be mentioned: for example, the above-mentioned water-based paint (or water-based coating agent composition) is coated on at least a part of the surface of the substrate, and dried as necessary. etc., thereby forming a coating film, but the manufacturing method is not limited thereto. For example, after applying the coating film of the present embodiment on a base material, the coating film may be peeled from the base material and bonded to another base material. Alternatively, after coating the coating film of the present embodiment on a base material, the coating film may be adhered to another base material in a state of close contact with the base material.

The water-based coating agent composition of this embodiment can be mixed as various water-based paints. Such a water-based paint can form a coating film excellent in appearance, stain resistance, transparency, weather resistance, mold resistance, algae resistance, and the like. As such, the coating film of the present embodiment is also excellent in appearance, stain resistance, further transparency, weather resistance, mold resistance, algae resistance, etc., and can be used in a wide range of applications including building exterior coatings and the like.

Example

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to the following examples. Various physical properties were measured by the following methods in Examples and Comparative Examples.

<Preparation of Substrate X Pre-coated with Enamel Coating>

· Preparation of pigment dispersion

Using a desktop sand mill (manufactured by Kanpehapio, batch type desktop sand mill), dispersant (manufactured by BASF Japan, "Pig. Disperser MD20") 5.35g, ammonia water 0.50g, propylene glycol 23.50g, water 147.50g, A mixture of 333.50 g of titanium dioxide (chlorine-process rutile type titanium dioxide; manufactured by Ishihara Sangyo Co., Ltd., "Taipake CR-97") and 2.85 g of a defoamer (modified silicone type; manufactured by SANNOPCO, "SN Defoamer 1310") was dispersed After 20 minutes, a pigment dispersion was obtained.

·Making of Enamel Coating X

To 109.0 g of the polymer emulsion X of Production Example 1, 10.0 g of 2,2,4-trimethyl-1,3-butanediol isobutyrate (manufactured by Chisso, "CS-12"), and 10.0 g of a mixed solution of 50 parts by mass of glycol monobutyl ether and 50 parts by mass of water, 51.4 g of the pigment dispersion obtained above, and 0.50% of a 10% aqueous solution of a thickener (manufactured by Asahi Denka Industries, Ltd., "ADEKANOL UH-438") g, mixed for 1 hour to obtain enamelled coating X.

・Preparation of substrate X coated with enamelled paint X in advance

Using a wire bar coater No.50, coat the enamel paint X obtained above on a sulfuric acid acid-resistant aluminum plate of 7 cm x 15 cm or 5 cm x 5 cm, and dry it for 48 hours at a temperature of 23 ° C and a relative humidity of 50% to obtain a precoat Substrate X loaded with Enamel Coating X.

<Preparation of Substrate Y Pre-coated with Enamel Coating>

·The production of lacquer coating Y

Enamel paint Y was obtained in the same manner as enamel paint X except that 109.0 g of polymer emulsion X of manufacture example 1 was used instead of 109.0 g of polymer emulsion Y of manufacture example 2.

・Preparation of base material Y pre-coated with enamelled coating material Y

Using a wire bar coater No.50, coat the enamelled coating Y obtained above on a sulfuric acid acid-resistant aluminum plate of 7 cm × 15 cm or 5 cm × 5 cm, and dry it for 48 hours at a temperature of 23 ° C and a relative humidity of 50% to obtain a precoat Substrate Y loaded with Enamel Coating Y.

1. Content of each component and solid content

2 g of the sample was taken in an aluminum pan, and heated at 150° C. for 1 hour. The mass of the sample before and after heating was measured, and the solid content (mass %) was calculated from the difference. According to this method, the content of each component and the solid content in the composition are respectively measured.

2. Number average particle size

Ion-exchanged water was added and diluted so that the loading index (loading index) would be 1.5 to 3.0, and it measured using a wet particle size analyzer (manufactured by Nikkiso Co., Ltd., "microtrack UPA-9230"). The measurement conditions are as follows.

·Load index: 1.5～3.0

·Measurement time: 60 seconds

· Measurement times: 3 times

3. Viscosity

Measurement was performed using a BM-type viscometer (manufactured by Toki Sangyo Co., Ltd.). The measurement conditions are as follows.

·Temperature: 23°C

·Rotor: No.1

·Rotation speed: 60rpm

4. Glass transition temperature

Using "DCS6220" manufactured by Seiko Instruments, the temperature increase rate was measured under the measurement conditions of 10°C/min, and the glass transition temperature was obtained from the inflection point of the obtained DSC curve. In addition, measurement conditions are as follows.

· Measuring cell: aluminum container

- Preparation of a sample for measurement: 40 mg of an emulsion as a measurement sample was placed in an aluminum container, and dried at 130° C. for 1 hour.

5. Weather resistance test: gloss retention rate after 3000 hours

On the substrate X or substrate Y of 7 cm × 15 cm coated with enamelling paint, the coating of the aqueous composition is carried out by spraying, so that the coating amount of the aqueous composition is 17 g/m ² or 50 g/m ² ratio. Keep the coated substrate horizontally, and let it stand for 48 hours at a temperature of 23° C. and a relative humidity of 50%, as a test plate. The exposure test (black panel temperature 63 degreeC, rain 18 minutes/2 hours) was performed using the "sunshine weather resistance test box" manufactured by SUGA test equipment. The 60° glossiness after exposure for 3000 hours was measured using a gloss meter (manufactured by BYK Gardner, "micro-tri-gloss").

And the gloss retention was calculated based on the following formula. It should be noted that, as a result of evaluating only substrates coated with an enamelled paint in advance, the gloss retention rate of substrate X after 3000 hours of exposure was 80%, and the gloss retention rate of substrate Y after 3000 hours of exposure was 80%. The rate is 88%, and these values show that the weather resistance is good when the value of the gloss retention rate is large.

Gloss retention (%) = 60° gloss after exposure test/60° gloss before exposure test × 100

6. Pollution resistance

On the substrate X or substrate Y of 7 cm × 15 cm coated with enamelling paint, the coating of the aqueous composition is carried out by spraying, so that the coating amount of the aqueous composition is 17 g/m ² or 50 g/m ² ratio. Keep the coated substrate horizontally, and let it stand for 48 hours at a temperature of 23° C. and a relative humidity of 50%, as a test plate. Attach the test panel to the fence facing the general road (about 500 to 1000 trucks per day), and let it stand for 6 months or 1 year. The degree of contamination of the test plate after leaving still was visually evaluated based on the following reference|standard. In addition, the evaluation results of only the base material X or Y coated with the enamel paint in advance were "x" evaluations after standing still for 6 months and 1 year.

◯: Stains were hardly recognized.

△: Slight staining was confirmed, but practically no problem.

×: A large amount of dirt was confirmed.

7. Mildew resistance

On the substrate X or substrate Y of 5 cm × 5 cm coated with enameled paint, the coating of the aqueous composition is carried out by spraying, so that the coating amount of the aqueous composition is 17 g/m ² or 50 g/m ² ratio. Keep the coated substrate horizontally, and let it stand for 48 hours at a temperature of 23° C. and a relative humidity of 50%, as a test plate.

For conditions other than the above, use Aspergillus niger, Penicillium pinophilum, Cladosporium cladosporium, Aureobasidium pullulans, Trichoderma viridans in accordance with "8 Paint test" of JIS Z-2911 (Test method for mold resistance). , and Alternaria alternata mixed substances were tested. After the test, evaluation was performed based on the following criteria.

⊚: Growth of mycelium was not confirmed on the coating film.

◯: The area of the growth part of mycelium confirmed on the coating film is more than 0 and 1/3 or less with respect to the total area.

Δ: The area of the growth part of mycelium confirmed on the coating film exceeds 1/3 and 2/3 or less of the total area.

X: The area of the growth part of the hyphae confirmed on the coating film exceeded 2/3 with respect to the total area.

8. Anti-algae performance

On the substrate X or substrate Y of 5 cm × 5 cm coated with enameled paint, the coating of the aqueous composition is carried out by spraying, so that the coating amount of the aqueous composition is 17 g/m ² or 50 g/m ² ratio. Keep the coated substrate horizontally, and let it stand for 48 hours at a temperature of 23° C. and a relative humidity of 50%, as a test plate.

Instead of using mold, use a mixture of Chlorella vulgaris and Vibrating algae, and use the above-mentioned test piece, and use "7c) Fiber products based on JIS Z-2911 (Test method for mold resistance) The test "wet method" was tested. After the test, evaluation was performed based on the following criteria.

⊚: Growth of algae was not confirmed on the coating film.

◯: The area of the growth part of the algae confirmed on the coating film is more than 0 and 1/3 or less with respect to the total area.

Δ: The area of the growth part of algae confirmed on the coating film exceeds 1/3 and 2/3 or less of the total area.

X: The area of the growth part of the algae confirmed on the coating film exceeds 2/3 with respect to the total area.

9. Wet decomposition performance

On the substrate X or substrate Y of 7 cm × 15 cm coated with enamelling paint, the coating of the aqueous composition is carried out by spraying, so that the coating amount of the aqueous composition is 17 g/m ² or 50 g/m ² ratio. Keep the coated substrate horizontally, and let it stand for 48 hours at a temperature of 23° C. and a relative humidity of 50%, as a test plate. About this test plate, it tested based on JISR1703-2 (fine ceramics-self-cleaning performance test method of a photocatalyst material-Part 2: wet decomposition performance), and calculated|required the decomposition|disassembly activity index. The higher the decomposition activity index, the better the self-cleaning property.

[manufacturing example 1]

Synthesis of Polymer Emulsion X

292 g of ion-exchanged water and a reactive emulsifier (manufactured by ADEKA Corporation, "Adeka Reasoap SR-1025"; an aqueous solution with a solid content of 25% by mass) were put into a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device. ) 8g, the temperature in the reactor was heated to 80°C under stirring. 10 g of 2% by mass ammonium persulfate aqueous solution was added to the reactor, and after 5 minutes, 15 g of methyl methacrylate, methacrylic acid cyclo 10 g of hexyl ester, 65 g of butyl acrylate, 5 g of methacrylic acid, 10 g of 2-hydroxyethyl methacrylate, a reactive emulsifier (manufactured by ADEKA Corporation, "Adeka Reasoap SR-1025"; solid content of 25 mass % aqueous solution) 4 g, 15 g of 2% by mass ammonium persulfate aqueous solution, and 49 g of ion-exchanged water. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 60 minutes.

Then, 80 g of methyl methacrylate, 90 g of cyclohexyl methacrylate, 222 g of butyl acrylate, 8 g of methacrylic acid, and a reactive emulsifier (manufactured by ADEKA Corporation, "Adeka Co. Reasoap SR-1025"; an aqueous solution with a solid content of 25% by mass) 16g, 60g of 2% by mass of ammonium persulfate aqueous solution, and 196g of ion-exchanged water; and 3-methacryloyloxypropyl A mixed liquid composed of 1 g of trimethoxysilane, 20 g of dimethyldimethoxysilane, and 20 g of methyltrimethoxysilane. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 120 minutes. After cooling to room temperature, the hydrogen ion concentration of the reaction liquid in the reactor was measured, and the pH was 2.2. After adding 25% ammonia solution to the reaction solution to adjust the pH to 8, the reaction solution was filtered through a 100-mesh metal mesh to obtain a polymer emulsion X for enamelling coating. The solid content of the obtained polymer emulsion X was 44.5% by mass. Regarding the polymer contained in this polymer emulsion X, the glass transition temperature obtained from the inflection point of the DSC curve based on the method described above was 1°C.

[Manufacturing example 2]

Synthesis of Polymer Emulsion Y

292 g of ion-exchanged water and a reactive emulsifier (manufactured by ADEKA Corporation, "Adeka Reasoap SR-1025"; an aqueous solution with a solid content of 25% by mass) were put into a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device. ) 8g, the temperature in the reactor was heated to 80°C under stirring. 10 g of 2% by mass ammonium persulfate aqueous solution was added to the reactor, and after 5 minutes, 15 g of methyl methacrylate, methacrylic acid cyclo 10 g of hexyl ester, 65 g of butyl acrylate, 5 g of methacrylic acid, 10 g of 2-hydroxyethyl methacrylate, a reactive emulsifier (manufactured by ADEKA Corporation, "Adeka Reasoap SR-1025"; solid content of 25 mass % aqueous solution) 4 g, 15 g of 2% by mass ammonium persulfate aqueous solution, and 49 g of ion-exchanged water. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 60 minutes.

Then, 150 g of methyl methacrylate, 90 g of cyclohexyl methacrylate, 152 g of butyl acrylate, 8 g of methacrylic acid, and a reactive emulsifier (manufactured by ADEKA Corporation, "Adeka Co. Reasoap SR-1025"; an aqueous solution with a solid content of 25% by mass) 16g, 60g of 2% by mass of ammonium persulfate aqueous solution, and 196g of ion-exchanged water; and 3-methacryloyloxypropyl A mixed liquid composed of 1 g of trimethoxysilane, 20 g of dimethyldimethoxysilane, and 20 g of methyltrimethoxysilane. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 120 minutes. After cooling to room temperature, the hydrogen ion concentration of the reaction liquid in the reactor was measured, and the pH was 2.2. After adding 25% ammonia solution to the reaction solution to adjust the pH to 8, the reaction solution was filtered through a 100-mesh metal mesh to obtain a polymer emulsion Y for enamelling coating. The solid content of the obtained polymer emulsion Y was 44.5% by mass. Regarding the polymer contained in the polymer emulsion Y, the glass transition temperature obtained from the inflection point of the DSC curve based on the above method was 20°C.

[Manufacturing example 3]

Synthesis of Aqueous Dispersion (CD-1) of Polymer (C-1)

After dropping into the dodecylbenzenesulfonic acid aqueous solution 5.6g of ion-exchanged water 850g, 10 mass % in the reactor with reflux condenser, dropping tank, thermometer and stirring device, the temperature in the reactor is heated to 80°C. While keeping the temperature in the reactor at 80°C, 110.0 g of dimethyldimethoxysilane, 73.0 g of phenyltrimethoxysilane, methyltrimethoxy A mixed solution consisting of 29.4 g of silane. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 5.6 g of a 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, after injecting 6.6 g of 2% by mass ammonium persulfate aqueous solution, 22.5 g of methyl methacrylate, n-butyl acrylate, and 11.2g, 12.3g of phenyltrimethoxysilane, 28.6g of tetraethoxysilane, 1.1g of 3-methacryloxypropyltrimethoxysilane; and 0.9g of acrylic acid, reactive emulsifier Agent (manufactured by ADEKA Corporation, "Adeka Reasoap SR-1025"; solid content is 25 mass% aqueous solution) 1.2g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; solid content is 25% by mass aqueous solution) 1.2 g, 30 g of a 2.0% by mass aqueous solution of ammonium persulfate, and 286.4 g of ion-exchanged water. Furthermore, after maintaining the temperature in the reactor at 80° C. and continuing to stir for about 1 hour, it was cooled to room temperature, and 25% ammonia solution was added to the reaction solution to adjust the pH to 8, and then filtered with a 100-mesh metal mesh. It adjusted with ion-exchanged water so that the solid content would be 10.0 mass %, and the aqueous dispersion (CD-1) of the polymer (C-1) whose number average particle diameter was 155 nm was obtained as a polymer.

The dimethyldimethoxysilane used for synthesizing the aqueous dispersion was 36.9% by mass in the polymer (C-1) in terms of hydrolysis and condensation products.

In addition, the methyltrimethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane used in the synthesis of the aqueous dispersion were converted into polymers ( 7.9% by mass, 30.2% by mass, and 0.4% by mass in C-1) are 38.5% by mass in total.

In addition, the content in conversion of the hydrolysis-condensation product with respect to each said monomer was computed based on the following formula.

For example, in the case of component (a), the reactive group (alkoxy group, etc.) of component (a) is converted into a silanol bond by hydrolysis or condensation reaction, and becomes a condensate of the structural unit (A). The conversion factor of the (a) component is its mass ratio (the total amount of the condensate/the total amount of the (a) component), and can be represented by the following formula (i).

In addition, for example, in the case of component (b), the reactive group (alkoxy group, etc.) of component (b) is converted into a silanol bond by hydrolysis or condensation reaction, and becomes a condensate having a structural unit (B). The conversion factor of the (b) component mentioned above is its mass ratio (the total amount of the condensate/the total amount of the (b) component), and can be represented by the following formula (ii).

The content (mass%) of the structural unit (A) in the polymer (C) = [the amount (g) of component (a) × conversion factor] ÷ total solid content (g) × 100

【Number 1】

α: Molecular weight of component (a)

r ₂ : the molecular weight of R ² in the general formula (1)

γ: Atomic weight of oxygen

The conversion factors of the respective components calculated as described above are as follows.

Dimethyldimethoxysilane: 0.617

Diethoxydimethylsilane: 0.500

Diisopropyldimethoxysilane: 0.739

Diphenyldimethoxysilane: 0.811

Dimethoxymethylphenylsilane: 0.747

The content (mass%) of the structural unit (B) in the polymer (C) = [the amount (g) of component (b) × conversion factor] ÷ total solid content (g) × 100

【Number 2】

β: Molecular weight of component (b)

r ₄ : the molecular weight of R ⁴ of the general formula (2)

γ: Atomic weight of oxygen

The conversion factors of the respective components calculated as described above are as follows.

Methyltrimethoxysilane: 0.493

Phenyltrimethoxysilane: 0.652

3-methacryloxypropyltrimethoxysilane: 0.722

[Manufacturing example 4]

Synthesis of Aqueous Dispersion (CD-2) of Polymer (C-2)

After dropping into the reactor with reflux condenser, dropping tank, thermometer and stirring device 8.0 g of ion-exchanged water 850 g, 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor is heated to 80°C. 105.0 g of dimethyldimethoxysilane, 10.0 g of phenyltrimethoxysilane, 10.0 g of phenyltrimethoxysilane, and 65.7 g of the mixed liquid. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 16.8 g of a 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, after adding 6.6 g of 2% by mass ammonium persulfate aqueous solution, 26.8 g of phenyltrimethoxysilane, tetraethoxy A mixed liquid composed of 28.6 g of silane and 1.1 g of 3-methacryloxypropyltrimethoxysilane; and 0.9 g of acrylic acid and a reactive emulsifier (manufactured by ADEKA, "Adeka Reasoap SR-1025"; solid content Aqueous solution with a content of 25% by mass) 2.3 g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; aqueous solution with a solid content of 25% by mass) 2.3 g, 2.0% by mass of ammonium persulfate A mixed liquid consisting of 30 g of aqueous solution and 170.0 g of ion-exchanged water. Further maintain the temperature in the reactor at 80° C. and continue stirring for about 1 hour, then cool to room temperature, add 25% ammonia solution to the reaction solution to adjust the pH to 8, and filter with a 100-mesh metal mesh. It adjusted with ion-exchanged water so that the solid content would be 10.0 mass %, and the aqueous dispersion (CD-2) of the polymer (C-2) with a number average particle diameter of 133 nm was obtained as a polymer.

The dimethyldimethoxysilane used for synthesizing the aqueous dispersion was 47.9% by mass in the polymer (C-2) in terms of hydrolysis-condensation products.

In addition, the methyltrimethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane used in the synthesis of the aqueous dispersion were converted into polymer (C 24.0 mass %, 17.7 mass % and 0.6 mass % in -2) are 42.3 mass % in total.

[Manufacturing example 5]

Synthesis of Aqueous Dispersion (CD-3) of Polymer (C-3)

After dropping into the reactor with reflux condenser, dropping tank, thermometer and stirring device 8.0 g of ion-exchanged water 850 g, 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor is heated to 80°C. With the temperature in the reactor kept at 80°C, 125.0 g of dimethyldimethoxysilane, 10.0 g of phenyltrimethoxysilane, methyltrimethoxy A mixed solution consisting of 40.0 g of silane. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 16.8 g of a 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, after adding 6.6 g of 2% by mass ammonium persulfate aqueous solution, 26.8 g of phenyltrimethoxysilane, tetraethoxy A mixed liquid composed of 28.6 g of silane and 1.1 g of 3-methacryloxypropyltrimethoxysilane; and 0.9 g of acrylic acid and a reactive emulsifier (manufactured by ADEKA, "Adeka Reasoap SR-1025"; solid content Aqueous solution with a content of 25% by mass) 2.3 g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; aqueous solution with a solid content of 25% by mass) 2.3 g, 2.0% by mass of ammonium persulfate A mixed liquid consisting of 30 g of aqueous solution and 170.0 g of ion-exchanged water. Further maintain the temperature in the reactor at 80° C. and continue stirring for about 1 hour, then cool to room temperature, add 25% ammonia solution to the reaction solution to adjust the pH to 8, and filter with a 100-mesh metal mesh. It adjusted with ion-exchanged water so that the solid content would be 10.0 mass %, and the aqueous dispersion (CD-3) of the polymer (C-3) with a number average particle diameter of 170 nm was obtained as a polymer.

The dimethyldimethoxysilane used for synthesizing the aqueous dispersion was 57.2% by mass in the polymer (C-3) in terms of hydrolysis-condensation products.

In addition, the methyltrimethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane used in the synthesis of the aqueous dispersion were converted into polymer (C 14.6 mass %, 17.8 mass % and 0.6 mass % in -3) are 33.0 mass % in total.

[Manufacturing example 6]

Synthesis of Aqueous Dispersion (CD-4) of Polymer (C-4)

After dropping into the reactor with reflux condenser, dropping tank, thermometer and stirring device 7.0 g of ion-exchanged water 810 g, 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor is heated to 80°C. With the temperature in the reactor kept at 80°C, 158.0 g of dimethyldiethoxysilane, 16.8 g of phenyltrimethoxysilane, methyltrimethoxy A mixed solution consisting of 33.1 g of silane. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 16.8 g of a 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, after adding 6.6 g of 2% by mass ammonium persulfate aqueous solution, 20.0 g of phenyltrimethoxysilane, tetraethoxy A mixed liquid composed of 28.6 g of silane and 1.1 g of 3-methacryloxypropyltrimethoxysilane; and 0.9 g of acrylic acid and a reactive emulsifier (manufactured by ADEKA, "Adeka Reasoap SR-1025"; solid content Aqueous solution with a content of 25% by mass) 2.3 g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; aqueous solution with a solid content of 25% by mass) 2.3 g, 2.0% by mass of ammonium persulfate A mixed liquid consisting of 30 g of aqueous solution and 170.0 g of ion-exchanged water. Further maintain the temperature in the reactor at 80° C. and continue stirring for about 1 hour, then cool to room temperature, add 25% ammonia solution to the reaction solution to adjust the pH to 8, and filter with a 100-mesh metal mesh. It adjusted with ion-exchanged water so that the solid content would be 10.0 mass %, and the aqueous dispersion (CD-4) of the polymer (C-4) with a number average particle diameter of 180 nm was obtained as a polymer.

The diethoxydimethylsilane used in synthesizing the aqueous dispersion was 59.4% by mass in the polymer (C-4) in terms of hydrolysis and condensation products.

In addition, the methyltrimethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane used in the synthesis of the aqueous dispersion were converted into polymer (C 12.3% by mass, 18.0% by mass and 0.6% by mass in -4) are 30.9% by mass in total.

Synthesis of Aqueous Dispersion (CD-5) of Polymer (C-5)

After dropping into the reactor with reflux condenser, dropping tank, thermometer and stirring device 7.0 g of ion-exchanged water 830 g, 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor is heated to 80°C. With the temperature in the reactor kept at 80°C, 101.5 g of diisopropyldimethoxysilane, 10.0 g of phenyltrimethoxysilane, methyltrimethoxysilane, and A mixed solution consisting of 33.1 g of silane. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 16.8 g of a 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, after adding 6.6 g of 2% by mass ammonium persulfate aqueous solution, 26.8 g of phenyltrimethoxysilane, tetraethoxy A mixed liquid composed of 28.6 g of silane and 1.1 g of 3-methacryloxypropyltrimethoxysilane; and 0.9 g of acrylic acid and a reactive emulsifier (manufactured by ADEKA, "Adeka Reasoap SR-1025"; solid content Aqueous solution with a content of 25% by mass) 2.3 g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; aqueous solution with a solid content of 25% by mass) 2.3 g, 2.0% by mass of ammonium persulfate A mixed liquid consisting of 30 g of aqueous solution and 170.0 g of ion-exchanged water. Further maintain the temperature in the reactor at 80° C. and continue stirring for about 1 hour, then cool to room temperature, add 25% ammonia solution to the reaction solution to adjust the pH to 8, and filter with a 100-mesh metal mesh. It adjusted with ion-exchanged water so that the solid content would be 10.0 mass %, and the aqueous dispersion (CD-5) of the polymer (C-5) with a number average particle diameter of 180 nm was obtained as a polymer.

Diisopropyldimethoxysilane used for synthesizing this aqueous dispersion was 58.1% by mass in the polymer (C-5) in terms of hydrolysis and condensation products.

In addition, the methyltrimethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane used in the synthesis of the aqueous dispersion were converted into polymer (C 12.6 mass %, 18.6 mass % and 0.6 mass % in -5) are 31.8 mass % in total.

[Manufacturing example 8]

Synthesis of Aqueous Dispersion (CD-6) of Polymer (C-6)

After dropping into the reactor with reflux condenser, dropping tank, thermometer and stirring device 7.0 g of ion-exchanged water 850 g, 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor is heated to 80°C. With the temperature in the reactor kept at 80°C, 71.3 g of dimethyldimethoxysilane, 49.3 g of diphenyldimethoxysilane, and phenyltrimethylsilane were added dropwise to the reactor over about 2 hours. A liquid mixture consisting of 36.8 g of oxysilane and 33.1 g of methyltrimethoxysilane. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 16.8 g of a 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, 28.6 g of tetraethoxysilane, 3-methyl A mixed solution consisting of 1.1 g of acryloxypropyltrimethoxysilane; and 0.9 g of acrylic acid and a reactive emulsifier (manufactured by ADEKA, "Adeka Reasoap SR-1025"; aqueous solution with a solid content of 25% by mass) 2.3g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; aqueous solution with a solid content of 25 mass%) 2.3g, 2.0 mass% aqueous solution of ammonium persulfate 30g, ion-exchanged water 170.0g formed mixture. Further maintain the temperature in the reactor at 80° C. and continue stirring for about 1 hour, then cool to room temperature, add 25% ammonia solution to the reaction solution to adjust the pH to 8, and filter with a 100-mesh metal mesh. It adjusted with ion-exchanged water so that the solid content would be 10.0 mass %, and the aqueous dispersion (CD-6) of the polymer (C-6) with a number average particle diameter of 180 nm was obtained as a polymer.

The dimethyldimethoxysilane and diphenyldimethoxysilane used in synthesizing the aqueous dispersion were 31.9% by mass and 29.0% by mass in the polymer (C-6) in terms of complete hydrolysis and condensate, respectively. %.

In addition, the methyltrimethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane used in the synthesis of the aqueous dispersion were converted into polymer (C 11.8% by mass, 17.4% by mass and 0.6% by mass in -6), a total of 29.8% by mass.

[Manufacturing example 9]

Synthesis of Aqueous Dispersion (CD-7) of Polymer (C-7)

After dropping into the reactor with reflux condenser, dropping tank, thermometer and stirring device 7.0 g of ion-exchanged water 850 g, 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor is heated to 80°C. With the temperature in the reactor kept at 80°C, 109.7 g of dimethoxymethylphenylsilane, 10.0 g of phenyltrimethoxysilane, methyltrimethoxy A mixed solution consisting of 33.1 g of silane. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 16.8 g of a 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, after adding 6.6 g of 2% by mass ammonium persulfate aqueous solution, 26.8 g of phenyltrimethoxysilane, tetraethoxy A mixed liquid composed of 28.6 g of silane and 1.1 g of 3-methacryloxypropyltrimethoxysilane; and 0.9 g of acrylic acid and a reactive emulsifier (manufactured by ADEKA, "Adeka Reasoap SR-1025"; solid content Aqueous solution with a content of 25% by mass) 2.3 g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; aqueous solution with a solid content of 25% by mass) 2.3 g, 2.0% by mass of ammonium persulfate A mixed liquid consisting of 30 g of aqueous solution and 170.0 g of ion-exchanged water. Further maintain the temperature in the reactor at 80° C. and continue stirring for about 1 hour, then cool to room temperature, add 25% ammonia solution to the reaction solution to adjust the pH to 8, and filter with a 100-mesh metal mesh. It adjusted with ion-exchanged water so that the solid content would be 10.0 mass %, and the aqueous dispersion (CD-7) of the polymer (C-7) with a number average particle diameter of 170 nm was obtained as a polymer.

The dimethoxymethylphenylsilane used for synthesizing the aqueous dispersion was 60.3% by mass in the polymer (C-7) in terms of hydrolysis and condensation products.

In addition, the methyltrimethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane used in the synthesis of the aqueous dispersion were converted into polymer (C 12.0% by mass, 17.6% by mass and 0.6% by mass in -7) are 30.2% by mass in total.

[Manufacturing example 10]

Synthesis of Aqueous Dispersion (CD-8) of Polymer (C-8)

After dropping into the reactor with reflux condenser, dropping tank, thermometer and stirring device 10.0 g of ion-exchanged water 850 g, 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor is heated to 80°C. With the temperature in the reactor kept at 80°C, 140.0 g of dimethyldimethoxysilane, 20.0 g of phenyltrimethoxysilane, methyltrimethoxy A mixed solution consisting of 5.0 g of silane. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 16.8 g of a 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, after adding 6.6 g of 2% by mass ammonium persulfate aqueous solution, 26.8 g of phenyltrimethoxysilane, tetraethoxy A mixed liquid composed of 28.6 g of silane and 1.1 g of 3-methacryloxypropyltrimethoxysilane; and 0.9 g of acrylic acid and a reactive emulsifier (manufactured by ADEKA, "Adeka Reasoap SR-1025"; solid content Aqueous solution with a content of 25% by mass) 2.3 g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; aqueous solution with a solid content of 25% by mass) 2.3 g, 2.0% by mass of ammonium persulfate A mixed liquid consisting of 30 g of aqueous solution and 170.0 g of ion-exchanged water. Further maintain the temperature in the reactor at 80° C. and continue stirring for about 1 hour, then cool to room temperature, add 25% ammonia solution to the reaction solution to adjust the pH to 8, and filter with a 100-mesh metal mesh. It adjusted with ion-exchanged water so that the solid content would be 10.0 mass %, and the aqueous dispersion (CD-8) of the polymer (C-8) with a number average particle diameter of 119 nm was obtained as a polymer.

The dimethyldimethoxysilane used in synthesizing the aqueous dispersion was 64.7% by mass in the polymer (C-8) in terms of hydrolysis and condensation products.

In addition, the methyltrimethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane used in the synthesis of the aqueous dispersion were converted into polymer (C 1.8% by mass, 22.8% by mass and 0.6% by mass in -8) are 25.2% by mass in total.

[Manufacturing example 11]

Synthesis of Aqueous Dispersion (CD-9) of Polymer (C-9)

After dropping into the reactor with reflux condenser, dropping tank, thermometer and stirring device 10.0 g of ion-exchanged water 850 g, 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor is heated to 80°C. A liquid mixture consisting of 140.0 g of dimethyldimethoxysilane and 40.0 g of methyltrimethoxysilane was added dropwise to the reactor over about 2 hours while maintaining the temperature in the reactor at 80°C. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 16.8 g of a 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, after adding 6.6 g of 2% by mass ammonium persulfate aqueous solution, 30.0 g of methyltrimethoxysilane, tetraethoxy A mixed liquid composed of 28.6 g of silane and 1.1 g of 3-methacryloxypropyltrimethoxysilane; and 0.9 g of acrylic acid and a reactive emulsifier (manufactured by ADEKA, "Adeka Reasoap SR-1025"; solid content Aqueous solution with a content of 25% by mass) 2.3 g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; aqueous solution with a solid content of 25% by mass) 2.3 g, 2.0% by mass of ammonium persulfate A mixed liquid consisting of 30 g of aqueous solution and 170.0 g of ion-exchanged water. Further maintain the temperature in the reactor at 80° C. and continue stirring for about 1 hour, then cool to room temperature, add 25% ammonia solution to the reaction solution to adjust the pH to 8, and filter with a 100-mesh metal mesh. It adjusted with ion-exchanged water so that the solid content would be 10.0 mass %, and the aqueous dispersion (CD-9) of the polymer (C-9) with a number average particle diameter of 150 nm was obtained as a polymer.

The dimethyldimethoxysilane used for synthesizing the aqueous dispersion was 63.9% by mass in the polymer (C-9) in terms of hydrolysis-condensation products.

In addition, the methyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane used in the synthesis of this aqueous dispersion were converted to hydrolysis and condensation products, and it was 25.5 mass in the polymer (C-9). % and 0.6% by mass, the total is 26.1% by mass.

[Manufacturing example 12]

Synthesis of Aqueous Dispersion (CD-10) of Polymer (C-10)

After dropping into the reactor with reflux condenser, dropping tank, thermometer and stirring device 10.0 g of ion-exchanged water 850 g, 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor is heated to 80°C. A liquid mixture consisting of 140.0 g of dimethyldimethoxysilane and 25.0 g of phenyltrimethoxysilane was added dropwise to the reactor over about 2 hours while maintaining the temperature in the reactor at 80°C. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 16.8 g of a 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, after adding 6.6 g of 2% by mass ammonium persulfate aqueous solution, 26.8 g of phenyltrimethoxysilane, tetraethoxy A mixed liquid composed of 28.6 g of silane and 1.1 g of 3-methacryloxypropyltrimethoxysilane; and 0.9 g of acrylic acid and a reactive emulsifier (manufactured by ADEKA, "Adeka Reasoap SR-1025"; solid content Aqueous solution with a content of 25% by mass) 2.3 g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; aqueous solution with a solid content of 25% by mass) 2.3 g, 2.0% by mass of ammonium persulfate A mixed liquid consisting of 30 g of aqueous solution and 170.0 g of ion-exchanged water. Further maintain the temperature in the reactor at 80° C. and continue stirring for about 1 hour, then cool to room temperature, add 25% ammonia solution to the reaction solution to adjust the pH to 8, and filter with a 100-mesh metal mesh. It adjusted with ion-exchanged water so that the solid content would be 10.0 mass %, and the aqueous dispersion (CD-10) of the polymer (C-10) with a number average particle diameter of 160 nm was obtained as a polymer.

The dimethyldimethoxysilane used for synthesizing the aqueous dispersion was 64.3% by mass in the polymer (C-10) in terms of hydrolysis-condensation products.

In addition, the phenyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane used when synthesizing the aqueous dispersion were converted into hydrolysis and condensation products, and it was 25.1 mass in the polymer (C-10). % and 0.6 mass%, the total is 25.7 mass%.

[Manufacturing example 13]

Synthesis of Aqueous Dispersion (C'D-11) of Polymer (C'-11)

After dropping into the dodecylbenzenesulfonic acid aqueous solution 5.6g of ion-exchanged water 850g, 10 mass % in the reactor with reflux condenser, dropping tank, thermometer and stirring device, the temperature in the reactor is heated to 80°C. With the temperature in the reactor kept at 80°C, 81.0 g of dimethyldimethoxysilane, 124.8 g of phenyltrimethoxysilane, and methyltrimethoxysilane were added dropwise to the reactor over about 2 hours. A mixed solution consisting of 29.4 g of silane. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 5.6 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, after injecting 6.6 g of 2% by mass ammonium persulfate aqueous solution, 12.3 g of phenyltrimethoxysilane, tetraethoxy A mixed liquid composed of 28.6 g of silane and 1.1 g of 3-methacryloxypropyltrimethoxysilane; and 0.9 g of acrylic acid and a reactive emulsifier (manufactured by ADEKA, "Adeka Reasoap SR-1025"; solid content Aqueous solution with a content of 25% by mass) 1.2 g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; aqueous solution with a solid content of 25% by mass) 1.2 g, 2.0% by mass of ammonium persulfate A mixed liquid consisting of 30 g of aqueous solution and 286.4 g of ion-exchanged water. Further maintain the temperature in the reactor at 80° C. and continue stirring for about 1 hour, then cool to room temperature, add 25% ammonia solution to the reaction solution to adjust the pH to 8, and filter with a 100-mesh metal mesh. Adjustment was made with ion-exchanged water so that the solid content was 10.0% by mass, and an aqueous dispersion (C'D-11) of a polymer (C'-11) having a number average particle diameter of 160 nm was obtained as a polymer.

The dimethyldimethoxysilane used in synthesizing the aqueous dispersion was 30.1% by mass in the polymer (C'-11) in terms of hydrolysis and condensation products.

In addition, the methyltrimethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane used in the synthesis of the aqueous dispersion were converted into polymer (C 8.7% by mass, 53.8% by mass and 0.5% by mass in '-11), the total is 63.0% by mass.

[Manufacturing example 14]

Synthesis of Aqueous Dispersion (C'D-12) of Polymer (C'-12)

After dropping into the dodecylbenzenesulfonic acid aqueous solution 5.6g of ion-exchanged water 850g, 10 mass % in the reactor with reflux condenser, dropping tank, thermometer and stirring device, the temperature in the reactor is heated to 80°C. With the temperature in the reactor kept at 80°C, 81.0 g of dimethyldimethoxysilane, 73.0 g of phenyltrimethoxysilane, methyltrimethoxy A mixed solution consisting of 30.0 g of silane. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 5.6 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, after 6.6 g of a 2% by mass ammonium persulfate aqueous solution was introduced, 22.5 g of methyl methacrylate and 11.2 g of n-butyl acrylate were added dropwise for about 2 hours while keeping the temperature in the reactor at 80°C. g, 12.3g of phenyltrimethoxysilane, 28.6g of tetraethoxysilane, 1.1g of 3-methacryloxypropyltrimethoxysilane; and 0.9g of acrylic acid, reactive emulsifier (manufactured by ADEKA Corporation, "AdekaReasoap SR-1025"; solid content is 25% by mass of aqueous solution) 1.2g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; solid content is 25% by mass) % aqueous solution) 1.2 g, 30 g of a 2.0 mass % aqueous solution of ammonium persulfate, and 286.4 g of ion-exchanged water. Further maintain the temperature in the reactor at 80° C. and continue stirring for about 1 hour, then cool to room temperature, add 25% ammonia solution to the reaction solution to adjust the pH to 8, and filter with a 100-mesh metal mesh. Adjustment was made with ion-exchanged water so that the solid content was 10.0% by mass, and an aqueous dispersion (C'D-12) of a polymer (C'-12) having a number average particle diameter of 157 nm was obtained as a polymer.

The dimethyldimethoxysilane used for synthesizing the aqueous dispersion was 30.1% by mass in the polymer (C'-12) in terms of hydrolysis and condensation products.

In addition, the methyltrimethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane used in the synthesis of the aqueous dispersion were converted into polymer (C 8.9% by mass, 33.4% by mass and 0.5% by mass in '-12), the total is 42.8% by mass.

[Manufacturing example 15]

Synthesis of Aqueous Dispersion (C'D-13) of Polymer (C'-13)

After dropping into the reactor with reflux condenser, dropping tank, thermometer and stirring device 10.0 g of ion-exchanged water 850 g, 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor is heated to 80°C. A liquid mixture consisting of 168.0 g of dimethyldimethoxysilane and 10.0 g of phenyltrimethoxysilane was added dropwise to the reactor over about 2 hours while maintaining the temperature in the reactor at 80°C. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 16.8 g of a 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, after adding 6.6 g of 2% by mass ammonium persulfate aqueous solution, 26.8 g of phenyltrimethoxysilane, tetraethoxy A mixed liquid composed of 28.6 g of silane and 1.1 g of 3-methacryloxypropyltrimethoxysilane; and 0.9 g of acrylic acid and a reactive emulsifier (manufactured by ADEKA, "Adeka Reasoap SR-1025"; solid content Aqueous solution with a content of 25% by mass) 2.3 g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; aqueous solution with a solid content of 25% by mass) 2.3 g, 2.0% by mass of ammonium persulfate A mixed liquid consisting of 30 g of aqueous solution and 170.0 g of ion-exchanged water. Further maintain the temperature in the reactor at 80° C. and continue stirring for about 1 hour, then cool to room temperature, add 25% ammonia solution to the reaction solution to adjust the pH to 8, and filter with a 100-mesh metal mesh. Adjustment was made with ion-exchanged water so that the solid content was 10.0% by mass, and an aqueous dispersion (C'D-13) of a polymer (C'-13) having a number average particle diameter of 146 nm was obtained as a polymer.

The dimethyldimethoxysilane used in synthesizing the aqueous dispersion was 73.1% by mass in the polymer (C'-13) in terms of hydrolysis and condensation products.

In addition, in terms of hydrolysis and condensation products of phenyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane used in the synthesis of this aqueous dispersion, it was 16.9% of the polymer (C'-13). % by mass and 0.6% by mass are 17.5% by mass in total.

[Manufacturing example 16]

Synthesis of Aqueous Dispersion (C'D-14) of Polymer (C'-14)

After dropping into the dodecylbenzenesulfonic acid aqueous solution 5.6g of ion-exchanged water 850g, 10 mass % in the reactor with reflux condenser, dropping tank, thermometer and stirring device, the temperature in the reactor is heated to 80°C. With the temperature in the reactor kept at 80°C, 150.0 g of dimethyldimethoxysilane, 30.0 g of phenyltrimethoxysilane, methyltrimethoxy A mixed solution consisting of 10.0 g of silane. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 5.6 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, after 6.6 g of a 2% by mass ammonium persulfate aqueous solution was introduced, 22.5 g of methyl methacrylate and 11.2 g of n-butyl acrylate were added dropwise for about 2 hours while keeping the temperature in the reactor at 80°C. g, 12.3g of phenyltrimethoxysilane, 28.6g of tetraethoxysilane, 1.1g of 3-methacryloxypropyltrimethoxysilane; and 0.9g of acrylic acid, reactive emulsifier (manufactured by ADEKA Corporation, "Adeka Reasoap SR-1025"; solid content is an aqueous solution of 25% by mass) 1.2 g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; solid content is 25% % aqueous solution) 1.2 g, 30 g of a 2.0 mass % aqueous solution of ammonium persulfate, and 286.4 g of ion-exchanged water. Further maintain the temperature in the reactor at 80° C. and continue stirring for about 1 hour, then cool to room temperature, add 25% ammonia solution to the reaction solution to adjust the pH to 8, and filter with a 100-mesh metal mesh. Adjustment was made with ion-exchanged water so that the solid content was 10.0% by mass, and an aqueous dispersion (C'D-14) of a polymer (C'-14) having a number average particle diameter of 163 nm was obtained as a polymer.

The dimethyldimethoxysilane used in synthesizing the aqueous dispersion was 54.2% by mass in the polymer (C'-14) in terms of hydrolysis and condensation products.

In addition, the methyltrimethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane used in the synthesis of the aqueous dispersion were converted into polymer (C 2.9% by mass, 16.1% by mass and 0.5% by mass in '-14), the total is 19.5% by mass.

[Manufacturing example 17]

Synthesis of Aqueous Dispersion (C'D-15) of Polymer (C'-15)

After dropping into the reactor with reflux condenser, dropping tank, thermometer and stirring device 7.0 g of ion-exchanged water 850 g, 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor is heated to 80°C. 140.0 g of dimethoxymethylphenylsilane, 8.0 g of phenyltrimethoxysilane, methyltrimethoxy A mixed solution consisting of 10.0 g of silane. Thereafter, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after throwing in 16.8 g of a 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. Here, after adding 6.6 g of 2% by mass ammonium persulfate aqueous solution, 26.8 g of phenyltrimethoxysilane, tetraethoxy A mixed liquid composed of 28.6 g of silane and 1.1 g of 3-methacryloxypropyltrimethoxysilane; and 0.9 g of acrylic acid and a reactive emulsifier (manufactured by ADEKA, "Adeka Reasoap SR-1025"; solid content Aqueous solution with a content of 25% by mass) 2.3 g, reactive emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Aquaron KH-1025"; aqueous solution with a solid content of 25% by mass) 2.3 g, 2.0% by mass of ammonium persulfate A mixed liquid consisting of 30 g of aqueous solution and 170.0 g of ion-exchanged water. Further maintain the temperature in the reactor at 80° C. and continue stirring for about 1 hour, then cool to room temperature, add 25% ammonia solution to the reaction solution to adjust the pH to 8, and filter with a 100-mesh metal mesh. Adjustment was made with ion-exchanged water so that the solid content was 10.0% by mass, and an aqueous dispersion (C'D-15) of a polymer (C'-15) having a number average particle diameter of 178 nm was obtained as a polymer.

The dimethoxymethylphenylsilane used in synthesizing the aqueous dispersion was 71.7% by mass in the polymer (C'-15) in terms of hydrolysis and condensation products.

In addition, the methyltrimethoxysilane, phenyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane used in the synthesis of the aqueous dispersion were converted into polymer (C 3.4% by mass, 15.6% by mass and 0.5% by mass in '-15), the total is 19.5% by mass.

The composition of each polymer is listed in Table 1.

【Table 1】

[Manufacturing example 18]

Synthesis of Inorganic Oxides (E-1) with Photocatalytic Activity

Silica Modified Rutile Titanium Dioxide

While maintaining the pH of the reaction solution at 5-9, 700 mL of an aqueous titanium tetrachloride solution having a concentration of 200 g/L as TiO ₂ and an aqueous sodium hydroxide solution having a concentration of 100 g/L as Na ₂ O were added. Thereafter, after adjusting the pH of the reaction solution to 7, it was filtered and washed until the conductivity of the filtrate was 100 μS/cm to obtain a titanium dioxide wet cake 1 with a solid content of 28.3% by mass. The titanium dioxide wet cake 1 contains fine particles having a rutile structure, and the number average particle diameter of the primary particles is 8 nm.

The obtained titanium dioxide wet cake 1 was diluted with pure water to prepare a 1 mol/liter slurry. 1 L of this slurry was put into a 3 L flask, 1 equivalent of nitric acid was further added so that the molar ratio of titanium dioxide/nitric acid became 1/1, the temperature was heated to 95° C., and the temperature was maintained for 2 hours to perform acid heat treatment. The slurry after acid heat treatment was cooled to room temperature, neutralized with 28% ammonia water to pH 6.7, and filtered. Thereafter, washing was performed until the electrical conductivity of the filtrate was 100 μS/cm, and a titanium dioxide wet cake 2 having a solid content of 25% by mass was obtained.

A 10% aqueous solution of sodium hydroxide was added to the obtained titanium dioxide wet cake 2 to perform repulping, and thereafter, it was dispersed with an ultrasonic cleaner for 3 hours to obtain alkaline titanium dioxide having a pH of 10.5 and a solid content of 10% by mass. Sol. Put 2 L of this alkaline titanium dioxide sol into a 3 L flask, raise the temperature to 70° C., add 69.4 mL of an aqueous sodium silicate solution having a concentration of 432 g/L as SiO ₂ , then raise the temperature to 90° C. and maintain it for 1 hour. , adding 10% sulfuric acid to adjust the pH to 6 to obtain a titanium dioxide sol in which the surface of titanium dioxide was surface-treated with silicon hydrous oxide.

The obtained titania sol was cooled to room temperature, 5.4 L of pure water was added, impurities were removed and concentrated using a desalination and concentration device, and a neutral rutile type with a pH of 7.3, a solid content of 29% by mass, and an electrical conductivity of 1.18 mS/cm was obtained. Titanium dioxide sol. This neutral rutile-type titania sol contains 15% by mass of a silicon hydrous oxide based on SiO ₂ relative to TiO ₂ . The number average particle diameter of primary particles of titanium dioxide in this sol was 9 nm.

[Manufacturing example 19]

Synthesis of Inorganic Oxides (E-2) with Photocatalytic Activity

Silica Modified Anatase Titanium Dioxide

The titanium sulfate solution obtained by reacting titanium ore and sulfuric acid was heated and hydrolyzed, and the generated aggregated metatitanic acid was made into an aqueous slurry of 30% by mass in terms of TiO ₂ . Ammonia water was added to the slurry to neutralize it to pH 7, and sulfate ions were removed by filtration and washing to obtain a dehydrated filter cake. Peptization treatment was performed by adding nitric acid to the obtained dehydrated cake to obtain an acidic titanium dioxide sol at pH 1.5 consisting of titanium dioxide fine particles (primary particle number average particle diameter: 7 nm) having an anatase crystal structure .

The obtained acidic titania sol was diluted with pure water to prepare 600 mL of a titania sol having a concentration of 200 g/L in terms of TiO _{2 .} % sulfuric acid was added simultaneously. Thereafter, aging was carried out for 30 minutes. Next, after adding 10% sodium hydroxide aqueous solution to adjust the pH to 8, the pH was adjusted to 6 with 2% sulfuric acid aqueous solution, and filtered and washed to obtain a wet cake. This wet cake was reslurried in pure water, and ultrasonically dispersed to obtain an anatase-type titanium dioxide sol (solid content: 20% by mass, pH: 7.5) stable in the neutral region. Among them, aggregated silica was coated on the surface of titanium dioxide fine particles in a porous state, and its content was 7 parts by mass in terms of SiO ₂ relative to 100 parts by mass of TiO ₂ .

[Example 1]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 60.0g, ethanol 50.0g, and ion-exchanged water 210.0g were stirred to obtain a water-based coating agent composition (K -1). The viscosity of this water-based coating agent composition (K-1) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enameled paint in advance) on the single side (coated with enameled paint) in advance, utilize spray to coat water-based coating agent composition (K-1) so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-1) in which a coating film was formed on the substrate. Table 2 lists various physical properties and evaluation results of the water-based coating agent composition (K-1), the coating film, and the test panel (L-1).

[Example 2]

Instead of using 180.0 g of the aqueous dispersion (CD-1) of the polymer (C-1), 180.0 g of the aqueous dispersion (CD-2) of the polymer (C-2) (10.0% by mass of the solid content) was used, Except for this, it carried out similarly to Example 1, and obtained the aqueous coating agent composition (K-2) whose solid content was 6.0 mass %. The viscosity of this water-based coating agent composition (K-2) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint in advance) that is coated with enamelled paint in advance, utilize spraying to coat water-based coating agent composition (K-2) so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-2) in which a coating film was formed on the substrate. Table 2 lists various physical properties and evaluation results of the water-based coating agent composition (K-2), the coating film, and the test panel (L-2).

[Example 3]

Water-dispersed colloidal silica (D-2) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex O"; solid content 30% by mass) 40.0g, ethanol 50.0g, and ion-exchanged water 230.0g, and stirred to obtain a water-based coating agent composition (K -3). The viscosity of this water-based coating agent composition (K-3) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint) in advance, the water-based coating agent composition (K-3) is applied by spraying so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-3) in which a coating film was formed on the substrate. Table 2 lists various physical properties and evaluation results of the water-based coating agent composition (K-3), coating film, and test panel (L-3).

[Example 4]

Instead of using 180.0 g of the aqueous dispersion (CD-1) of the polymer (C-1), 180.0 g of the aqueous dispersion (CD-3) of the polymer (C-3) (10.0% by mass of the solid content) was used, Except for this, it carried out similarly to Example 1, and obtained the aqueous coating agent composition (K-4) whose solid content was 6.0 mass %. The viscosity of this water-based coating agent composition (K-4) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enameled paint in advance) on the single side (coated with enameled paint) in advance, utilize spray to coat water-based coating agent composition (K-4) so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-4) in which a coating film was formed on the substrate. Table 2 lists various physical properties and evaluation results of the water-based coating agent composition (K-4), coating film, and test panel (L-4).

[Example 5]

Utilize spray to coat the water-based coating agent composition (K-4) on one side of the 7cm × 15cm substrate Y (coated with the enamelled surface) that has been coated with the enamelled paint in advance so that the coating The amount is 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-5) in which a coating film was formed on the substrate. Various physical properties and evaluation results of the test plate (L-5) are listed in Table 2.

[Example 6]

Water-dispersed colloidal silica (D-3) with a number average particle diameter of 25 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex O-40"; solid content 40% by mass) 30.0 g, ethanol 50.0 g, and ion-exchanged water 240.0 g were stirred to obtain a water-based coating agent composition with a solid content of 6.0 mass % (K-6). The viscosity of this water-based coating agent composition (K-6) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint in advance) that is coated with enamelled paint in advance, utilize spraying to coat water-based coating agent composition (K-6) so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-6) in which a coating film was formed on the substrate. Table 2 lists various physical properties and evaluation results of the water-based coating agent composition (K-6), the coating film, and the test panel (L-6).

[Example 7]

Instead of using 180.0 g of the aqueous dispersion (CD-1) of the polymer (C-1), 180.0 g of the aqueous dispersion (CD-4) of the polymer (C-4) (solid content: 10.0 mass %) was used, Except for this, it carried out similarly to Example 1, and obtained the aqueous coating agent composition (K-7) whose solid content was 6.0 mass %. The viscosity of this water-based coating agent composition (K-7) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint in advance) on the single side (coated with enamelled paint) in advance, utilize spray to coat water-based coating agent composition (K-7) so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-7) in which a coating film was formed on the substrate. Table 2 lists various physical properties and evaluation results of the water-based coating agent composition (K-7), the coating film, and the test panel (L-7).

[Example 8]

Instead of using 180.0 g of the aqueous dispersion (CD-1) of the polymer (C-1), 180.0 g of the aqueous dispersion (CD-5) of the polymer (C-5) (solid content: 10.0% by mass) was used, Except for this, it carried out similarly to Example 1, and obtained the water-based coating agent composition (K-8) whose solid content was 6.0 mass %. The viscosity of this water-based coating agent composition (K-8) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint in advance) that is coated with enamelled paint in advance, utilize spraying to coat water-based coating agent composition (K-8) so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-8) in which a coating film was formed on the substrate. Table 2 lists various physical properties and evaluation results of the water-based coating agent composition (K-8), the coating film, and the test panel (L-8).

[Example 9]

Instead of using 180.0 g of the aqueous dispersion (CD-1) of the polymer (C-1), 180.0 g of the aqueous dispersion (CD-6) of the polymer (C-6) (solid content: 10.0% by mass) was used, Except for this, it carried out similarly to Example 1, and obtained the aqueous coating agent composition (K-9) whose solid content was 6.0 mass %. The viscosity of this water-based coating agent composition (K-9) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint) in advance, the water-based coating agent composition (K-9) is applied by spraying so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-9) in which a coating film was formed on the substrate. Table 2 lists various physical properties and evaluation results of the water-based coating agent composition (K-9), the coating film, and the test panel (L-9).

[Example 10]

Instead of using 180.0 g of the aqueous dispersion (CD-1) of the polymer (C-1), 180.0 g of the aqueous dispersion (CD-7) of the polymer (C-7) (solid content: 10.0 mass %) was used, Except for this, it carried out similarly to Example 1, and obtained the aqueous coating agent composition (K-10) whose solid content was 6.0 mass %. The viscosity of this water-based coating agent composition (K-10) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint) in advance, the water-based coating agent composition (K-10) is applied by spraying so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-10) in which a coating film was formed on the substrate. Table 2 lists various physical properties and evaluation results of the water-based coating agent composition (K-10), the coating film, and the test panel (L-10).

[Example 11]

Instead of using 180.0 g of the aqueous dispersion (CD-1) of the polymer (C-1), 180.0 g of the aqueous dispersion (CD-8) of the polymer (C-8) (solid content: 10.0 mass %) was used, Except for this, it carried out similarly to Example 1, and obtained the aqueous coating agent composition (K-11) whose solid content was 6.0 mass %. The viscosity of this water-based coating agent composition (K-11) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint) in advance, the water-based coating agent composition (K-11) is applied by spraying so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-11) in which a coating film was formed on the substrate. Table 2 lists various physical properties and evaluation results of the water-based coating agent composition (K-11), coating film, and test panel (L-11).

[Example 12]

Instead of using 180.0 g of the aqueous dispersion (CD-1) of the polymer (C-1), 180.0 g of the aqueous dispersion (CD-9) of the polymer (C-9) (solid content: 10.0 mass %) was used, Except for this, it carried out similarly to Example 1, and obtained the water-based coating agent composition (K-12) whose solid content was 6.0 mass %. The viscosity of this water-based coating agent composition (K-12) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enameled paint in advance) on the single side (coated with enamelled paint) in advance, utilize spray to coat water-based coating agent composition (K-12) so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-12) in which a coating film was formed on the substrate. Table 2 lists various physical properties and evaluation results of the water-based coating agent composition (K-12), the coating film, and the test panel (L-12).

[Example 13]

Instead of using 180.0 g of the aqueous dispersion (CD-1) of the polymer (C-1), 180.0 g of the aqueous dispersion (CD-10) of the polymer (C-10) (10.0% by mass of the solid content) was used, Except for this, it carried out similarly to Example 1, and obtained the aqueous coating agent composition (K-13) whose solid content was 6.0 mass %. The viscosity of this water-based coating agent composition (K-13) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint in advance) that is coated with enamelled paint in advance, utilize spraying to coat water-based coating agent composition (K-13) so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-13) in which a coating film was formed on the substrate. Table 2 lists various physical properties and evaluation results of the water-based coating agent composition (K-13), the coating film, and the test panel (L-13).

[Example 14]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 30.0g, ethanol 50.0g, and ion-exchanged water 180.0g, and stirred to obtain a solid content of 6.0% by mass water-based coating agent composition (K -14). The viscosity of this water-based coating agent composition (K-14) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint in advance) that is coated with enamelled paint in advance, utilize spraying to coat water-based coating agent composition (K-14) so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-14) in which a coating film was formed on the substrate. Table 3 lists various physical properties and evaluation results of the water-based coating agent composition (K-14), the coating film, and the test panel (L-14).

[Example 15]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 45.0g, ethanol 50.0g, and ion-exchanged water 195.0g, and stirred to obtain a solid content of 6.0% by mass water-based coating agent composition (K -15). The viscosity of this water-based coating agent composition (K-15) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint in advance) that is coated with enamelled paint in advance, utilize spray to coat water-based coating agent composition (K-15) so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-15) in which a coating film was formed on the substrate. Table 3 lists various physical properties and evaluation results of the water-based coating agent composition (K-15), the coating film, and the test panel (L-15).

[Example 16]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 37.5 g, photocatalytically active inorganic oxide (E-1) 5.2 g (solid content 29 mass %), ethanol 50.0 g, and ion-exchanged water 197.3 g, and stirred to obtain a water-based coating agent composition (K-16) with a solid content of 6.0% by mass. The viscosity of this water-based coating agent composition (K-16) was 2 mPa·s.

Then, on one side (the face coated with enamelled paint) of the 7 cm × 15 cm substrate X previously coated with enameled paint, utilize spraying to coat the above-mentioned water-based coating agent composition (K-16) to The coating amount was made to be 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-16) in which a coating film was formed on the substrate. Table 3 lists various physical properties and evaluation results of the water-based coating agent composition (K-16), the coating film, and the test panel (L-16).

[Example 17]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 30.0 g, photocatalytically active inorganic oxide (E-1) 10.3 g (solid content 29 mass %), ethanol 50.0 g, and ion-exchanged water 199.7 g, and stirred to obtain a water-based coating agent composition (K-17) with a solid content of 6.0% by mass. The viscosity of this water-based coating agent composition (K-17) was 2 mPa·s.

Then, on one side (the face coated with enamelled paint) of 7 cm × 15 cm substrate X previously coated with enamelled paint, utilize spraying to coat the above-mentioned water-based coating agent composition (K-17) to The coating amount was made to be 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-17) in which a coating film was formed on the substrate. Table 3 lists various physical properties and evaluation results of the water-based coating agent composition (K-17), the coating film, and the test panel (L-17).

[Example 18]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 22.5 g, photocatalytically active inorganic oxide (E-1) 15.5 g (solid content 29 mass %), ethanol 50.0 g, and ion-exchanged water 202.0 g, and stirred to obtain a water-based coating agent composition (K-18) with a solid content of 6.0% by mass. The viscosity of this water-based coating agent composition (K-18) was 2 mPa·s.

Then, on one side (the face coated with enamelled paint) of 7 cm × 15 cm substrate X previously coated with enamelled paint, utilize spraying to coat the above-mentioned water-based coating agent composition (K-18) to The coating amount was made to be 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-18) in which a coating film was formed on the substrate. Table 3 lists various physical properties and evaluation results of the water-based coating agent composition (K-18), the coating film, and the test panel (L-18).

[Example 19]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 37.5 g, photocatalytically active inorganic oxide (E-2) 7.5 g (solid content 20 mass %), ethanol 50.0 g, and ion-exchanged water 195.0 g, and stirred to obtain a water-based coating agent composition (K-19) with a solid content of 6.0% by mass. The viscosity of this water-based coating agent composition (K-19) was 2 mPa·s.

Then, on one side (the face coated with enamelled paint) of 7 cm × 15 cm substrate X previously coated with enamelled paint, utilize spraying to coat the above-mentioned water-based coating agent composition (K-19) to The coating amount was made to be 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-19) in which a coating film was formed on the substrate. Table 3 lists various physical properties and evaluation results of the water-based coating agent composition (K-19), the coating film, and the test panel (L-19).

[Example 20]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 30.0g, photocatalytically active inorganic oxide (E-1) 10.3g (solid content 29% by mass), fluorocarbon surfactant (F- 1) (manufactured by DIC Corporation, "MEGAFAC F-444") 0.2 g, 50.0 g of ethanol, and 199.5 g of ion-exchanged water were stirred to obtain a water-based coating agent composition (K- 20). The viscosity of this water-based coating agent composition (K-20) was 2 mPa·s.

Then, on one side (the face coated with enamelled paint) of 7 cm × 15 cm substrate X previously coated with enamelled paint, utilize spraying to coat the above-mentioned water-based coating agent composition (K-20) to The coating amount was made to be 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-20) in which a coating film was formed on the substrate. Table 3 lists various physical properties and evaluation results of the water-based coating agent composition (K-20), the coating film, and the test panel (L-20).

[Example 21]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 30.0g, photocatalytically active inorganic oxide (E-1) 10.3g (solid content 29% by mass), fluorocarbon surfactant (F- 2) (manufactured by AGC SEIMI CHEMICAL, "Surflon S-232"; solid content 30% by mass) 0.7g, 50.0g of ethanol, and 199.0g of ion-exchanged water were stirred to obtain a solid content of 6.0% by mass. Water-based coating agent composition (K-21). The viscosity of this water-based coating agent composition (K-21) was 2 mPa·s.

Then, on one side (the face coated with enamelled paint) of the 7 cm × 15 cm substrate X previously coated with enamelled paint, utilize spraying to coat the above-mentioned water-based coating agent composition (K-21) to The coating amount was made to be 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-21) in which a coating film was formed on the substrate. Table 3 lists various physical properties and evaluation results of the water-based coating agent composition (K-21), the coating film, and the test panel (L-21).

[Example 22]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 30.0g, photocatalytically active inorganic oxide (E-1) 10.3g (solid content 29% by mass), fluorocarbon surfactant (F- 1) (manufactured by DIC Corporation, "MEGAFAC F-444") 0.2 g, a discoloring dye (G-1) (manufactured by Kishida Chemical Corporation, "methylene blue" adjusted to a solid content of 1.0% by mass with ion-exchanged water ) 3.0 g, 50.0 g of ethanol, and 196.5 g of ion-exchanged water were stirred to obtain an aqueous coating agent composition (K-22) with a solid content of 6.0% by mass. The viscosity of this water-based coating agent composition (K-22) was 2 mPa·s.

Then, on one side (the face coated with enamelled paint) of 7 cm × 15 cm substrate X previously coated with enamelled paint, utilize spraying to coat the above-mentioned water-based coating agent composition (K-22) to The coating amount was made to be 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-22) in which a coating film was formed on the substrate. Table 3 lists various physical properties and evaluation results of the water-based coating agent composition (K-22), the coating film, and the test panel (L-22).

[Example 23]

Instead of using 3.0 g of a discoloring dye (G-1) (manufactured by Kishida Chemical, "Methylene Blue") adjusted to have a solid content of 1.0% by mass using ion-exchanged water, use ion-exchanged water that was adjusted so that the solid content 3.0 g of discoloring pigment (G-2) (manufactured by Hodogaya Chemical Industry Co., Ltd., "acid red") of 1.0 mass %, except that, obtain a water-based coating agent with a solid content of 6.0 mass % in the same manner as in Example 21 Composition (K-23). The viscosity of this water-based coating agent composition (K-23) was 2 mPa·s.

Then, on one side (the face coated with enamelled paint) of 7 cm × 15 cm substrate X previously coated with enamelled paint, utilize spraying to coat the above-mentioned water-based coating agent composition (K-23) to The coating amount was made to be 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-23) in which a coating film was formed on the substrate. Table 3 lists various physical properties and evaluation results of the water-based coating agent composition (K-23), the coating film, and the test panel (L-23).

[Example 24]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Manufactured, "Snowtex OS"; 7.5 g of solid content 20% by mass), 5.2 g of photocatalytically active inorganic oxide (E-1) (29 mass %) of solid content, fluorocarbon surfactant (F-1 ) (manufactured by DIC Corporation, "MEGAFAC F-444") 0.2 g, a discoloring dye (G-1) (manufactured by Kishida Chemical Corporation, "methylene blue") adjusted to a solid content of 1.0% by mass with ion-exchanged water 1.0 g, 40.0 g of a cellulose-based thickener (H-1) (manufactured by Daicelfinechem, "HEC Daicel SP900") adjusted to a solid content of 1.0% by mass with ion-exchanged water, 50.0 g of ethanol, and ion-exchanged 336.1 g of water were stirred, and the water-based coating agent composition (K-24) whose solid content was 1.9 mass % was obtained. The viscosity of this water-based coating agent composition (K-24) was 15 mPa·s.

Then, on one side (the face coated with enamelled paint) of 7 cm × 15 cm substrate X previously coated with enamelled paint, utilize spraying to coat the above-mentioned water-based coating agent composition (K-24) to The coating amount was made to be 50 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-24) in which a coating film was formed on the substrate. Table 3 lists various physical properties and evaluation results of the water-based coating agent composition (K-24), the coating film, and the test panel (L-24).

[Example 25]

Utilize spray to coat the water-based coating agent composition (K-24) on the single side of the 7cm×15cm substrate Y (coated with enamelled paint) on the 7cm * 15cm substrate Y that has been coated with enamelled paint in advance, so that the coating The amount is 50 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-25) in which a coating film was formed on the substrate. Various physical properties and evaluation results of the test plate (L-25) are listed in Table 3.

[Example 26]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 7.5g, photocatalytically active inorganic oxide (E-1) 5.2g (solid content 29% by mass), fluorocarbon surfactant (F- 1) (manufactured by DIC Corporation, "MEGAFAC F-444") 0.2 g, a discoloring dye (G-1) (manufactured by Kishida Chemical Corporation, "methylene blue" adjusted to a solid content of 1.0% by mass with ion-exchanged water ) 1.0 g, 80.0 g of a cellulose-based thickener (H-1) (manufactured by Daicelfinechem, "HEC Daicel SP900") adjusted to a solid content of 1.0% by mass with ion-exchanged water, 50.0 g of ethanol, and ion 296.1 g of water was exchanged and stirred to obtain a water-based coating agent composition (K-26) with a solid content of 2.0% by mass. The viscosity of this water-based coating agent composition (K-26) was 28 mPa·s.

Then, on the single side (face coated with enamelled paint) of 7 cm × 15 cm substrate X previously coated with enamelled paint, utilize spraying to coat the above-mentioned water-based coating agent composition (K-26) to The coating amount was made to be 50 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-26) in which a coating film was formed on the substrate. Table 3 lists various physical properties and evaluation results of the water-based coating agent composition (K-26), the coating film, and the test panel (L-26).

[Example 27]

Instead of using 60.0 g of the aqueous dispersion (CD-3) of the polymer (C-3), 60.0 g of the aqueous dispersion (CD-7) of the polymer (C-7) (solid content: 10.0 mass %) was used, Except for this, it carried out similarly to Example 25, and obtained the water-based coating agent composition (K-27) of 2.0 mass % of solid content. The viscosity of this water-based coating agent composition (K-27) was 26 mPa·s.

Then, on one side (the face coated with enamelled paint) of 7 cm × 15 cm substrate X previously coated with enamelled paint, utilize spraying to coat the above-mentioned water-based coating agent composition (K-27) to The coating amount was made to be 50 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-27) in which a coating film was formed on the substrate. Table 4 lists various physical properties and evaluation results of the water-based coating agent composition (K-27), the coating film, and the test panel (L-27).

[Example 28]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 7.5g, photocatalytically active inorganic oxide (E-1) 5.2g (solid content 29% by mass), fluorocarbon surfactant (F- 1) (manufactured by DIC Corporation, "MEGAFAC F-444") 0.2 g, a discoloring dye (G-1) (manufactured by Kishida Chemical Corporation, "methylene blue" adjusted to a solid content of 1.0% by mass with ion-exchanged water ) 1.0 g, 80.0 g of a cellulose-based thickener (H-2) (manufactured by Shin-Etsu Chemical Co., Ltd., "METOLOSE 90SH-30000") adjusted to have a solid content of 1.0% by mass with ion-exchanged water, 50.0 g of ethanol g and 296.1 g of ion-exchanged water were stirred to obtain a water-based coating agent composition (K-28) with a solid content of 2.0% by mass. The viscosity of this water-based coating agent composition (K-28) was 25 mPa·s.

Then, on the single side (coated with enamelled paint) on the single side (coated with enamelled paint in advance) of the 7cm * 15cm base material X that is coated with enamelled paint in advance, utilize spraying to coat above-mentioned water-based coating agent composition (K-28) to The coating amount was made to be 50 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-28) in which a coating film was formed on the substrate. Table 4 lists various physical properties and evaluation results of the water-based coating agent composition (K-28), the coating film, and the test panel (L-28).

[Example 29]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 29.4g, photocatalytically active inorganic oxide (E-1) 10.1g (solid content 29% by mass), fluorocarbon surfactant (F- 1) (manufactured by DIC Corporation, "MEGAFAC F-444") 0.2 g, a discoloring dye (G-1) (manufactured by Kishida Chemical Corporation, "methylene blue" adjusted to a solid content of 1.0% by mass with ion-exchanged water ) 3.0 g, anti-algae/anti-mold agent (J-1) (manufactured by Dow Chemical, "KLARIX4000", isothiazoline compound; active ingredient 4% by mass) 15.0 g, ethanol 50.0 g, and ion-exchanged water 186.5 g, And it stirred, and obtained the water-based coating agent composition (K-29) whose solid content was 6.0 mass %. The viscosity of this water-based coating agent composition (K-29) was 2 mPa·s.

Then, utilize spraying to coat the above-mentioned water-based coating agent composition (K -29) so that the coating amount is 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-29) in which a coating film was formed on the substrate. Table 4 lists various physical properties and evaluation results of the water-based coating agent composition (K-29), the coating film, and the test panel (L-29).

[Example 30]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; 29.6 g of solid content 20% by mass), 10.2 g of photocatalytically active inorganic oxide (E-1) (29% by mass of solid content), fluorocarbon surfactant (F- 1) (manufactured by DIC Corporation, "MEGAFAC F-444") 0.2 g, a discoloring dye (G-1) (manufactured by Kishida Chemical Corporation, "methylene blue" adjusted to a solid content of 1.0% by mass with ion-exchanged water ) 3.0 g, anti-algae/fungal agent (J-2) (manufactured by Dow Chemical, "ROCIMA345", a mixture of isothiazoline-based compounds and triazine-based compounds; active ingredient 12% by mass) 3.0 g, ethanol 50.0 g It stirred with 196.8 g of ion-exchanged water, and obtained the water-based coating agent composition (K-30) whose solid content was 6.0 mass %. The viscosity of this water-based coating agent composition (K-30) was 2 mPa·s.

Then, utilize spraying to coat the above-mentioned water-based coating agent composition (K -30) so that the coating amount is 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-30) in which a coating film was formed on the substrate. Table 4 lists various physical properties and evaluation results of the water-based coating agent composition (K-30), the coating film, and the test panel (L-30).

[Example 31]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; 28.2 g of solid content 20% by mass), 9.7 g of photocatalytically active inorganic oxide (E-1) (29% by mass of solid content), fluorocarbon surfactant (F- 1) (manufactured by DIC Corporation, "MEGAFAC F-444") 0.2 g, a discoloring dye (G-1) (manufactured by Kishida Chemical Corporation, "methylene blue" adjusted to a solid content of 1.0% by mass with ion-exchanged water ) 3.0 g, anti-algae/anti-mold agent (J-3) (manufactured by Nippon Soda Corporation, "Biocut-N35", a mixture of imidazole-based compounds and triazine-based compounds; active ingredient 35% by mass) 5.0 g, ethanol 50.0 g, and 206.5 g of ion-exchange water was stirred, and the water-based coating agent composition (K-31) whose solid content was 6.0 mass % was obtained. The viscosity of this water-based coating agent composition (K-31) was 2 mPa·s.

Then, utilize spraying to coat the above-mentioned water-based coating agent composition (K -31) so that the coating amount is 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-31) in which a coating film was formed on the substrate. Table 4 lists various physical properties and evaluation results of the water-based coating agent composition (K-31), the coating film, and the test panel (L-31).

[Example 32]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 7.3g, photocatalytically active inorganic oxide (E-1) 5.0g (solid content 29% by mass), fluorocarbon surfactant (F- 1) (manufactured by DIC Corporation, "MEGAFAC F-444") 0.2 g, a discoloring dye (G-1) (manufactured by Kishida Chemical Corporation, "methylene blue" adjusted to a solid content of 1.0% by mass with ion-exchanged water ) 1.0 g, 80.0 g of a cellulose-based thickener (H-1) (manufactured by Daicelfinechem, "HEC Daicel SP900") adjusted to have a solid content of 1.0% by mass with ion-exchanged water, anti-algae/anti-mold Agent (J-1) (manufactured by Dow Chemical, "KLARIX4000", isothiazoline compound; active ingredient 4% by mass) 10.0 g, ethanol 50.0 g, and ion-exchanged water 288.5 g were stirred to obtain the solid content A 2.0% by mass water-based coating agent composition (K-32). The viscosity of this water-based coating agent composition (K-32) was 28 mPa·s.

Then, utilize spraying to coat the above-mentioned water-based coating agent composition (K -32) so that the coating amount is 50 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-32) in which a coating film was formed on the substrate. Table 4 lists various physical properties and evaluation results of the water-based coating agent composition (K-32), the coating film, and the test panel (L-32).

[Example 33]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 7.5g, photocatalytically active inorganic oxide (E-1) 5.2g (solid content 29% by mass), fluorocarbon surfactant (F- 1) (manufactured by DIC Corporation, "MEGAFAC F-444") 0.2 g, a discoloring dye (G-1) (manufactured by Kishida Chemical Corporation, "methylene blue" adjusted to a solid content of 1.0% by mass with ion-exchanged water ) 1.0 g, 80.0 g of a cellulose-based thickener (H-1) (manufactured by Daicelfinechem, "HEC Daicel SP900") adjusted to have a solid content of 1.0% by mass with ion-exchanged water, anti-algae/anti-mold Agent (J-2) (manufactured by Dow Chemical Company, "ROCIMA345", a mixture of isothiazoline compounds and triazine compounds; active ingredient 12% by mass) 1.3g, ethanol 50.0g and ion-exchanged water 294.9g, and carried out Stirring was carried out to obtain a water-based coating agent composition (K-33) with a solid content of 2.0% by mass. The viscosity of this water-based coating agent composition (K-33) was 27 mPa·s.

Then, utilize spraying to coat the above-mentioned water-based coating agent composition (K -33) so that the coating amount is 50 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-33) in which a coating film was formed on the substrate. Table 4 lists various physical properties and evaluation results of the water-based coating agent composition (K-33), the coating film, and the test panel (L-33).

[Example 34]

Water-dispersed colloidal silica (D-1) with a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd. Co., Ltd., "Snowtex OS"; solid content 20% by mass) 6.8g, photocatalytically active inorganic oxide (E-1) 4.7g (solid content 29% by mass), fluorocarbon surfactant (F- 1) (manufactured by DIC Corporation, "MEGAFAC F-444") 0.2 g, a discoloring dye (G-1) (manufactured by Kishida Chemical Corporation, "methylene blue" adjusted to a solid content of 1.0% by mass with ion-exchanged water ) 1.0 g, 80.0 g of a cellulose-based thickener (H-1) (manufactured by Daicelfinechem, "HEC Daicel SP900") adjusted to have a solid content of 1.0% by mass with ion-exchanged water, anti-algae/anti-mold Agent (J-3) (manufactured by Nippon Soda Corporation, "Biocut-N35", a mixture of imidazole-based compounds and triazine-based compounds; active ingredient 35% by mass) 2.8 g, 50.0 g of ethanol, and 300.2 g of ion-exchanged water were stirred , thereby obtaining a water-based coating agent composition (K-34) with a solid content of 2.0% by mass. The viscosity of this water-based coating agent composition (K-34) was 28 mPa·s.

Then, utilize spraying to coat the above-mentioned water-based coating agent composition (K -34) so that the coating amount is 50 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-34) in which a coating film was formed on the substrate. Table 4 lists various physical properties and evaluation results of the water-based coating agent composition (K-34), the coating film, and the test panel (L-34).

[Comparative example 1]

Instead of using 180.0 g of the aqueous dispersion (CD-1) of the polymer (C-1), 180.0 g of the aqueous dispersion (C'D-11) of the polymer (C'-11) was used (solid content 10.0 mass %), and obtained a solid content content of 6.0% by mass of the water-based coating agent composition (K-35) in the same manner as in Example 1. The viscosity of this water-based coating agent composition (K-35) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint in advance) that is coated with enamelled paint in advance, utilize spraying to coat water-based coating agent composition (K-35) so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-35) in which a coating film was formed on the substrate. Table 4 lists various physical properties and evaluation results of the water-based coating agent composition (K-35), the coating film, and the test panel (L-35).

[Comparative example 2]

Instead of using 180.0 g of the aqueous dispersion (CD-1) of the polymer (C-1), 180.0 g of the aqueous dispersion (C'D-12) of the polymer (C'-12) was used (solid content 10.0 mass %), and obtained a solid content of 6.0% by mass of the water-based coating agent composition (K-36) in the same manner as in Example 1. The viscosity of this water-based coating agent composition (K-36) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enameled paint in advance) that is coated with enamelled paint in advance, utilize spraying to coat water-based coating agent composition (K-36) so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-36) in which a coating film was formed on the substrate. Table 4 lists various physical properties and evaluation results of the water-based coating agent composition (K-36), the coating film, and the test panel (L-36).

[Comparative example 3]

Instead of using 180.0 g of the aqueous dispersion (CD-1) of the polymer (C-1), 180.0 g of the aqueous dispersion (C'D-13) of the polymer (C'-13) was used (solid content 10.0 mass %), and obtained a solid content of 6.0% by mass of the water-based coating agent composition (K-37) in the same manner as in Example 1. The viscosity of this water-based coating agent composition (K-37) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint) in advance, the water-based coating agent composition (K-37) is applied by spraying so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left still at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-37) in which a coating film was formed on the substrate. Table 4 lists various physical properties and evaluation results of the water-based coating agent composition (K-37), the coating film, and the test panel (L-37).

[Comparative example 4]

Instead of using 180.0 g of the aqueous dispersion (CD-1) of the polymer (C-1), 180.0 g of the aqueous dispersion (C'D-14) of the polymer (C'-14) was used (solid content 10.0 mass %), and a solid content content of 6.0% by mass of the water-based coating agent composition (K-38) was obtained in the same manner as in Example 1. The viscosity of this water-based coating agent composition (K-38) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint in advance) that is coated with enamelled paint in advance, utilize spraying to coat water-based coating agent composition (K-38) so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-38) in which a coating film was formed on the substrate. Table 4 lists various physical properties and evaluation results of the water-based coating agent composition (K-38), the coating film, and the test panel (L-38).

[Comparative Example 5]

Instead of using 180.0 g of the aqueous dispersion (CD-1) of the polymer (C-1), 180.0 g of the aqueous dispersion (C'D-15) of the polymer (C'-15) was used (solid content: 10.0 mass %), and obtained a solid content of 6.0% by mass of the water-based coating agent composition (K-39) in the same manner as in Example 1. The viscosity of this water-based coating agent composition (K-39) was 2 mPa·s.

Then, on one side of the 7cm × 15cm substrate X (coated with enamelled paint) on one side (coated with enamelled paint) in advance, the water-based coating agent composition (K-39) is applied by spraying so that The coating amount was 17 g/m ² . The coated substrate was kept horizontal, and it was left to stand at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a test panel (L-39) in which a coating film was formed on the substrate. Table 4 lists various physical properties and evaluation results of the water-based coating agent composition (K-39), the coating film, and the test panel (L-39).

From the above, it was confirmed that all the water-based coating agent compositions of the present examples can form coating films capable of maintaining high levels of appearance and stain resistance.

Industrial Applicability

The water-based coating agent composition, coating film, and painted product of the present invention can be used as various parts such as architectural exterior applications, exterior display applications, automotive parts, optical parts such as displays or lenses, and the like.

Claims (12)

1. a kind of aqueous coating agent composition, contains：

The dispersion (CD) of copolymer (C), the copolymer (C) include structural unit (A) and structural unit (B), the structure list First (A) is derived from as the silane (a) shown in the following general formula (1), and the structural unit (B) is derived from by the following general formula (2) Suo Shi Silane (b)；With

Inorganic oxide (D)；

The content of the structural unit (A) in the copolymer (C) is scaled the matter of 47 mass %~70 with hydrolytic condensate Measure %,

The content of the structural unit (B) in the copolymer (C) is scaled the matter of 23 mass %~45 with hydrolytic condensate Measure %,

(R¹)₂-Si-(R²)₂···(1)

In formula (1), R¹Each independently represent hydrogen atom, the aliphatic alkyl that carbon number is 1~16, carbon number are 6~10 Aryl, carbon number be 5~6 cycloalkyl, carbon number be 1~10 acrylic acid alkyl ester group or carbon number be 1 ~10 alkyl methacrylate base, R²Each independently represent carbon number be 1~8 alkoxy, acetoxyl group or Hydroxyl,

R³-Si-(R⁴)₃···(2)

In formula (2), R³Represent that aliphatic alkyl, carbon number that hydrogen atom, carbon number are 1~16 are 6~10 aryl, carbon original The methyl that the acrylic acid alkyl ester group or carbon number that cycloalkyl that subnumber is 5~6, carbon number are 1~10 are 1~10 Acrylic acid alkyl ester group, R⁴Each independently represent alkoxy, acetoxyl group or the hydroxyl that carbon number is 1~8.

2. aqueous coating agent composition as described in claim 1, wherein, the dispersion (CD) of the copolymer (C) is to pass through At least using the silane (a) and the silane (b) and obtained from carrying out emulsion polymerization.

3. aqueous coating agent composition as claimed in claim 1 or 2, wherein, the inorganic oxide (D) is silica.

4. aqueous coating agent composition as claimed in claim 1 or 2, wherein, the composition further contains urges with light Change the inorganic oxide (E) of activity.

5. aqueous coating agent composition as claimed in claim 1 or 2, wherein, the composition further contains fluorocarbon surface Activating agent (F).

6. aqueous coating agent composition as claimed in claim 1 or 2, wherein, the composition further contains fadedness color Plain (G).

7. aqueous coating agent composition as claimed in claim 1 or 2, wherein, the composition is further containing cellulose-based Thickener (H).

8. aqueous coating agent composition as claimed in claim 1 or 2, wherein, the composition, which further contains, to be selected from by preventing The substance of one or more of the group of algae agent and mould inhibitor (J) composition.

9. a kind of aqueous coating contains claim 1~8 any one of them aqueous coating agent composition.

10. a kind of film, is obtained as the aqueous coating described in claim 9.

11. a kind of coated articles, containing the film described in base material and claim 10, which is formed at the table of the base material At least a portion in face.

12. coated articles as claimed in claim 11, wherein, the base material is organic substrate.