JP6637534B2 - Water-based compositions, water-based paints, coatings, and painted products - Google Patents

Description

  The present invention relates to an aqueous composition, an aqueous paint, a coating film, and a coated product.

The surface of outdoor structures such as architectural exteriors, bridges, tanks, etc. are painted with paint, etc., but the surface of the paint film may be dust, soot, sand, etc. Pollutants discharged from the discharge port of the soil, and organisms represented by algae mold and the like. Such coating stains are usually dark or green in color and significantly impair the aesthetics of buildings and outdoor structures.
As an aqueous overcoating composition that suppresses contamination of the coating film as described above, the applicant has an undercoat layer, and an overcoat layer provided on the undercoat layer, wherein the undercoat layer is composed of water and an emulsifier. The coating film of the undercoating coating composition (I) containing the polymer emulsion particles (A) obtained by the method including the step of polymerizing the vinyl monomer and the hydrolyzable silicon compound in the presence of Wherein the overcoat layer comprises a step of polymerizing a metal oxide particle (B) having photocatalytic activity, and a vinyl monomer and a hydrolyzable silicon compound in the presence of water and an emulsifier, respectively. A coating film of a top coating composition (II) containing the polymer emulsion particles (C) obtained by the method and colloidal silica (D) is formed by drying. A film, a multilayer coating film has been proposed (e.g., see Patent Documents 1 and 2).

JP 2010-005595 A Japanese Patent No. 5411574

The technique described in Patent Document 1 uses a material having a high glass transition temperature as the undercoat layer, so that even the overcoat layer formed from the coating composition for the overcoat has sufficient stain resistance and weather resistance. However, there is a problem that there is room for improvement as described later.
That is, the case where the coating agent composition for overcoating 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 widely used for architectural exteriors and the like. Assuming that the overcoat layer formed from the overcoating agent composition may not be able to sufficiently follow the substrate that expands and contracts due to a change in external temperature or the like. In such a case, cracks or the like may occur in the overcoat layer, and the cracks may cause a decrease in gloss and impair the appearance. Further, the undercoat layer is often colored with a pigment or the like, and has a problem that appearance may be impaired such as white turbidity when overcoated on a dark base material having an L * value of about 10 to 40. . If such points can be improved with respect to the coating film, the coating film having excellent physical properties such as appearance and stain resistance over a long period of time without being limited by the base material and color of the undercoat layer. Realization can be expected.
Further, the technology described in Patent Document 2 obtains stain resistance by setting the porosity and constituent components in a specific range in a coating film, but is represented by dirt or algal mold eluted from the sealing. There is a problem that there is room for improvement with respect to biological contamination. Regarding such biological contamination, the technique of Patent Document 1 described above also has a problem that there is room for improvement.

  Therefore, in the present invention, in view of the above-described circumstances, even when a dark-colored base material is used, the appearance is not impaired, and over a long period of time, the appearance, stain resistance, sealing stain resistance, and biological stain resistance are at a high level. It is an object of the present invention to provide a composition capable of forming a coating film that can be maintained.

The present inventors have conducted intensive studies to solve the above-described problems of the related art,
An aqueous dispersion (AD) of a polymer (A) having a predetermined number average particle diameter, silicon dioxide (B), and an inorganic oxide (C) having photocatalytic activity; By using an aqueous composition whose mass ratio with the silicon dioxide (B) (polymer (A) / silicon dioxide (B)) is within a predetermined range, the above-mentioned problem of the prior art can be solved. And found that the present invention was completed.
That is, the present invention is as follows.

[1]
An aqueous dispersion (AD) of the polymer (A) having a number average particle diameter of 10 to 40 nm,
Silicon dioxide (B),
An inorganic oxide (C) having photocatalytic activity;
, Containing
The polymer (A) is a poly (meth) acrylate-based polymer, and is a shea recone modified (meth) any one or more selected from an acrylic polymer or Ranaru group,
The mass ratio of the polymer (A) and the silicon dioxide (B) (polymer (A) / silicon dioxide (
B)) is 1/22 or more and less than 1/4.
[2]
The aqueous composition according to [1], wherein the polymer (A) contains a structural unit derived from dimethyldimethoxysilane (a) in an amount of 20 to 70% by mass in terms of a hydrolyzed condensate.
[3]
The aqueous composition according to the above [1] or [2], further comprising a fluorocarbon surfactant (D).
[4]
The aqueous composition according to any one of the above [1] to [3], further comprising a fading dye (E).
[5]
An aqueous paint containing the aqueous composition according to any one of the above [1] to [4].
[6]
A coating film formed from the water-based paint according to the above [5].
[7]
A substrate,
The coating film according to (6), which is formed on at least a part of the surface of the substrate,
, Including, painted products.
[8]
The coated product according to [7], wherein the substrate is an organic substrate.

  According to the present invention, a coating film capable of maintaining a high level of appearance, stain resistance, sealing stain resistance, and biological stain resistance over a long period of time without impairing the appearance even when a dark-colored substrate is used is formed. Possible compositions can be provided.

Hereinafter, embodiments for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail.
The following embodiment is an exemplification for describing the present invention, and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist.

(Aqueous composition)
The aqueous composition of the present embodiment is
An aqueous dispersion (AD) of the polymer (A) having a number average particle diameter of 10 to 40 nm,
Silicon dioxide (B),
An inorganic oxide (C) having photocatalytic activity;
, Containing
The mass ratio of the polymer (A) to the silicon dioxide (B) (polymer (A) / silicon dioxide (B)) is not less than 1/22 and less than 1/4.
The coating film obtained from the water-based composition of the present embodiment does not impair the appearance even with a dark-colored substrate, and maintains a high level of appearance, stain resistance, sealing stain resistance, and biological stain resistance for a long period of time. Can be.

(Number average particle diameter of polymer (A))
The aqueous composition of the present embodiment contains an aqueous dispersion (AD) of the polymer (A) having a number average particle size of 10 to 40 nm.
The polymer (A) is not particularly limited, and for example, a polymer obtained by a method such as emulsion polymerization can be used. Specific examples thereof include, but are not limited to, polymers obtained by performing any one of radical polymerization, anionic polymerization, and cationic polymerization in an aqueous medium.
The number average particle size of the polymer (A) is from 10 nm to 40 nm.
By using the polymer (A) having the number average particle diameter in the above range, the aqueous composition of the present embodiment does not have white turbidity even when applied to a dark base material, and the obtained coating film does not impair the appearance. . Furthermore, when the number average particle diameter of the polymer (A) is 10 nm or more, the stain resistance of the coating film is further improved, and when the number average particle diameter of the polymer (A) is 40 nm or less, The weather resistance of the film is further improved.
The lower limit of the number average particle size of the polymer (A) is 10 nm, preferably 12 nm, and more preferably 15 nm.
The upper limit of the number average particle size of the polymer (A) is 40 nm, preferably 38 nm, and more preferably 35 nm.

The method for controlling the number average particle size of the polymer (A) to the above-mentioned range is not particularly limited. By increasing the amount of the activator, the number average particle diameter can be reduced.
The number average particle diameter of the polymer (A) can be measured using a wet particle size analyzer, and specifically, can be measured by a method described in Examples described later.

(Mass ratio of polymer (A) and silicon dioxide (B))
The aqueous composition of the present embodiment contains silicon dioxide (B).
In the aqueous composition of the present embodiment, the mass ratio of the polymer (A) and the silicon dioxide (B) (polymer (A) / silicon dioxide (B)) is not less than 1/22 and less than 1/4. .
The water-based composition of the present embodiment has a mass ratio of the polymer (A) to the silicon dioxide (B) within the above range. Does not impair the appearance.
Further, when the mass ratio between the polymer (A) and the silicon dioxide (B) is less than 1/4, the stain resistance and the biological stain resistance of the coating film are further improved, and When the mass ratio with silicon (B) is 1/22 or more, the weather resistance of the coating film is further improved.
The mass ratio of the polymer (A) and the silicon dioxide (B) (polymer (A) / silicon dioxide (B)) is at least 1/22 and less than 1/4, preferably at least 1/21 and 1/4. And more preferably 1/21 or more and 1 / 4.2 or less.

(Ingredient of aqueous composition)
<Aqueous dispersion (AD) of polymer (A)>
The aqueous composition of the present embodiment contains an aqueous dispersion (AD) of the polymer (A).
In this specification, the polymer (A) may be described as a component (A).
The component (A) is not limited to the following, but may be, for example, a poly (meth) acrylate polymer, a polyvinyl acetate polymer, a vinyl acetate- (meth) acrylic polymer, or an ethylene vinyl acetate polymer. Copolymer, silicone polymer, fluorine polymer, polybutadiene polymer, styrene butadiene polymer, NBR polymer, polyvinyl chloride polymer, chlorinated polypropylene polymer, polyethylene polymer, polystyrene polymer Homopolymers or copolymers, such as coalesced polymers, vinylidene chloride polymers, polystyrene- (meth) acrylate polymers, styrene-maleic anhydride polymers, silicone-modified (meth) acrylic polymers, fluorine -(Meth) acrylic polymer, (meth) acrylic-silicone polymer, epoxy- (meth) acrylic Modified copolymer represented by the system polymer, and the like.
These may be used alone or in combination of two or more.
In addition, “(meth) acrylate” means “acrylate” and the corresponding “methacrylate”, and “(meth) acryl” means “acryl” and the corresponding “methacryl”.

  The homopolymer, copolymer, modified copolymer, etc. of the above-mentioned polymer (A) (hereinafter sometimes collectively referred to as "polymer") may be obtained in the form of an aqueous dispersion. preferable. Preferred embodiments of these polymers include emulsions, and specific examples thereof include, but are not particularly limited to, acrylic emulsions, acrylic silicone emulsions, and silicone emulsions. These are not particularly limited, but can be obtained, for example, by emulsion polymerization of a monomer such as a (meth) acrylic acid ester or a hydrolyzable silicon compound described later.

  The aqueous composition of the present embodiment may further include, in addition to the component (A), a compound having a functional group that reacts with a functional group contained in the polymer (A). Examples of such a compound include, but are not limited to, a (poly) isocyanate compound, a (poly) epoxy compound, an amino compound, a (poly) carboxy compound, a (poly) hydroxy compound, a glycol compound, and a silanol. Examples include compounds, silyl compounds, alkoxy compounds, (meth) acrylate compounds, and the like. These may be used alone or in combination of two or more.

A vinyl monomer can be used as a polymer component of the polymer (A).
The vinyl monomer that can be used in the production of the component (A) is not limited to the following, but includes, for example, a (meth) acrylate, an aromatic vinyl compound, a vinyl cyanide compound, and a carboxyl group-containing compound. Vinyl compounds having a functional group such as vinyl compounds, hydroxyl group-containing vinyl compounds, glycidyl group-containing vinyl compounds, vinyl compounds having a secondary and / or tertiary amide group, and anionic vinyl compounds are exemplified.

The (meth) acrylic acid ester is not limited to the following, but includes, for example, a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 50 carbon atoms and an ethylene oxide group having 1 to 100 carbon atoms ( And poly) oxyethylene di (meth) acrylate. Specific examples of these are not limited to the following, but for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Methylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, and the like.
Examples of the (poly) oxyethylene di (meth) acrylate include, but are not limited to, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol methoxy (meth) acrylate, And tetraethylene glycol di (meth) acrylate.

Examples of the aromatic vinyl compound include, but are not limited to, styrene, α-methylstyrene, p-tert-butylstyrene, chlorostyrene, vinyltoluene, and the like.
Examples of the vinyl cyanide compound include, but are not limited to, (meth) acrylonitrile and α-chloroacrylonitrile.

Examples of the carboxyl group-containing vinyl compound include, but are not limited to, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, or itaconic acid, maleic acid, and fumaric acid. Half-esters of dibasic acids such as acids. By using a carboxyl group-containing vinyl monomer, a carboxyl group can be introduced into the component (A). Thus, it is presumed that the stability as an emulsion can be further improved, and high resistance to the dispersion breaking action from the outside can be imparted to the coating film. The operation of the present embodiment is not limited to these.
A part or all of the carboxyl group to be introduced can be neutralized with amines such as ammonia, triethylamine and dimethylethanolamine, and bases such as NaOH and KOH. The use amount of the carboxyl group-containing vinyl monomer in the total amount of the above-mentioned vinyl monomers is preferably 0 to 50% by mass from the viewpoint of water resistance, but is not limited thereto.

  Examples of the hydroxyl group-containing vinyl compound include, but are not limited to, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. Hydroxyalkyl esters of (meth) acrylic acid such as (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl mono (Poly) oxyethylene mono (meth) acrylate having 1 to 100 butyl fumarate, allyl alcohol and ethylene oxide groups; (poly) oxypropylene mono (meth) acrylate having 1 to 100 propylene oxide groups, further , And (trade name manufactured by Daicel Chemical Industries caprolactone addition monomer) "PLACCEL FM, FA monomer", and other alpha, hydroxyalkyl esters of β- ethylenically unsaturated carboxylic acid.

  Examples of the (poly) oxyethylene mono (meth) acrylate include, but are not limited to, ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and methoxy. Examples thereof include diethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, and tetraethylene glycol methoxy (meth) acrylate.

  Examples of the (poly) oxypropylene mono (meth) acrylate include, but are not limited to, propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, and dipropylene glycol (meth) acrylate. And dipropylene glycol methoxy (meth) acrylate, tetrapropylene glycol (meth) acrylate, tetrapropylene glycol methoxy (meth) acrylate, and the like.

  The proportion of the hydroxyl group-containing vinyl monomer in the total amount of the above-mentioned vinyl monomers is not limited to the following, but from the viewpoint of the water resistance of the coating film, is preferably 0 to 80% by mass, and more preferably. Is 0.1 to 50% by mass, and more preferably 0.1 to 45% by mass.

Examples of the glycidyl group-containing vinyl compound include, but are not limited to, glycidyl (meth) acrylate, allyl glycidyl ether, allyl dimethyl glycidyl ether, and the like.
When a glycidyl group-containing vinyl monomer is used among the above-mentioned vinyl monomers, the reactivity of the component (A) is further improved. Therefore, by performing crosslinking using a hydrazine derivative, a carboxylic acid derivative, an isocyanate derivative, or the like, a coating film having more excellent solvent resistance and the like can be obtained. From this viewpoint, the total amount of the glycidyl group-containing vinyl monomer in the total amount of the above-mentioned vinyl monomers is preferably 0 to 50% by mass, more preferably 0 to 45% by mass, and Preferably it is 0 to 40% by mass.

Examples of the vinyl compound having a secondary and / or tertiary amide group include, but are not limited to, N-alkyl-substituted (meth) acrylamide and N-alkylene-substituted (meth) acrylamide.
Examples of the N-alkyl-substituted (meth) acrylamide include, but are not limited to, 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, Nn-propyl (meth) acrylamide, N-methyl-NNn-propyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N- (meth) acryloylpyrrolidine, N- (meth) acryloylpiperidine, N-acryloylhexahydroazepine, N- (meth) acryloylmorpholine, N-vinylpyrrolidone, N- Vinyl caprolactam, N, N'-methyle And bis (meth) acrylamide, N-vinylacetamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide and the like.

Examples of the vinyl monomer other than the above-described vinyl monomer include, but are not limited to, olefins such as (meth) acrylamide, ethylene, propylene, and isobutylene; dienes such as butadiene; and vinyl chloride. , Vinylidene vinyl chloride, haloolefins such as tetrafluoroethylene and chlorotrifluoroethylene; vinyl acetate, vinyl propionate, n-vinyl butyrate, vinyl benzoate, p-tert-butyl vinyl benzoate, vinyl pivalate, Carboxylic acid vinyl esters such as vinyl 2-ethylhexanoate, vinyl versatate and vinyl laurate; carboxylic acid isopropenyl esters such as isopropenyl acetate and isopropenyl propionate; ethyl vinyl ether, isobutyl vinyl ether and cyclohexylbi Vinyl ethers such as toluene ether; aromatic vinyl compounds such as styrene and vinyl toluene; allyl esters such as allyl acetate and allyl benzoate; allyl ethers such as allyl ethyl 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, Examples include perfluoropropylmethyl (meth) acrylate, vinylpyrrolidone, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, and the like.
These may be used alone or in combination of two or more.

When the component (A) is produced by a polymerization reaction, a chain transfer agent may be used for the purpose of controlling the molecular weight of a polymerization product of a vinyl monomer to be used.
Examples of the chain transfer agent include, but are not limited to, alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan; and aromatic mercaptans such as benzyl mercaptan and dodecyl benzyl mercaptan. Thiocarboxylic acids such as thiomalic acid or salts thereof or alkyl esters thereof; polythiols; disulfides such as diisopropylxanthogen disulfide and di (methylenetrimethylolpropane) xanthogen disulfide; dimers such as thioglycol and α-methylstyrene; Allyl compounds and the like can be mentioned.
These may be used alone or in combination of two or more.
The use amount of the chain transfer agent with respect to the total amount of the above-mentioned vinyl monomers is not particularly limited, but is preferably 0.001 to 30% by mass, and more preferably 0.05 to 10% by mass.

As a preferred embodiment, the polymer (A) is produced by a polymerization reaction of the above-mentioned vinyl monomer and a hydrolyzable silicon compound.
The hydrolyzable silicon compound used in the reaction for producing the polymer (A) is not limited to the following. For example, a compound represented by the following formula (1), a silane coupling agent, Condensates are preferred.
SiW _x R _y (1)
In the above formula (1), W is an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group. And at least one selected from the group consisting of amide groups.
R represents a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms substituted with a halogen atom. At least one group selected from the group consisting of
x is an integer of 1 or more and 4 or less, y is an integer of 0 or more and 3 or less, and satisfies the relationship of x + y = 4.
When there are a plurality of Ws, and when there are a plurality of Rs, each W and R may be the same or different from each other.

  The compound represented by the formula (1) is not limited to the following, but includes, for example, a silicon alkoxide represented by the formula (1). As the silicon alkoxide, a tetrafunctional silicon alkoxide is preferable from the viewpoint of the hydrolysis rate.

Examples of the silane coupling agent include, but are not limited to, a hydrolyzable group (for example, an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, hydrogen) Atom, at least one selected from the group consisting of an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group and an amide group) and a functional group having reactivity with another compound (for example, a vinyl polymerizable group) , An epoxy group, an amino group, a methacryl group, a thiol group, an isocyanate group, etc.) (a silane coupling agent).
By using such a silane coupling agent as a hydrolyzable silicon compound, a polycondensate of the hydrolyzable silicon compound and a vinyl monomer can be chemically bonded to each other. Thereby, the compatibility is further improved, and the transparency of the coating film is further improved.
As the silane coupling agent, among the above, a silane coupling agent having at least a vinyl polymerizable group and / or a thiol group is preferable, and a silane coupling agent having at least a vinyl polymerizable group is more preferable.

Since the vinyl polymerizable group and the thiol group have high reactivity with the vinyl monomer described above, a chemical bond can be efficiently formed by a copolymerization reaction or a chain transfer reaction with the vinyl monomer. Therefore, by using a silane coupling agent having a vinyl polymerizable group or a thiol group, it can be efficiently compounded with another component (for example, a vinyl monomer or the like) constituting the component (A). By using the component (A) in which a hydrolyzable silicon compound (or a polymerization product thereof) and / or a vinyl monomer (or a polymerization product thereof) and the like are combined by a chemical bond, the weather resistance is improved. A coating film with further improved strength and strength can be obtained.
The effect of the present embodiment is not limited to the characteristics.

  Examples of the silane coupling agent having a vinyl polymerizable group include, but are not limited to, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, -(Meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltri Preferred are methoxysilane, 2-trimethoxysilylethyl vinyl ether and the like.

  Examples of the silane coupling agent having a thiol group include, but are not limited to, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

Examples of the hydrolyzable silicon compound and the silane coupling agent represented by the formula (1) are not limited to the following. For example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra Tetraalkoxysilanes such as isopropoxysilane and tetra-n-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, Isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-o Tyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3- Chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- Hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyl Limethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycid Xypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meta ) Acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyl Trialkoxysilanes such as lysopropoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyl Dimethoxysilane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n- Pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane Dialkoxy such as di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and 3- (meth) acryloyloxypropylmethyldimethoxysilane Silanes; monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane;
Among these, tetraalkoxysilanes, trialkoxysilanes, and dialkoxysilanes are preferable, and tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, and dimethyldimethoxysilane Are more preferable, and tetramethoxysilane and tetraethoxysilane, which are tetrafunctional silicon alkoxides, are further preferable from the viewpoint of high hydrolysis rate.

As the hydrolyzed silicon compound used for producing the polymer (A), a compound represented by the formula (1) or a condensate of a silane coupling agent is preferably used.
When a compound represented by the formula (1) or a condensate of a silane coupling agent is applied as a hydrolyzable silicon compound used in a reaction for producing the polymer (A), the compound represented by the formula (1) is used. The polystyrene equivalent weight average molecular weight of the condensate of the silane coupling agent and the silane coupling agent is not particularly limited, but is preferably from 200 to 5,000, more preferably from 300 to 1,000, and still more preferably from 300 to 950.
By using a condensate having a weight average molecular weight within the above range, polymerization stability is further improved.

  As the silicon alkoxide and the silane coupling agent represented by the formula (1), only one kind may be used alone, or two or more kinds may be used in combination. Among them, it is preferable to use the silicon alkoxide represented by the formula (1) in combination with the silane coupling agent from the viewpoint of improving the performance of the aqueous composition and the obtained coating film, and tetraethoxysilane and methyltrimethoxysilane. More preferably, at least one selected from the group consisting of phenyltrimethoxysilane and dimethyldimethoxysilane is used in combination with 3- (meth) acryloxypropyltrimethoxysilane.

  The total amount of the silane coupling agent having at least a vinyl polymerizable group and / or a thiol group in 100 parts by mass of the component (A) is preferably 0.01 to 20 parts by mass from the viewpoint of polymerization stability. More preferably, it is 0.1 to 10 parts by mass.

In the present embodiment, as the hydrolyzable silicon compound used for producing the polymer (A), a cyclic siloxane oligomer can be used in addition to the above-mentioned compounds. By using a cyclic siloxane oligomer in combination, a coating film having more excellent flexibility and the like can be obtained.
Examples of the cyclic siloxane oligomer include, but are not limited to, compounds represented by the following formula (2).
(R ' ₂ SiO) _m ... (2)

  In the formula (2), R ′ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and 1 to 20 carbon atoms. And at least one selected from the group consisting of an alkoxy group having 6 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms substituted with a halogen atom. m is an integer of 2 or more and 20 or less.

  Among the cyclic siloxane oligomers, a cyclic dimethylsiloxane oligomer such as octamethylcyclotetrasiloxane is preferable from the viewpoint of reactivity and the like.

When producing the component (A), a titanium alkoxide, a zirconium alkoxide, a condensation product or a chelate thereof can be used together with the hydrolyzable silicon compound. By using these compounds in combination, it is possible to obtain a coating film having more excellent water resistance and the like.
Examples of the titanium alkoxide include, but are not limited to, tetramethoxytitanium, tetraethoxytitanium, tetra-i-propoxytitanium, tetra-n-propoxytitanium, tetra-n-butoxytitanium, tetra-sec- Butoxytitanium, tetra-tert-butoxytitanium and the like.
As the titanium alkoxide, a condensate thereof may be used. In that case, the weight average molecular weight of the condensate in terms of polystyrene is not particularly limited, but is preferably 200 to 5,000, and more preferably 300 to 1,000. .
Examples of the zirconium alkoxide include, but are not limited to, tetramethoxy zirconium, tetraethoxy zirconium, tetra-i-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, and tetra-sec- Butoxyzirconium and tetra-tert-butoxyzirconium.
As the zirconium alkoxide, a condensate thereof may be used. In that case, the weight average molecular weight of the condensate in terms of polystyrene is not particularly limited, but is preferably 200 to 5,000, and more preferably 300 to 1,000. .

  The mass ratio of the hydrolyzable silicon compound to the vinyl monomer used when polymerizing the polymer (A) is preferably 0.5 / 99.5 to 99.5 / 0.5, more preferably 0/9. 0.5 / 99.5 to 15/85.

The component (A) preferably contains a structural unit derived from dimethyldimethoxysilane (a) in an amount of from 20 to 70% by mass in terms of hydrolysis and condensation.
The lower limit of the content of the structural unit derived from dimethyldimethoxysilane in the component (A) is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 35% by mass or less, in terms of a hydrolyzed condensate. % By mass or more.
The upper limit of the content of the structural unit derived from dimethyldimethoxysilane in the component (A) is preferably 70% by mass or less, more preferably 68% by mass or less, and even more preferably 65% by mass or less in terms of a hydrolyzed condensate. % By mass or less.
When the content of the structural unit derived from dimethyldimethoxysilane in the component (A) is within the above range, the effect of improving the weather resistance of the coating film can be obtained.
Here, the hydrolysis condensate is a condensate in which a reactive group (for example, an alkoxy group) of dimethyldimethoxysilane is converted into a silanol bond by hydrolysis or a condensation reaction.
The content (% by mass) of the dimethyldimethoxysilane in terms of hydrolysis and condensation is calculated from the content of the polymer (A) (the total solid content) determined as the heating residue of the (AD) component and the charged amount of the dimethyldimethoxysilane. , Can be calculated.
Content (% by mass) of dimethyldimethoxysilane in terms of hydrolysis-condensation product = prepared amount of dimethyldimethoxysilane (g) × 0.617 / total solid content (g) × 100
The content of dimethyldimethoxysilane in terms of hydrolysis and condensation can be controlled within the above numerical range by adjusting the amount of dimethyldimethoxysilane charged.

In producing the component (A), a chelating agent that coordinates with a free metal ion of a metal compound to form a chelate may be used in combination.
Preferred chelating agents include, but are not limited to, alkanolamines such as diethanolamine and triethanolamine; glycols such as ethylene glycol, diethylene glycol and propylene glycol; acetylacetone; and ethyl acetoacetate. Can be
The molecular weight of the chelating agent is not limited to the following, but is preferably 10,000 or less.
By using these chelating agents, the rate of polymerization of the hydrolyzable silicon compound or the like can be controlled, and the polymerization stability in the presence of water and an emulsifier is further improved.
The amount of the chelating agent is not particularly limited, but is preferably 0.1 to 2 mol per 1 mol of the free metal ion to be coordinated.

The emulsifier that can be used in the production of the component (A) is not limited to the following. For example, alkyl benzene sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulfate, polyoxyethylene alkyl aryl Acid emulsifiers such as sulfuric acid and polyoxyethylene distyrylphenyl ether sulfonic acid; alkali metal (Li, Na, K, etc.) salts of the acid emulsifier, ammonium salts of the acid emulsifier; anionic surfactants such as fatty acid soap; For example, quaternary ammonium salts such as alkyltrimethylammonium bromide, alkylpyridinium bromide, imidazolinium laurate, pyridinium salt, imidazolinium salt type cationic surfactants; polyoxyethylene alkyl aryl ether, polio Shi sorbitan fatty acid esters, polyoxyethylene polyoxypropylene block copolymer, nonionic surface active agent polyoxyethylene distyryl phenyl ether; reactive emulsifier or the like having a radical polymerizable double bond.
Among these emulsifiers, a reactive emulsifier having a radical polymerizable double bond (reactive emulsifier) is preferable. By using such a reactive emulsifier, the aqueous dispersion stability of the polymer (A) is extremely improved, and the water resistance of the obtained coating film is further improved.

Examples of the anionic reactive emulsifier include, but are not limited to, an ethylenically unsaturated monomer having a sulfonic acid group, a sulfonate group or a sulfate group and a salt thereof, and the like. A compound having an acid group or a group that is an ammonium salt or an alkali metal salt thereof (an ammonium sulfonate group or an alkali metal sulfonate group) is preferable.
For example, alkyl allyl sulfosuccinates (for example, "Eleminol (trademark) JS-20" manufactured by Sanyo Chemical Industries, Ltd .; for example, "Latemul (trademark) S-120", "Latemul S-180A", "Latemul" manufactured by Kao Corporation S-180 "), for example, polyoxyethylene alkylpropenyl phenyl ether sulfate (for example," Aqualon (trademark) HS-10 "manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), for example. , Α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-polyoxyethylene sulfate (for example, “ADEKA REAL SOAP (trademark) SE-10N” manufactured by ADEKA). For example, ammonium-α-sulfonato-ω-1- (allyloxymethyl) alkyloxypolyoxyethyl (For example, "Aqualon KH-1025" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), for example, styrene sulfonate (for example, "Spinomer (registered trademark) NaSS" manufactured by Tosoh Organic Chemicals, Inc.) ), For example, α- [2-[(allyloxy) -1- (alkyloxymethyl) ethyl] -ω-polyoxyethylene sulfate (for example, “ADEKA REAL SOAP (trademark) SR-1025” manufactured by ADEKA) And the like.), For example, polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether sulfate (for example, "Latemul (trademark) PD-104" manufactured by Kao Corporation). ) And the like.
Among them, ammonium-α-sulfonato-ω-1- (allyloxymethyl) alkyloxypolyoxyethylene, α- [2-[(allyloxy) -1- (alkyloxymethyl) ethyl] -ω-polyoxyethylene Sulfate salts are preferred.

  The nonionic reactive emulsifier is not limited to the following, but may be, for example, α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene (For example, (Adekaria Soap NE-20, Adecaria Soap NE-30, Adecaria Soap NE-40) manufactured by ADEKA, etc.), for example, polyoxyethylene alkylpropenyl phenyl ether (For example, "AQUALON RN-10", "AQUALON RN-20", "AQUALON RN-30", "AQUALON RN-50", etc., manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), for example, α- [2 -[(Allyloxy) -1- (alkyloxymethyl) ethyl] -ω-hydroxypolyoxyethylene (for example, manufactured by ADEKA "Adecaria Soap (trademark) ER-10" etc.), for example, polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (for example, "Latemul (trademark) PD-" manufactured by Kao Corporation) 420 ").

  The amount of the emulsifier used is preferably 10 parts by mass or less based on 100 parts by mass of the total amount of the raw materials of the polymer (A) component (for example, the hydrolyzable silicon compound and the vinyl monomer). Preferably it is 0.001-5 mass parts. When the amount of the emulsifier used is in the above range, the polymerization stability is further improved, and the water resistance of the coating film is further improved.

The polymerization of the vinyl monomer and the hydrolyzable silicon compound when producing the polymer (A) is preferably carried out in the presence of a polymerization catalyst.
The polymerization catalyst for the vinyl monomer is not particularly limited, but is preferably a radical polymerization catalyst that undergoes radical decomposition by heat or a reducing substance to cause addition polymerization of the vinyl monomer.
Such radical polymerization catalysts are not limited to the following, but include, for example, persulfates, peroxides, azobis compounds and the like. These may be water-soluble or oil-soluble.
Examples of the radical polymerization catalyst include, but are not limited to, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, tert-butylperoxybenzoate, and 2,2. -Azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like.
The blending amount of the radical polymerization catalyst is not particularly limited, but is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of the vinyl monomer. When it is desired to accelerate the polymerization rate or efficiently polymerize at a low temperature (for example, 70 ° C. or lower), for example, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, or Rongalite is used as a radical polymerization catalyst. It is preferable to use together.
Examples of the polymerization catalyst for the hydrolyzable silicon compound include, but are not limited to, hydrogen halides such as hydrochloric acid and hydrofluoric acid; carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid, and lactic acid; And sulfonic acids such as p-toluenesulfonic acid; acidic emulsifiers such as alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylenealkylsulfuric acid, polyoxyethylenealkylarylsulfuric acid, and polyoxyethylene distyrylphenyl 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 methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine The Basic compounds such as zabicycloundecene, ethylenediamine, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane; dibutyltin octylate, dibutyltin dilaurate, etc. Of a tin compound.
Among these, acidic emulsifiers are preferred as the polymerization catalyst for the hydrolyzable silicon compound, from the viewpoint of having not only a polymerization catalyst but also a function as an emulsifier. As the acidic emulsifiers, alkylbenzenesulfonic acids having 5 to 30 carbon atoms (for example, dodecylbenzenesulfonic acid and the like) are more preferable.

The polymerization of the vinyl monomer and the hydrolyzable silicon compound can be carried out separately, but it is preferable to carry out the polymerization at the same time, since the complex can be efficiently achieved.
As a suitable method for obtaining the component (A), for example, so-called emulsion polymerization in which a vinyl monomer and a hydrolyzable silicon compound are polymerized in the presence of water in an amount sufficient for an emulsifier to form micelles is used. No. The specific method of the emulsion polymerization is not particularly limited, and, for example, the vinyl monomer and the hydrolyzable silicon compound are directly or emulsified, collectively or dividedly, or continuously dropped into the reaction vessel. And a method in which polymerization is performed at a reaction temperature of about 30 to 150 ° C. in the presence of a polymerization catalyst, preferably at a pressure of atmospheric pressure to 10 MPa.
The reaction temperature and the reaction pressure may not be the above conditions depending on the reaction conditions and the like.
The solid content in the emulsion obtained by emulsion polymerization is not particularly limited, but is preferably 0.1 to 70% by mass, more preferably 1 to 55% by mass, and still more preferably 5 to 30% by mass. is there.
If it is desired to control the particle size more during the emulsion polymerization, it is preferable to employ a seed polymerization method in which emulsion particles are present in an aqueous phase in advance and polymerized. In this case, the pH of the polymerization system is not particularly limited, but is preferably 1.0 to 10.0, and more preferably 1.0 to 6.0. This pH can be adjusted using a pH buffer such as disodium phosphate, sodium tetraborate (such as borax), sodium bicarbonate, and ammonia.
The method for producing the component (A) is not particularly limited. For example, a polymerization product is obtained by polymerizing a hydrolyzable silicon compound and a vinyl monomer in the presence of water and an emulsifier in the presence of a solvent if necessary. Can be employed to further add water until the emulsion becomes an emulsion. However, from the viewpoint of easily controlling the particle size of the obtained component (A), emulsion polymerization is preferred.

The component (A) preferably has a core / shell structure having a core and one or more shell layers.
Having a core / shell structure is preferable because the mechanical properties (such as balance between strength and flexibility) of the obtained coating film are further improved.
Confirmation of the core / shell structure of the component (A) can be performed by, for example, morphological observation with a transmission electron microscope or the like or analysis by viscoelasticity measurement.
A method for producing the component (A) having a core / shell structure is not particularly limited, but a multistage emulsion polymerization is a preferred method.
The term "multi-stage emulsion polymerization" as used herein refers to a method in which two or more reaction solutions containing a vinyl monomer and a hydrolyzable silicon compound having different compositions are prepared, and these are separated into different stages and polymerized.

As an example of the multi-stage emulsion polymerization, a method of synthesizing the component (A) having a core / shell structure by two-stage emulsion polymerization will be mainly described.
The two-stage emulsion polymerization is not particularly limited. For example, a step (first stage) of polymerizing a vinyl monomer and / or a hydrolyzable silicon compound in the presence of water and an emulsifier to obtain seed particles, A method including a step (second stage) of polymerizing a hydrolyzable silicon compound and a vinyl monomer in the presence of the obtained seed particles, and the like.
The production of the component (A) by two-stage emulsion polymerization is carried out by first-stage polymerization in which a first series (a vinyl monomer and / or a hydrolyzable silicon compound) is supplied and emulsion polymerization is performed. The second series (vinyl monomer and / or hydrolyzable silicon compound) is supplied, and the polymerization is performed in a two-stage polymerization process including a second-stage polymerization in which an emulsion polymerization is further performed in an aqueous medium. At this time, the mass ratio ((M1) / (M2)) of the solid content (M1) in the first series to the solid content (M2) in the second series is not particularly limited, but is preferably 9/1 to 1 / 9.
By performing such multi-stage emulsion polymerization, polymer particles having a more uniform particle size can be obtained. As a method of adding the raw materials in the multi-stage emulsion polymerization, a method in which seed particles (core) are prepared in the first-stage polymerization, and thereafter, another monomer and the like are additionally added is preferable. Thereby, the particle diameter of the polymer particles obtained in the second stage polymerization can be increased without changing the ratio of the volume average particle diameter / number average particle diameter of the seed particles (core) obtained in the first stage polymerization. It is also possible to do.
When performing three or more stages of multi-stage emulsion polymerization, the number of polymerization stages may be increased in the same manner as in two-stage polymerization.

The content of the component (A) in the aqueous composition of the present embodiment is not particularly limited, but is preferably 0.1 to 5.0% by mass, and more preferably 0.1 to 4.0% by mass. And more preferably 0.1 to 3.0% by mass.
By setting the content of the component (A) in the aqueous composition within the above range, a coating film having further excellent appearance, weather resistance, stain resistance, sealing stain resistance, and biological stain resistance on a dark-colored substrate can be obtained. Obtainable.
The content of the component (A) in the coating film obtained from the aqueous composition of the present embodiment is preferably 1.0 to 15.0% by mass, more preferably 1.0 to 14.0% by mass, More preferably, it is 2.0 to 14.0% by mass, and still more preferably 3.0 to 14.0% by mass. By setting the content of the component (A) in the coating film within the above range, a coating film having a more excellent appearance, weather resistance, stain resistance, sealing stain resistance, and biological stain resistance on a dark-colored substrate can be obtained. be able to.

<Silicon dioxide (B)>
The aqueous composition of the present embodiment contains silicon dioxide (B).
In this specification, silicon dioxide (B) may be simply described as a component (B).
The silicon dioxide (B) is preferably colloidal silica. Examples of the colloidal silica include colloidal silica which is a dispersion of water or a water-soluble solvent of silica having silicon dioxide as a basic unit.
The method for producing colloidal silica is not particularly limited, and can be prepared, for example, by a sol-gel method. When preparing by the sol-gel method, Werner Stober et al .; Journal of Colloid And Interface Science, vol. 26, pp. 62-69 (1968), Rickey D. Badley et al .; Lang muir 6, 792-801 (1990), "Journal of the Society of Color Materials", 61 [9] 488-493 (1988), and the like.

The number average particle diameter of the component (B) is not particularly limited, but is preferably 1 to 100 nm, more preferably 4 to 30 nm, and still more preferably 8 to 25 nm.
By setting the number average particle size of the component (B) to 1 nm or more, the storage stability of the aqueous composition is further improved. By setting the number average particle diameter of the component (B) to 100 nm or less, the appearance when a dark-colored base material is used is further improved. The number average particle diameter can be measured using a wet type particle size analyzer.

Colloidal silica may be acidic or basic in the form of an aqueous dispersion.
Commercial products can also be used as the acidic colloidal silica using water as a dispersion medium.
Examples of such commercially available products include, but are not limited to, "Snowtex (trademark) -OXS", "Snowtex-OS", "Snowtex-O", manufactured by Nissan Chemical Industries, Ltd. "Snowtex-O-40", "Snowtex-OL" and "Snowtex-OYL", "ADELITE (trademark) AT-20Q" manufactured by ADEKA, "Clezol (trademark) 20H12" manufactured by Clariant Japan, and "Clevazole 30CAL25" and the like.
Examples of the basic colloidal silica include, but are not limited to, colloidal silica stabilized by adding an alkali metal ion, an ammonium ion, an amine, or the like. These can also use a commercial item. Such commercially available products are not limited to the following. For example, “Snowtex-XS”, “Snowtex-S”, “Snowtex-30”, “Snowtex” manufactured by Nissan Chemical Industries, Ltd. -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" Snowtex-PS-M "; manufactured by ADEKA Adelite AT-20, Adelite AT-30, Adelite AT-20N, Adelite AT-30N, Adelaite "AT-20A", "Adelite AT-30A", "Adelite AT-40" and "Adelite AT-50";"Clevosol30R9","Clevozole30R50","Clevozole50R50" manufactured by Clariant Japan, manufactured by DuPont "Ludox (trademark) HS-40", "Ludox HS-30", "Ludox LS", and "Ludox SM-30".
As the colloidal silica using a water-soluble solvent as a dispersion medium, a commercially available product can also be used. Such commercially available products are not limited to the following, but for example, “MA-ST-M (methanol dispersion type having a particle size of 20 to 25 nm)” and “IPAST (particle size)” manufactured by Nissan Chemical Industries, Ltd. 10-15 nm isopropyl alcohol dispersion type), "EG-ST (ethylene glycol dispersion type with particle diameter of 10-15 nm)", "EG-ST-ZL (ethylene glycol dispersion type with particle diameter of 70-100 nm)", " NPC-ST (ethylene glycol monopropyl ether dispersion type having a particle diameter of 10 to 15 nm) "and the like.
The above-mentioned colloidal silica may be used alone or in combination of two or more. Further, as a small component, alumina, sodium aluminate and the like may be contained. Further, the colloidal silica may contain an inorganic base (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia) or an organic base (such as tetramethylammonium) as a stabilizer.

The content of the component (B) in the aqueous composition of the present embodiment is not particularly limited, but is preferably from 0.3 to 8.0% by mass, and more preferably from 1.0 to 6.0% by mass. And more preferably 1.2 to 4.8% by mass.
By setting the content of the component (B) in the aqueous composition within the above range, a coating film having more excellent appearance, weather resistance, stain resistance, sealing stain resistance, and biological stain resistance on a dark-colored substrate can be obtained. Obtainable.
The content of the component (B) in the coating film obtained from the aqueous composition of the present embodiment is preferably 50.0 to 95.0% by mass, more preferably 50.0 to 84.0% by mass. And more preferably 56.0 to 84.0% by mass.
By setting the content of the component (B) in the coating film within the above range, a coating film having further excellent appearance, weather resistance, stain resistance, sealing stain resistance, and biological stain resistance on a dark-colored substrate can be obtained. be able to.

<Inorganic oxide (C) having photocatalytic activity>
The aqueous composition of the present embodiment contains an inorganic oxide (C) having photocatalytic activity.
Thereby, the photocatalytic activity and hydrophilicity can be exhibited by irradiating the coating film with light.
In the present specification, the inorganic oxide (C) having photocatalytic activity may be simply referred to as the component (C).
The inorganic oxide having photocatalytic activity (C) may be any inorganic oxide having photocatalytic activity, and its type is not particularly limited.
The component (C) is not limited to the following, but 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 ; Ti, Nb, Ta, and Layered oxide having at least one element selected from the group consisting of V (for example, JP-A-62-074522, JP-A-02-172535, JP-A-07-024329, JP-A-08-089799). JP-A-08-089800, JP-A-08-089804, JP-A-09-248465, JP-A-10-099694, and JP-A-10-244165. Etc.) and the like.
The component (C) is preferably TiO ₂ (titanium oxide) from the viewpoints of chemical stability, toxicity, environmental aspects and the like. The titanium oxide may have any crystal structure of anatase type, rutile type, or brookite type.

The component (C) is an inorganic oxide having photocatalytic activity, and is preferably an inorganic oxide having photocatalytic activity whose particle surface has been modified.
By modifying the particle surface, the generation amount of active oxygen species such as H ₂ O ₂ and .OH can be suppressed, and the damage to the underlying coating film can be further suppressed.
The substance that modifies the particle surface is not limited to the following, but examples include silica, aluminum, copper oxide, and iron oxide. Among these, silica is preferred. The same effect can be obtained by modifying the particle surface with a metal such as Fe, Cu, Al or Pt, or a complex such as chloroplatinic acid.
The method of modifying the surface of the component (C) will be described by taking titanium oxide as an example.
The method for modifying the surface of the titanium oxide is not particularly limited, and includes, for example, a method of adding a silicon compound to a slurry of titanium oxide and precipitating a hydrated oxide of silicon through a step of neutralization and the like. Can be
The silicon compound is not particularly limited, and for example, a water-soluble alkali metal silicate such as sodium silicate can be used. Among these, sodium silicate is preferred from the viewpoint that it is colorless and the titanium oxide sol is not colored.
The modification treatment amount of the silicon hydrate with the hydrated oxide is preferably 3 to 25% by mass, more preferably 4 to 23% by mass, and still more preferably 5 to 20% by mass based on titanium oxide.
When the amount of the modification treatment is equal to or more than the lower limit, an increase in the amount of active oxygen species can be suppressed, so that damage to the underlying coating film can be prevented. When the amount of the modification treatment is equal to or less than the upper limit, the aggregation of titanium oxide is suppressed and the increase in the viscosity of the sol can be suppressed, so that the dispersibility and the transparency are further improved.

The component (C) is an inorganic oxide obtained by modifying the surface of a particle having photocatalytic activity, the inorganic oxide having a metal element such as gold, silver, copper, platinum or zinc supported on the inorganic oxide. Things can also be used.
The method for supporting the metal on the component (C) is not particularly limited. For example, a titanium oxide having a particle surface modified, and copper chloride dihydrate, silver nitrate, tetrachloroauric acid tetrahydrate, or the like may be used. Examples thereof include a method obtained by reacting with trisodium citrate dihydrate, tannic acid, or the like. The amount of metal carried is preferably 0.1 to 5% by mass, more preferably 0.1 to 4.8% by mass, and more preferably 0.1 to 4.6% by mass of titanium oxide based on titanium oxide. % Is more preferable.
When the loading amount is in the above range, sedimentation of the metal-supported titanium oxide can be suppressed, and a coating film having excellent resistance to biological contamination can be obtained.

The content of the component (C) in the aqueous composition of the present embodiment is usually 0.05 to 2.5% by mass, more preferably 0.10 to 2.0% by mass, and still more preferably 0 to 2.0% by mass. .15 to 1.4% by mass.
When the content of the component (C) is in the above range, a coating film having a more excellent appearance, weather resistance, stain resistance, sealing stain resistance, and biological stain resistance on a dark-colored substrate can be obtained.
The content of the component (C) in the coating film obtained from the aqueous composition of the present embodiment is not particularly limited, but is preferably 2.0 to 34.0% by mass, and more preferably 7.0 to 34% by mass. 0.0% by mass, more preferably 7.0 to 29.0% by mass.
When the content of the component (C) is in the above range, a coating film having a more excellent appearance, weather resistance, stain resistance, sealing stain resistance, and biological stain resistance on a dark-colored substrate can be obtained.

<Fluorocarbon surfactant (D)>
It is preferable that the aqueous composition of the present embodiment further contains a fluorocarbon surfactant (D).
In this specification, the fluorocarbon surfactant (D) may be simply described as the component (D).
By containing the component (D), the wettability to an organic substrate or the like when coating with the aqueous composition of the present embodiment or the aqueous paint containing the same is further improved, and the appearance such as repellency is improved. Trouble can be further suppressed. Further, the uniformity of the coating film is further improved. Although the reasons for these are not clear, it is presumed that the surface tension of the aqueous composition can be reduced by containing the component (D). The operation of the present embodiment is not limited to these.

The component (D) is not particularly limited, but is preferably an amphoteric surfactant.
The amphoteric surfactant is not particularly limited, and examples thereof include a nonionic amphoteric surfactant, an anionic amphoteric surfactant, a cationic amphoteric surfactant, and the like. Preferred specific examples include, for example, amphoteric surfactants having a perfluoroalkyl group having 3 to 20 carbon atoms.
Examples of the amphoteric surfactant having a perfluoroalkyl group having 3 to 20 carbon atoms include, but are not limited to, a perfluoroalkyl sulfonate, a perfluoroalkyl carboxylate, a perfluoroalkylamine oxide, a perfluoroalkyl Examples include ethylene oxide adducts and perfluoroalkyl compounds having an anionic group and a cationic group. Among these, a perfluoroalkylethylene oxide adduct and a perfluoroalkyl compound having an anionic group and a cationic group are preferable from the viewpoint of lowering the surface tension of the paint.
Examples of the perfluoroalkylsulfonic acid salt include, but are not limited to, ammonium salts and potassium salts of perfluorooctanesulfonic acid.
As the perfluoroalkyl carboxylate, for example, a commercially available product can be used.
Examples of such commercially available products include, but are not limited to, "Surflon S-211" manufactured by AGC Seimi Chemical Co., Ltd., and the like.
As the perfluoroalkylamine oxide, for example, a commercially available product can be used. Examples of such commercially available products include, but are not limited to, "Surflon S-241" manufactured by AGC Seimi Chemical Co., Ltd., and the like.
As the perfluoroalkylethylene oxide adduct, for example, a commercially available product can also be used. Examples of such commercially available products include, but are not limited to, "Megafac F-444" manufactured by DIC, "Surflon S-242" manufactured by AGC Seimi Chemical Co., Ltd., and the like.
As the perfluoroalkyl compound having an anionic group and a cationic group, for example, a commercially available product can be used. Examples of such commercially available products include, but are not limited to, “Surflon S-231”, “Surflon S-232”, and “Surflon S-233” manufactured by AGC Seimi Chemical Co., Ltd.
These may be used alone or in combination of two or more.

The content of the component (D) in the aqueous composition is not particularly limited, but is preferably 0.0001 to 0.50% by mass, more preferably 0.001 to 0.40% by mass, and still more preferably. Is 0.01 to 0.25% by mass.
When the content of the component (D) is in the above range, a coating film having a more excellent appearance, weather resistance, stain resistance, sealing stain resistance, and biological stain resistance on a dark-colored substrate can be obtained.
The content of the component (D) in the coating film obtained from the aqueous composition of the present embodiment is not particularly limited, but is preferably 0.002% by mass to 17.5% by mass, and more preferably 0.1% by mass. It is from 0.1% by mass to 10.0% by mass, more preferably from 0.15% by mass to 10.0% by mass. By setting the content of the component (D) in the above range, an aqueous composition having excellent wettability and spray suitability can be obtained, and appearance, weather resistance, stain resistance, and sealing stain on a dark-colored base material can be obtained. In addition, a coating film having more excellent biofouling resistance can be obtained.

<Fading dye (E)>
It is preferable that the aqueous composition of the present embodiment further contains a fading dye (E).
In the present specification, the bleaching dye (E) may be simply described as a component (E).
When the aqueous composition of the present embodiment contains the fading pigment (E), troubles such as forgetting to apply the coating, overlapping coating, and uneven coating can be prevented.
As the component (E), those which do not lose color by irradiation with sunlight and do not impair the design of the base are preferable. Although the time until the color loss varies depending on the season, the irradiation direction, and the like, usually, the period until the color loss is visually confirmed is preferably 20 days or less, more preferably 10 days or less, and still more preferably 3 days or less. Days or less.
The component (E) is not particularly limited as long as it has a property of being discolored by irradiation with sunlight. And one selected from the group consisting of Phloxine, Rose Bengal, Acid Red, and Fast Green FCF. Among these, methylene blue is preferred from the viewpoints of good color developability and high color loss rate.
These may be used alone or in combination of two or more.

The content of the component (E) in the aqueous composition of the present embodiment is not particularly limited, but is preferably 0.0005 to 0.04 mass%, more preferably 0.001 to 0.035 mass%. And more preferably 0.005 to 0.03% by mass. By setting the content of the component (E) in the aqueous composition within the above range, the coloring property and the fading property of the coating film are further improved. The term "color-forming property" as used herein refers to a property in which a painted surface and an unpainted surface are colored to such an extent that they can be visually distinguished from the difference in color. To do.
The content of the component (E) in the coating film obtained from the aqueous composition of the present embodiment is not particularly limited, but is preferably 0.01 to 1.0% by mass, and more preferably 0.05 to 0% by mass. 9.9% by mass, and more preferably 0.1 to 0.8% by mass. When the content of the component (E) is in the above range, a coating film having a more excellent appearance, weather resistance, stain resistance, sealing stain resistance, and biological stain resistance on a dark-colored substrate can be obtained.

The solid content (solid content) in the aqueous composition of the present embodiment is not particularly limited, but is preferably 0.5 to 10.0% by mass from the viewpoint of uniformity of the coating film, and more preferably. Is 1.0 to 8.0% by mass, more preferably 1.5 to 6.0% by mass.
By setting the content of the solid content in the aqueous composition to be equal to or more than the lower limit, the stain resistance is further improved. By setting the content of the solid content in the aqueous composition to the upper limit or less, the transparency is further improved.
The solid content here can be determined by the method described in Examples described later. Further, depending on the use of the coating film, the coating film may be required to be thin. Even in such a case, the solid content in the aqueous composition is equal to or less than the upper limit, and the physical properties such as weather resistance, stain resistance, sealing stain resistance, and biological stain resistance, even though the film thickness is small. It is possible to obtain an excellent coating film. When the amount of solids in the aqueous composition is equal to or more than the lower limit, the drying time required for forming a coating film can be reduced, and the working efficiency can be further improved.

(Water-based paint)
The water-based paint of the present embodiment contains the above-described water-based composition of the present embodiment.
The water-based paint of the present embodiment is obtained, for example, by mixing other components with the water-based composition described above as necessary.
Examples of the other components include, but are not limited to, an antifoaming agent, a freeze stabilizer, a matting agent, a crosslinking reaction catalyst, a pigment, a curing catalyst, a crosslinking agent, a filler, and an anti-skinning agent. , Dispersants, wetting agents, light stabilizers, antioxidants, UV absorbers, film-forming aids, rust inhibitors, plasticizers, thickeners, lubricants, reducing agents, preservatives, fungicides, and anti-algae Agents, deodorants, anti-yellowing agents, antistatic agents, charge control agents and the like.
These may be used alone or in combination of two or more.

Examples of the pigment include an inorganic oxide having no photocatalytic activity. Although not limited thereto, for example, copper (II) oxide (manufactured by CIK Nanotech, "CUAP15WT% -G180"), zinc oxide, aluminum oxide and the like are exemplified.
The content of the pigment in the coating film obtained from the water-based coating material of the present embodiment is not particularly limited, but is preferably 0.01 to 5.0% by mass, and more preferably 0.02 to 4.5% by mass. It is. When the content of the pigment is within the above range, a coating film having excellent appearance on a dark-colored substrate and excellent resistance to biological contamination can be obtained.

  The water-based paint of the present embodiment can be applied by a suitable method as appropriate according to its use and the material to be applied. Examples of the coating method include, but are not limited to, spraying, flow coating, roll coating, brush coating, dip coating, spin coating, screen printing, casting, and gravure printing. And flexographic printing.

(Coating)
The coating film of the present embodiment is obtained from the water-based paint of the present embodiment.
Specifically, it is obtained by applying the water-based paint to a predetermined application target and then drying it to remove volatile components. At this time, if necessary, a heat treatment at a temperature of about 40 to 120 ° C. or an ultraviolet irradiation treatment may be further performed.

[Painted products]
The coated product of the present embodiment includes a base material and the coating film formed on at least a part of the surface of the base material.
The coated product of the present embodiment is obtained, for example, by applying the above-described water-based paint to the surface of various substrates and drying.

The substrate used for the coated product of the present embodiment is not particularly limited as long as it can form a coating film on its surface, and may be any of an organic substrate and an inorganic substrate. From the viewpoint of improving the properties, an organic substrate is preferable.
Examples of the material of the base material include, but are not limited to, organic base materials such as synthetic resins and natural resins; and inorganic base materials such as metals, ceramics, glass, stone, cement, and concrete.
These may be used alone or in combination of two or more.

Examples of the synthetic resin include, but are not limited to, a thermoplastic resin and a curable resin (a thermosetting resin, a photocurable resin, a moisture-curable resin, and the like).
Examples of the synthetic resin include, but are not limited to, a silicone resin, an acrylic resin, a methacrylic resin, a fluororesin, an alkyd resin, an aminoalkyd resin, a vinyl resin, a polyester resin, a styrene-butadiene resin, a polyolefin resin, Polystyrene resin, polyketone resin, polyamide resin, polycarbonate resin, polyacetal resin, polyether ether ketone resin, polyphenylene oxide resin, polysulfone resin, polyphenylene sulfone resin, polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, urea resin, Phenol resins, melamine resins, epoxy resins, urethane resins, silicone-acrylic resins, and the like.
Examples of the natural resin include, but are not limited to, cellulosic resins, isoprene-based resins such as natural rubber, and protein-based resins such as casein.
When the substrate is a resin substrate using the above-described synthetic resin, natural resin, or the like, a surface treatment such as a corona discharge treatment, a flame treatment, and a plasma treatment may be performed as necessary.

The coated product of the present embodiment includes a base material and the coating film formed on the base material, and the coating film is also useful as a coating or the like.
The coating film obtained by the water-based paint of the present embodiment does not impair the appearance even with a dark-colored substrate, and can maintain a high level of appearance, antifouling property, sealing fouling property, and biofouling resistance for a long time. Can be suitably used in an environment where use was difficult.
From this point of view, the coating product of the present embodiment is not limited to the following, but includes, for example, building materials, building exteriors, building interiors, window frames, window glasses, various lenses, structural members, houses and other building equipment, Covers and window glasses for vehicle lighting, exteriors of machinery and articles, dustproof covers and coatings, display equipment, covers, traffic signs, various display devices, display materials such as advertising towers, sound insulation walls for roads, railways, etc. Exterior and coating of bridges and guardrails, interior and coating of tunnels, insulators, solar cell covers, solar water heater heat collector covers, and other external parts of electronic and electrical equipment, especially transparent members, greenhouses, greenhouses, etc. Is mentioned.

  As a method for manufacturing the coated product of the present embodiment, for example, at least a part of the surface of the base material is coated with the water-based paint of the present embodiment or the water-based composition of the present embodiment, and dried if necessary. Is carried out to form a coating film, but the method is not limited to this. For example, after applying the coating film of the present embodiment on a substrate, the coating film may be peeled from the substrate and adhered to another substrate. Alternatively, after the coating film of the present embodiment is applied on a substrate, it may be adhered to another substrate in a state of being in close contact with the substrate.

  The water-based composition of the present embodiment may be blended in various water-based paints. Such an aqueous paint can form a coating film having excellent appearance, stain resistance, sealing stain resistance, biological stain resistance, transparency, weather resistance, and the like. As described above, the coating film of the present embodiment is excellent in appearance, stain resistance, sealing stain resistance, and biological stain resistance, as well as excellent in transparency, weather resistance, and the like. Can be used for applications.

  Hereinafter, the present embodiment will be specifically described with reference to specific examples and comparative examples, but the present embodiment is not limited to the following examples.

A base material used for measurement of characteristics described below was produced as described below.
[Preparation of 7cm x 15cm base material pre-coated with enamel paint]
(Preparation of pigment dispersion)
5.35 g of dispersant (“Pig. Disperser MD20”, manufactured by BASF Japan), 0.5 g of aqueous ammonia, 23.5 g of propylene glycol, 147.5 g of water, titanium oxide (rutile titanium oxide by chlorine method; manufactured by Ishihara Sangyo Co., Ltd.) , "Taipaek CR-97") 333.5 g, an antifoaming agent (modified silicone type; manufactured by San Nopco, "SN Deformer 1310") 2.85 g of a blend, was mixed with a tabletop sand mill (Campe Papio, batch type tabletop sand mill). For 20 minutes to obtain a pigment dispersion.
(Preparation of enamel paint)
To 109.0 g of a polymer emulsion obtained in [Production Example 1] described later, 10.0 g of 2,2,4-trimethyl-1,3-butanediol isobutyrate ("CS-12", manufactured by Chisso Corporation) 10.0 g of a mixture of 50 parts by mass of ethylene glycol monobutyl ether and 50 parts by mass of water, 51.4 g of the pigment dispersion obtained as described above, a thickener ("ADEKANOL UH-438" manufactured by Asahi Denka Kogyo KK). )) And mixed for 1 hour to obtain an enamel paint X.
(Preparation of 7cm x 15cm base material pre-coated with enamel paint X)
The enamel paint X obtained as described above was coated on a 7 cm × 15 cm anodized sulfuric acid plate with a wire coater No. The enamel paint X was dried for 48 hours at a temperature of 23 ° C. and a relative humidity of 50% to obtain a base material of 7 cm × 15 cm to which an enamel paint X was previously applied.

Various physical properties were measured according to the following 1 to 3.
(1. Content and solid content of each component)
A 2.0 g sample was placed on an aluminum dish and heated at 150 ° C. for 1 hour. The mass of the sample before and after heating was measured, and the solid content (% by mass) was calculated from the difference. According to this method, the content of each component and the solid content in the aqueous composition were measured.

(2. Number average particle size)
Add ion-exchanged water and dilute so that the loading index becomes 1.5 to 3.0,
The number average particle diameter of the polymer in the aqueous dispersion was measured using a wet particle size analyzer (“Microtrack UPA-9230” manufactured by Nikkiso Co., Ltd.). The measurement conditions are shown below.
-Loading index: 1.5 to 3.0
-Measurement time: 60 seconds-Number of measurements: 3

(3. Glass transition temperature)
The measurement was performed using Seiko Instruments Inc. “DCS6220” under the measurement conditions of a heating rate of 10 ° C./min, and the glass transition temperature was determined from the inflection point of the obtained DSC curve. The measurement conditions are shown below.
-Measurement cell: aluminum container-Preparation of measurement sample: An aluminum container was charged with 40 mg of a polymer emulsion as a measurement sample, and dried at 130 ° C for 1 hour.

Various characteristics were measured by the following 4 to 8.
(4. Color difference before and after painting)
JIS K5600 paint general test method Spray so that the coating amount of the aqueous composition is 17.0 g / m ^{2 on} the black background (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.). And painted. The coated test paper was kept horizontal and left at 48 ° C. for 48 hours at a temperature of 23 ° C., a relative humidity of 50% and an illuminance of 20,000 lux to obtain a test plate. The color difference before and after the coating was measured using a “Color Guide” manufactured by BYK Gardner. If the color difference is 3.4 or less, it indicates that there is little change in the color difference on a dark-colored base and that the image is good.

(5. Weather resistance test: gloss retention after 3000 hours)
The enamel paint prepared as described above was applied to a 7 cm × 15 cm base material which had been coated in advance by using a spray so that the application amount of the aqueous composition was 17.0 g / m ² . The coated substrate was kept horizontal, left at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours to obtain a test plate. An exposure test (black panel temperature: 63 ° C., rainfall: 18 minutes / 2 hours) was performed using “Sunshine Weather Meter” manufactured by Suga Test Instruments. The gloss at 60 ° after 3000 hours of exposure was measured using a gloss meter (“Micro Trigloss μ” manufactured by BYK Gardner).
Then, the gloss retention was calculated based on the following equation. In addition, the result of evaluating only the base material which was previously coated with the enamel paint was a gloss retention of 80% after 3000 hours of exposure. Is shown.
Gloss retention (%) = 60 ° gloss after exposure test / 60 ° gloss before exposure test × 100

(6. Stain resistance)
The enamel paint prepared as described above was applied to a 7 cm × 15 cm base material which had been coated in advance by using a spray so that the application amount of the aqueous composition was 17.0 g / m ² . The coated substrate was kept horizontal, left at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours to obtain a test plate. The test plate was attached to a fence facing a general road (traffic volume of trucks: about 500 to 1000 vehicles / day) and allowed to stand for 6 months or 1 year.
The degree of contamination of the test plate after standing was visually evaluated based on the following criteria.
In addition, the result of evaluating only the base material which was previously coated with the enamel paint was "x" for 6 months and 1 year.
[Evaluation criteria]
：: Almost no dirt was observed.
Δ: Although some stains were confirmed, there was no practical problem.
X: A large amount of dirt was confirmed.

(7. Sealing contamination)
The enamel paint prepared as described above was applied to a 7 cm × 15 cm base material which had been coated in advance by using a spray so that the application amount of the aqueous composition was 17.0 g / m ² . The coated substrate was kept horizontal, left at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours to obtain a test plate. On a test plate, a one-component silicone-based sealing material, a silicone-based sealing material 8060 Pro (manufactured by Cemedine Co., Ltd.), is applied so that the size of the sealing material after drying is 1 cm × 2 cm and 1 cm in height, The sealant was dried for 10 days.
The test plate was attached to a fence facing a general road (traffic volume of trucks: about 500 to 1000 vehicles / day) and allowed to stand for a predetermined period.
The degree of contamination of the test plate after standing was measured by measuring the color difference (L value) before and after standing using a “color guide” manufactured by BYK Gardner.
The evaluation was based on the following criteria.
◎: Difference in L value after standing for 8 weeks is 2 or less, Difference in L value after standing for 12 weeks is 3 or less ○: Difference in L value after standing for 8 weeks is 2 or less, standing for 12 weeks And the difference of L value is more than 3 and 4 or less Δ: The difference of L value is 2 or less after standing for 8 weeks, the difference of L value is more than 4 after standing for 12 weeks ×: The L value is left after standing for 8 weeks Difference is more than 2

(8. Biological contamination resistance)
A 7 cm × 15 cm substrate previously coated with an enamel paint was applied using a spray so that the amount of the aqueous composition applied was 17.0 g / m ² . The coated substrate was kept horizontal, left at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours to obtain a test plate.
In Kasama City, Ibaraki Prefecture, attach the test plate to the fence facing the northern side of the building with trees surrounding it at an angle of 45 ° from the horizontal plane, and stick the painted surface upwards. The moon was left still.
The degree of contamination of the test plate after standing was visually evaluated based on the following criteria.
In addition, the result evaluated only by the base material previously coated with the enamel paint was evaluation of "x".
[Evaluation criteria]
：: Almost no algae or mold stains were observed.
Δ: Although some algal and mold stains were confirmed, there was no practical problem.
×: A large amount of algae and mold stains were observed.

In Production Example 1 below, the polymer emulsion for the enamel paint was produced.
[Production Example 1]
(Synthesis of polymer emulsion)
In a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device, 292.0 g of ion-exchanged water, a reactive emulsifier (Adekaria Soap SR-1025, manufactured by ADEKA; 25 mass% solid content aqueous solution) 8 Then, the reactor was heated to 80 ° C. while stirring. 10.0 g of a 2% by weight aqueous solution of ammonium persulfate was added to the reactor, and after 5 minutes, 10.0 g of methyl methacrylate, 5.0 g of cyclohexyl methacrylate, 75.0 g of n-butyl acrylate, 75.0 g of methacrylic acid 5.0 g, 2-hydroxyethyl methacrylate 10.0 g, reactive emulsifier (ADEKA Corp., "Adecaria Soap SR-1025"; solid content 25 mass% aqueous solution) 4.0 g, 2 mass% aqueous ammonium persulfate solution 15 0.0 g and 49.0 g of ion-exchanged water were added dropwise over 60 minutes 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 60 minutes.
Next, 70.0 g of methyl methacrylate, 90.0 g of cyclohexyl methacrylate, 232.0 g of n-butyl acrylate, 8.0 g of methacrylic acid, a reactive emulsifier (“ADEKAREASORP SR-1025” manufactured by ADEKA; solid) 16.0 g of a 25 mass% aqueous solution), 60.0 g of a 2 mass% aqueous solution of ammonium persulfate, 196.0 g of ion-exchanged water, 1.0 g of 3-methacryloxypropyltrimethoxysilane, 20 g of dimethyldimethoxysilane And a mixed solution consisting of 0.0 g of methyltrimethoxysilane and 20.0 g of methyltrimethoxysilane was added dropwise from separate dropping tanks over 160 minutes. 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 solution in the reactor was measured and found to be pH 2.2. After adjusting the pH to 8.0 by adding a 25% by mass aqueous ammonia solution to the reaction solution, the reaction solution was filtered through a 100-mesh wire net to obtain the above-described polymer emulsion for enamel coating.
The solid content of the obtained polymer emulsion was 44.5% by mass. The glass transition temperature of the polymer contained in this polymer emulsion determined from the inflection point of the DSC curve according to the method described above was -5 ° C.

In the following Production Examples 2 to 8, polymer aqueous dispersions were produced.
[Production Example 2]
(Synthesis of Aqueous Dispersion of Polymer (A-1) (AD-1))
In a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirrer, 1364.2 g of ion-exchanged water, a reactive emulsifier (“ADEKAREASORP SR-1025” manufactured by ADEKA; aqueous solution with a solid content of 25% by mass) 28 Then, the reactor was heated to 80 ° C. while stirring. 10.0 g of a 2% by weight aqueous solution of ammonium persulfate was added to the reactor, and 5 minutes later, 40.0 g of methyl methacrylate, 36.0 g of n-butyl acrylate, 4.0 g of acrylic acid, and a reactive emulsifier (Adekaria Soap SR-1025, manufactured by ADEKA; solid content 25% by weight aqueous solution) 3.2 g of an emulsified mixed solution consisting of 2% by weight of an aqueous solution of ammonium persulfate 12.0 g and 34.8 g of ion-exchanged water were reacted. The solution was added dropwise over 60 minutes while keeping the temperature in the vessel at 80 ° C. Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 60 minutes.
Next, 250.0 g of methyl methacrylate, 66.0 g of n-butyl acrylate, 4.0 g of acrylic acid, and a reactive emulsifier (Adeka Soap SR-1025, manufactured by ADEKA; aqueous solution with a solid content of 25% by mass) 12 An emulsified mixed solution consisting of 8.8 g, 48.0 g of a 2 mass% aqueous solution of ammonium persulfate, and 149.2 g of ion-exchanged water was dropped from the dropping tank over 160 minutes. Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 120 minutes.
After cooling to room temperature, a 25% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0. The total solid content was 412.6 g. The reaction solution was filtered through a 100-mesh wire net. The reaction product was adjusted to a solid content of 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion (AD-1) of a polymer (A-1) having a number average particle diameter of 30 nm as a polymer.

[Production Example 3]
(Synthesis of Aqueous Dispersion of Polymer (A-2) (AD-2))
In a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirrer, 1364.2 g of ion-exchanged water, a reactive emulsifier (“ADEKAREASORP SR-1025” manufactured by ADEKA; aqueous solution with a solid content of 25% by mass) 28 Then, the reactor was heated to 80 ° C. while stirring. 10.0 g of a 2% by weight aqueous solution of ammonium persulfate was added to the reactor, and 5 minutes later, 40.0 g of methyl methacrylate, 36.0 g of n-butyl acrylate, 4.0 g of acrylic acid, and a reactive emulsifier (Adekaria Soap SR-1025, manufactured by ADEKA; solid content 25% by weight aqueous solution) 3.2 g of an emulsified mixed solution consisting of 2% by weight of an aqueous solution of ammonium persulfate 12.0 g and 34.8 g of ion-exchanged water were reacted. The solution was added dropwise over 60 minutes while keeping the temperature in the vessel at 80 ° C. Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 60 minutes.
Next, 250.0 g of methyl methacrylate, 66.0 g of n-butyl acrylate, 4.0 g of acrylic acid, and a reactive emulsifier (Adeka Soap SR-1025, manufactured by ADEKA; aqueous solution with a solid content of 25% by mass) 12 2.8 g, an emulsified mixed solution consisting of 48.0 g of a 2% by mass aqueous solution of ammonium persulfate and 149.2 g of ion-exchanged water, 2.0 g of 3-methacryloxypropyltrimethoxysilane, 20.0 g of dimethyldimethoxysilane, and methyltrimethoxysilane A mixed solution consisting of 20.0 g was dropped from a separate dropping tank over 160 minutes. Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 120 minutes.
After cooling to room temperature, a 25% by mass aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0. The total solid content was 436.2 g. The reaction solution was filtered through a 100-mesh wire net. The reaction product was adjusted to a solid content of 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion (AD-2) of a polymer (A-2) having a number average particle diameter of 30 nm as a polymer.
The amount of dimethyldimethoxysilane used in synthesizing the aqueous dispersion was 2.8% by mass in the polymer (A-2) in terms of hydrolysis and condensation.

[Production Example 4]
(Synthesis of Aqueous Dispersion of Polymer (A-3) (AD-3))
After 850.0 g of ion-exchanged water and 40.0 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid were put into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device, the temperature in the reactor was stirred. Was warmed to 80 ° C. Into this reactor, a mixed solution composed of 85.5 g of dimethyldimethoxysilane and 193.0 g of methyltrimethoxysilane was added dropwise over 120 minutes 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 adding 14.8 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid, stirring was continued for 120 minutes while maintaining the temperature in the reactor at 80 ° C. After charging 6.6 g of a 2% by mass aqueous solution of ammonium persulfate, 22.5 g of methyl methacrylate, 11.2 g of n-butyl acrylate, 20.0 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, 3 -A mixture of 1.1 g of methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, 1.2 g of a reactive emulsifier ("ADEKAREASORP SR-1025" manufactured by ADEKA; aqueous solution with a solid content of 25% by mass); A mixed liquid comprising 1.2 g of a reactive emulsifier (“AQUALON KH-1025” manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; aqueous solution of 25% by mass solid content), 30.0 g of a 2% by mass aqueous solution of ammonium persulfate, and 286.4 g of ion-exchanged water Were simultaneously added dropwise over 120 minutes while maintaining the temperature in the reactor at 80 ° C.
Furthermore, after stirring was continued for 60 minutes while maintaining the temperature in the reactor at 80 ° C., the reactor was cooled to room temperature, and a 25 mass% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0. The total solid content was 210.0 g. The reaction solution was filtered through a 100-mesh wire net. The reaction product was adjusted to a solid content of 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion (AD-3) of a polymer (A-3) having a number average particle diameter of 15 nm as a polymer.
When the amount of dimethyldimethoxysilane used in synthesizing the aqueous dispersion was converted to a hydrolyzed condensate, it was 25.0% by mass in the polymer (A-3).

[Production Example 5]
(Synthesis of Aqueous Dispersion of Polymer (A-4) (AD-4))
After 850.0 g of ion-exchanged water and 40.0 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid were put into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device, the temperature in the reactor was stirred. Was warmed to 80 ° C. Into this reactor, a mixed solution consisting of 109.0 g of dimethyldimethoxysilane, 29.5 g of phenyltrimethoxysilane, and 136.5 g of methyltrimethoxysilane was added for 120 minutes while maintaining the temperature in the reactor at 80 ° C. And dropped.
Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 30 minutes.
Next, after adding 14.8 g of a 10.0% by mass aqueous solution of dodecylbenzenesulfonic acid, stirring was continued for 120 minutes while maintaining the temperature in the reactor at 80 ° C. After charging 6.6 g of a 2% by mass aqueous solution of ammonium persulfate, 1.0 g of methyl methacrylate, 1.0 g of n-butyl acrylate, 29.5 g of phenyltrimethoxysilane, 27.8 g of tetraethoxysilane, 3 g -A mixed solution consisting of 1.1 g of methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, 4.5 g of a reactive emulsifier ("ADEKAREASORP SR-1025" manufactured by ADEKA; aqueous solution with a solid content of 25% by mass); 2.3 g of a reactive emulsifier (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "Aqualon KH-1025"; aqueous solution of 25% by mass of solid content); Were simultaneously added dropwise over 120 minutes while maintaining the temperature in the reactor at 80 ° C.
Furthermore, after stirring was continued for 60 minutes while maintaining the temperature in the reactor at 80 ° C., the reactor was cooled to room temperature, and a 25 mass% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0. The total solid content was 192.4 g. The reaction solution was filtered through a 100-mesh wire net. The reaction product was adjusted to a solid content of 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion (AD-4) of a polymer (A-4) having a number average particle diameter of 20 nm as a polymer.
When the amount of dimethyldimethoxysilane used in synthesizing the aqueous dispersion was converted to a hydrolyzed condensate, it was 35.0% by mass in the polymer (A-4).

[Production Example 6]
(Synthesis of Aqueous Dispersion (AD-5) of Polymer (A-5))
After 1000.0 g of ion-exchanged water and 40.0 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid were charged into a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device, the temperature in the reactor was stirred. Was warmed to 80 ° C. Into this reactor, a mixed solution consisting of 220.0 g of dimethyldimethoxysilane, 5.0 g of phenyltrimethoxysilane, and 106.0 g of methyltrimethoxysilane was applied for 120 minutes while maintaining the temperature in the reactor at 80 ° C. And dropped.
Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 30 minutes.
Next, after adding 14.8 g of a 10.0% by mass aqueous solution of dodecylbenzenesulfonic acid, stirring was continued for 120 minutes while maintaining the temperature in the reactor at 80 ° C. After charging 6.6 g of a 2% by mass aqueous solution of ammonium persulfate, 1.0 g of methyl methacrylate, 1.0 g of n-butyl acrylate, 5.0 g of phenyltrimethoxysilane, 10.0 g of tetraethoxysilane, 3 g of -A mixed solution consisting of 1.1 g of methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, 4.5 g of a reactive emulsifier ("ADEKAREASORP SR-1025" manufactured by ADEKA; aqueous solution with a solid content of 25% by mass); 2.3 g of a reactive emulsifier (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "Aqualon KH-1025"; aqueous solution of 25% by mass of solid content); Were simultaneously added dropwise over 120 minutes while maintaining the temperature in the reactor at 80 ° C.
Furthermore, after stirring was continued for 60 minutes while maintaining the temperature in the reactor at 80 ° C., the reactor was cooled to room temperature, and a 25 mass% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0. The total solid content was 208.9 g. The reaction solution was filtered through a 100-mesh wire net. The reaction product was adjusted to a solid content of 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion (AD-5) of a polymer (A-5) having a number average particle diameter of 35 nm as a polymer.
When the amount of dimethyldimethoxysilane used in synthesizing the aqueous dispersion was converted to a hydrolyzed condensate, it was 65.0% by mass in the polymer (A-5).

[Production Example 7]
(Synthesis of Aqueous Dispersion (A′D-6) of Polymer (A′-6))
In a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirrer, 335.8 g of ion-exchanged water, a reactive emulsifier (Adekaria Soap SR-1025, manufactured by ADEKA; aqueous solution with a solid content of 25% by mass) 19 Then, the reactor was heated to 80 ° C. while stirring. 10.0 g of a 2% by weight aqueous solution of ammonium persulfate was added to the reactor, and 5 minutes later, 40.0 g of methyl methacrylate, 36.0 g of n-butyl acrylate, 4.0 g of acrylic acid, and a reactive emulsifier (Adekaria Soap SR-1025, manufactured by ADEKA; solid content 25% by weight aqueous solution) 3.2 g of an emulsified mixed solution consisting of 2% by weight of an aqueous solution of ammonium persulfate 12.0 g and 34.8 g of ion-exchanged water were reacted. The solution was added dropwise over 60 minutes while keeping the temperature in the vessel at 80 ° C.
Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 60 minutes.
Next, 250.0 g of methyl methacrylate, 66.0 g of n-butyl acrylate, 4.0 g of acrylic acid, and a reactive emulsifier (Adeka Soap SR-1025, manufactured by ADEKA; aqueous solution with a solid content of 25% by mass) 12 An emulsified mixed solution consisting of 8.8 g, 48.0 g of a 2 mass% aqueous solution of ammonium persulfate, and 149.2 g of ion-exchanged water was dropped from the dropping tank over 160 minutes.
Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 120 minutes. After cooling to room temperature, a 25% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0. The total solid content was 410.2 g. The reaction solution was filtered through a 100-mesh wire net. The reaction product was adjusted to a solid content of 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion (A'D-6) of a polymer (A'-6) having a number average particle diameter of 60 nm as a polymer. .

[Production Example 8]
(Synthesis of Aqueous Dispersion (A′D-7) of Polymer (A′-7))
In a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirrer, 241.8 g of ion-exchanged water, a reactive emulsifier (“ADEKAREASORP SR-1025”, manufactured by ADEKA; aqueous solution with a solid content of 25% by mass) 3 Then, the reactor was heated to 80 ° C. while stirring. 10.0 g of a 2% by weight aqueous solution of ammonium persulfate was added to the reactor, and 5 minutes later, 40.0 g of methyl methacrylate, 36.0 g of n-butyl acrylate, 4.0 g of acrylic acid, and a reactive emulsifier (Adekaria Soap SR-1025, manufactured by ADEKA; solid content 25% by weight aqueous solution) 3.2 g of an emulsified mixed solution consisting of 2% by weight of an aqueous solution of ammonium persulfate 12.0 g and 34.8 g of ion-exchanged water were reacted. The solution was added dropwise over 60 minutes while keeping the temperature in the vessel at 80 ° C.
Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 60 minutes.
Next, 250.0 g of methyl methacrylate, 66.0 g of n-butyl acrylate, 4.0 g of acrylic acid, and a reactive emulsifier (Adeka Soap SR-1025, manufactured by ADEKA; aqueous solution with a solid content of 25% by mass) 12 2.8 g, an emulsified mixed solution consisting of 48.0 g of a 2% by mass aqueous solution of ammonium persulfate and 149.2 g of ion-exchanged water, 2.0 g of 3-methacryloxypropyltrimethoxysilane, 20.0 g of dimethyldimethoxysilane, and methyltrimethoxysilane A mixed solution consisting of 20.0 g was dropped from a separate dropping tank over 160 minutes.
Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 120 minutes. After cooling to room temperature, a 25% by mass aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0. The total solid content was 431.6 g. The reaction solution was filtered through a 100-mesh wire net. The reaction product was adjusted to a solid content of 10.0% by mass with ion exchanged water to obtain an aqueous dispersion (A'D-7) of a polymer (A'-7) having a number average particle diameter of 120 nm as a polymer. .
The amount of dimethyldimethoxysilane used in synthesizing the aqueous dispersion was 2.8% by mass in the polymer (A'-7) in terms of hydrolysis and condensation.

In the following Production Examples 9 to 15, inorganic oxides having photocatalytic activity were produced.
[Production Example 9]
(Synthesis of inorganic oxide (C-1) having photocatalytic activity)
<Silica-modified rutile-type titanium oxide>
700 mL of an aqueous solution of titanium tetrachloride having a concentration of 200 g / L as TiO ₂ and an aqueous solution of sodium hydroxide having a concentration of 100 g / L as Na ₂ O were added to the reactor while maintaining the pH of the reaction solution at 5 to 9. . Thereafter, the pH of the reaction solution was adjusted to 7, followed by filtration and washing until the conductivity of the filtrate became 100 μS / cm, to obtain a wet titanium oxide cake 1 having a solid content of 28.3% by mass. This titanium oxide wet cake 1 contained fine particles having a rutile structure, and the number average particle diameter of the primary particles was 8 nm.
The obtained titanium oxide wet cake 1 was diluted with pure water to prepare a 1 mol / L slurry.
1 L of this slurry is charged into a 3 L flask, 1N nitric acid is further added so that the molar ratio of titanium oxide / nitric acid becomes 1/1, heated to a temperature of 95 ° C., and maintained at this temperature for 2 hours. Then, an acid heat treatment was performed. The slurry after the acid heat treatment was cooled to room temperature, neutralized to pH 6.7 with 28% aqueous ammonia, and filtered. Thereafter, the filtrate was washed until the conductivity of the filtrate became 100 μS / cm to obtain a titanium oxide wet cake 2 having a solid content of 25% by mass.
To the obtained titanium oxide wet cake 2, an aqueous solution of sodium hydroxide having a concentration of 10% by mass was added and repulped. Thereafter, the mixture was dispersed with an ultrasonic cleaner for 3 hours to obtain a pH of 10.5 and a solid content of 10% by mass. An alkaline titanium oxide sol was obtained.
2 L of this alkaline titanium oxide sol is charged into a 3 L flask, and the flask is heated to a temperature of 70 ° C., 69.4 mL of an aqueous solution of sodium silicate having a concentration of 432 g / L as SiO ₂ is added, and then heated to 90 ° C. After heating and maintaining for 1 hour, the pH was adjusted to 6 by adding 10% sulfuric acid to obtain a titanium oxide sol in which the surface of titanium oxide was surface-treated with a hydrated oxide of silicon.
The obtained titanium oxide sol was cooled to room temperature, 5.4 L of pure water was added, impurities were removed and concentrated using a desalting / concentrating device, pH 7.3, solid content 29% by mass, conductivity 1.18 mS / cm neutral rutile type titanium oxide sol was obtained.
This neutral rutile-type titanium oxide sol contained 15% by mass, based on SiO ₂ , of hydrated silicon oxide with respect to TiO ₂ . The number average particle diameter of the primary particles of titanium oxide in this sol was 9 nm.

[Production Example 10]
(Synthesis of inorganic oxide (C-2) having photocatalytic activity)
<Silica-modified anatase-type titanium oxide>
Agglomerated metatitanic acid produced by heating and hydrolyzing a titanium sulfate solution obtained by reacting titanium ore with sulfuric acid was converted to an aqueous slurry of 30% by mass in terms of TiO ₂ . Ammonia water was added to the slurry to neutralize to pH 7, and then sulfate and ions were removed by filtration and washing to obtain a dehydrated cake.
The obtained dehydrated cake was peptized by adding nitric acid to obtain an acidic titanium oxide sol having a pH of 1.5 and comprising titanium oxide fine particles having an anatase crystal structure (number average particle diameter of primary particles: 7 nm).
The obtained acidic titanium oxide sol was diluted with pure water to obtain 600 mL of titanium oxide sol having a concentration of 200 g / L in terms of TiO ₂ , then heated to 70 ° C., and sodium silicate having a concentration of 432 g / L in terms of SiO _2. 20.8 mL of the aqueous solution was added to the reactor simultaneously with the 20% sulfuric acid. Thereafter, it was aged for 30 minutes.
Then, the pH of the reaction solution was adjusted to 8 by adding a 10% aqueous sodium hydroxide solution, and then the pH of the reaction solution was adjusted to 6 with a 2% aqueous sulfuric acid solution. Obtained.
The wet cake was repulped in pure water and then dispersed by ultrasonic waves to obtain an anatase-type titanium oxide sol (solid content: 20% by mass, pH 7.5) stable in a neutral region.
In this method, aggregated silica was adhered in a porous state on the surface of the titanium oxide fine particles, and the content was 7 parts by mass in terms of SiO _{2 with} respect to 100 parts by mass of TiO ₂ .

[Production Example 11]
(Synthesis of inorganic oxide (C-3) having photocatalytic activity)
<Copper-supported silica-modified rutile-type titanium oxide>
386.4 g of ion-exchanged water and 13.6 g of silica-coated titanium oxide were charged into a reactor having a reflux condenser, a thermometer and a stirrer, and the temperature in the reactor was heated to 80 ° C. with stirring.
Into this reactor, 0.3 g of copper chloride dihydrate and 4.0 g of ion-exchanged water were added, and 0.3 g of trisodium citrate dihydrate, 0.1 g of tannic acid and 13.2 g of ion-exchanged water were further added. 2 g were charged. The reactor temperature was maintained at 80 ° C. and stirring was continued for 60 minutes.
After cooling to room temperature, the mixture was filtered through a nylon mesh having a mesh size of 74 μm to obtain copper-supported silica-modified titanium oxide. The solid content of the copper-supported silica-modified titanium oxide was 2.0%, and the pH was 5.3.

[Production Example 12]
(Synthesis of inorganic oxide (C-4) having photocatalytic activity)
<Silver-supported silica-modified rutile-type titanium oxide>
386.4 g of ion-exchanged water and 13.6 g of inorganic oxide (C-1) were charged into a reactor having a reflux condenser, a thermometer and a stirrer, and the temperature in the reactor was increased to 80 ° C. with stirring. Warmed. Into this reactor, 0.1 g of silver nitrate and 2.4 g of ion-exchanged water, and 0.2 g of trisodium citrate dihydrate, 0.1 g of tannic acid and 7.8 g of ion-exchanged water were further charged.
The reactor temperature was maintained at 80 ° C. and stirring was continued for 60 minutes.
After cooling to room temperature, the mixture was filtered through a nylon mesh having a mesh size of 74 μm to obtain silver-supported silica-modified titanium oxide. The solid content of this silver-supported silica-modified titanium oxide was 2.0%, and the pH was 6.9.

[Production Example 13]
(Synthesis of inorganic oxide (C-5) having photocatalytic activity)
<Gold-supported silica-modified rutile-type titanium oxide>
386.4 g of ion-exchanged water and 13.6 g of inorganic oxide (C-1) were charged into a reactor having a reflux condenser, a thermometer and a stirrer, and the temperature in the reactor was increased to 80 ° C. with stirring. Warmed. Into this reactor, 0.1 g of tetrachloroauric acid tetrahydrate and 3.8 g of ion-exchanged water, and 0.01 g of tannic acid and 1.2 g of ion-exchanged water were further charged.
The reactor temperature was maintained at 80 ° C. and stirring was continued for 60 minutes.
After cooling to room temperature, the mixture was filtered through a nylon mesh having a mesh size of 74 μm to obtain gold-supported silica-modified titanium oxide. The solid content of this gold-supported silica-modified titanium oxide was 2.0%, and the pH was 7.2.

[Production Example 14]
(Synthesis of inorganic oxide (C-6) having photocatalytic activity)
<Silver-modified silica-supported rutile-type titanium oxide>
386.4 g of ion-exchanged water and 13.6 g of inorganic oxide (C-1) were charged into a reactor having a reflux condenser, a thermometer and a stirrer, and the temperature in the reactor was increased to 80 ° C. with stirring. Warmed. 0.1 g of silver nitrate and 2.4 g of ion-exchanged water were charged into this reactor, and 0.1 g of trisodium citrate dihydrate, 0.1 g of tannic acid and 7.1 g of ion-exchanged water were further charged. Stirring was continued for 45 minutes while maintaining the temperature of the reactor at 80 ° C. Next, 0.02 g of tannic acid and 1.6 g of ion-exchanged water were charged, and 0.1 g of copper chloride dihydrate and 2.0 g of ion-exchanged water were charged.
Stirring was continued for 45 minutes while maintaining the temperature of the reactor at 80 ° C.
After cooling to room temperature, the mixture was filtered through a nylon mesh having a mesh size of 74 μm to obtain silver- and copper-supported silica-modified titanium oxide. The solid content of the silver-copper-supported silica-coated titanium oxide was 2.0%, and the pH was 5.7.

[Production Example 15]
(Synthesis of inorganic oxide (C-7) having photocatalytic activity)
<Silver-gold-supported silica-modified rutile-type titanium oxide>
386.4 g of ion-exchanged water and 13.6 g of inorganic oxide (C-1) were charged into a reactor having a reflux condenser, a thermometer and a stirrer, and the temperature in the reactor was increased to 80 ° C. with stirring. Warmed. 0.1 g of silver nitrate and 2.4 g of ion-exchanged water were charged into the reactor, and 0.1 g of trisodium citrate dihydrate, 0.1 g of tannic acid and 6.9 g of ion-exchanged water were further charged.
Stirring was continued for 45 minutes while maintaining the temperature of the reactor at 80 ° C.
Next, 0.1 g of tetrachloroauric acid tetrahydrate and 3.8 g of ion-exchanged water were added. Stirring was continued for 45 minutes while maintaining the temperature of the reactor at 80 ° C.
After cooling to room temperature, the mixture was filtered through a nylon mesh having a mesh size of 74 μm to obtain silica-modified titanium oxide carrying silver and gold. The solid content of the silver-gold-supported silica-modified titanium oxide was 2.0%, and the pH was 6.5.

[Example 1]
5.5 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-1) of the polymer (A-1) was added to water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Industries, Ltd.) 12.9 g of “Snowtex OS”; solid content 20% by mass); 2.3 g of inorganic oxide (C-1) having photocatalytic activity (solid content 29% by mass); 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass, 10.0 g of ethanol, and 68.0 g of ion-exchanged water were mixed and stirred. As a result, an aqueous composition (F-1) having a solid content of 4.0% by mass was obtained.
Next, on a black background portion (L * value 7) of an opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material previously coated with an enamel paint (a surface previously coated with an enamel paint), The aqueous composition (F-1) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-1) having a coated film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-1) having a coating film formed on a substrate.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-1), the coating film and the test paper (G-1), and the coating film and the test plate (H-1).

[Example 2]
To 4.7 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-2) of the polymer (A-2), water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (Nissan Chemical Industries, Ltd.) (Snowtex OS; solid content 20% by mass), 13.7 g, 2.4 g (29 mass% solid content) of inorganic oxide (C-1) having photocatalytic activity, and solid content 10. 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass, 10.0 g of ethanol, and 68.2 g of ion-exchanged water were mixed and stirred. As a result, an aqueous composition (F-2) having a solid content of 4.0% by mass was obtained.
Next, a water-based material was applied to the black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side of a 7 cm × 15 cm base material previously coated with the enamel paint (the surface previously coated with the enamel paint). The composition (F-2) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-2) having a coated film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-2) having a coating film formed on a substrate.
Table 1 shows various physical properties and characteristics evaluation results of the aqueous composition (F-2), the coating film and the test paper (G-2), and the coating film and the test plate (H-2).

[Example 3]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm was added to 3.9 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-3) of the polymer (A-3) (Nissan Chemical Industries, Ltd.) 14.0 g of "Snowtex OS"; solid content of 20% by mass; 2.4 g of inorganic oxide (C-1) having photocatalytic activity (29% by mass of solid content); 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "MegaFac F-444") adjusted to 0% by mass, 10.0 g of ethanol, and 68.6 g of ion-exchanged water are mixed and stirred. Thereby, an aqueous composition (F-3) having a solid content of 4.0% by mass was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-3) was applied using a spray such that the coating amount was 17 g / m ² .
A test paper (G-3) having a coating film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-3) having a coating film formed on a substrate.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-3), the coating film and the test paper (G-3), and the coating film and the test plate (H-3).

[Example 4]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm was added to 1.5 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industries, Ltd.) 16.0 g of "Snowtex OS"; solid content of 20 mass%), 1.9 g of inorganic oxide (C-1) having photocatalytic activity (solid content of 29 mass%), and solid content of 10.10 g with ethanol. 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass, 10.0 g of ethanol, and 69.6 g of ion-exchanged water are mixed and stirred. Thereby, an aqueous composition (F-4) having a solid content of 4.0% by mass was obtained.
Next, a water-based material was applied to the black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side of a 7 cm × 15 cm base material previously coated with the enamel paint (the surface previously coated with the enamel paint). The composition (F-4) was applied using a spray so as to give a coating amount of 17 g / m ² .
A test paper (G-4) in which a coated film was formed on a black background portion of an opacity test paper while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-4) having a coating film formed on a substrate.
Table 1 shows the physical properties and characteristic evaluation results of the aqueous composition (F-4), the coating film and the test paper (G-4), and the coating film and the test plate (H-4).

[Example 5]
Aqueous dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm was added to 5.6 g (solid content: 10.0 mass%) of an aqueous dispersion (AD-4) of polymer (A-4) (Nissan Chemical Industries, Ltd.) (Snowtex OS; solid content 20% by mass), 11.6 g, inorganic oxide (C-1) having photocatalytic activity 3.5 g (solid content 29% by mass), and ethanol with a solid content of 10. 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass, 10.0 g of ethanol, and 68.3 g of ion-exchanged water are mixed and stirred. Thereby, an aqueous composition (F-5) having a solid content of 4.0% by mass was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-5) was applied using a spray such that the coating amount was 17 g / m ² .
A test paper (G-5) in which a coated film was formed on a black background portion of an opacity test paper while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-5) having a coating film formed on a substrate.
Table 1 shows the physical properties and characteristic evaluation results of the aqueous composition (F-5), the coating film and the test paper (G-5), and the coating film and the test plate (H-5).

[Example 6]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm was added to 1.8 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-5) of the polymer (A-5) (Nissan Chemical Industries, Ltd.) 17.0 g of “Snowtex OS”; solid content 20% by mass); 1.1 g of inorganic oxide (C-1) having photocatalytic activity (solid content 29% by mass); 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass, 10.0 g of ethanol, and 69.1 g of ion-exchanged water are mixed and stirred. Thereby, an aqueous composition (F-6) having a solid content of 4.0% by mass was obtained.
Next, a water-based material was applied to the black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side of a 7 cm × 15 cm base material previously coated with the enamel paint (the surface previously coated with the enamel paint). The composition (F-6) was applied using a spray such that the coating amount was 17 g / m ² .
A test paper (G-6) in which a coated film was formed on a black background portion of an opacity test paper while keeping the coated substrate horizontal and allowing it to stand for 48 hours at a temperature of 23 ° C., a relative humidity of 50% and an illuminance of 20,000 lux. And a test plate (H-6) having a coating film formed on a substrate.
Table 1 shows the physical properties and characteristic evaluation results of the aqueous composition (F-6), the coating film and the test paper (G-6), and the coating film and the test plate (H-6).

[Example 7]
5.3 g (solid content: 10.0 mass%) of an aqueous dispersion (AD-5) of the polymer (A-5) was added to an aqueous dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Industries, Ltd.) (Snowtex OS); 11.1 g of solid content: 20 mass%); 3.9 g of inorganic oxide (C-1) having photocatalytic activity (29 mass% of solid content); 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "MegaFac F-444") adjusted to 0% by mass, 10.0 g of ethanol, and 68.6 g of ion-exchanged water are mixed and stirred. Thereby, an aqueous composition (F-7) having a solid content of 4.0% by mass was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-7) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-7) having a coating film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-7) having a coating film formed on a substrate.
Table 1 shows the physical properties and characteristic evaluation results of the aqueous composition (F-7), the coating film and the test paper (G-7), and the coating film and the test plate (H-7).

Example 8
Water-dispersed colloidal silica (B-3) having a number average particle size of 25 nm (B-3) was added to 1.2 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-5) of the polymer (A-5) (Nissan Chemical Industries, Ltd.) 6.1 g of an inorganic oxide (C-1) having photocatalytic activity (solid content of 29 mass%) and ethanol, and the solid content was adjusted with ethanol. 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "MegaFac F-444") adjusted to 10.0% by mass, 10.0 g of ethanol, and 77.1 g of ion-exchanged water were mixed. By stirring, an aqueous composition (F-8) having a solid content of 4.0% by mass was obtained.
Next, a water-based material was applied to the black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side of a 7 cm × 15 cm base material previously coated with the enamel paint (the surface previously coated with the enamel paint). The composition (F-8) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-8) in which a coated film was formed on a black background portion of an opacity test paper while the coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. Then, a test plate (H-8) having a coating film formed on a substrate was obtained.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-8), the coating film and the test paper (G-8), and the coating film and the test plate (H-8).

[Example 9]
A water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm was added to 5.9 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-5) of the polymer (A-5) (Nissan Chemical Industries, Ltd.) 13.5 g of "Snowtex OS"; solid content of 20 mass%); 2.2 g of inorganic oxide (C-1) having photocatalytic activity (solid content of 29 mass%); 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass, 10.0 g of ethanol, and 67.5 g of ion-exchanged water are mixed and stirred. Thereby, an aqueous composition (F-9) having a solid content of 4.0% by mass was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-9) was applied using a spray such that the coating amount was 17 g / m ² .
Test paper (G-9) having a coated film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-9) having a coating film formed on a substrate.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-9), the coating film and the test paper (G-9), and the coating film and the test plate (H-9).

[Example 10]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm was added to 3.9 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-5) of the polymer (A-5) (Nissan Chemical Industries, Ltd.) 11.5 g of "Snowtex OS"; solid content 20% by mass); 4.2 g of inorganic oxide (C-1) having photocatalytic activity (solid content 29% by mass); 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass, 10.0 g of ethanol, and 69.4 g of ion-exchanged water are mixed and stirred. Thereby, an aqueous composition (F-10) having a solid content of 4.0% by mass was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-10) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-10) having a coated film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-10) having a coating film formed on a substrate.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-10), the coating film and the test paper (G-10), and the coating film and the test plate (H-10).

[Example 11]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm was added to 3.5 g (solid content: 10.0 mass%) of an aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industries, Ltd.) 16.6 g of "Snowtex OS"; solid content of 20 mass%); 0.8 g of inorganic oxide (C-1) having photocatalytic activity (solid content of 29 mass%); 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "MegaFac F-444") adjusted to 0% by mass, 10.0 g of ethanol, and 68.1 g of ion-exchanged water are mixed and stirred. Thereby, an aqueous composition (F-11) having a solid content of 4.0% by mass was obtained.
Next, a water-based material was applied to the black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side of a 7 cm × 15 cm base material previously coated with the enamel paint (the surface previously coated with the enamel paint). The composition (F-11) was applied using a spray so as to have a coating amount of 17 g / m ² .
The coated base material was kept horizontal, left at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-11) having a coating film formed on a substrate.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-11), the coating film and the test paper (G-11), and the coating film and the test plate (H-11).

[Example 12]
To 4.7 g (solid content 10.0 mass%) of an aqueous dispersion (AD-4) of the polymer (A-4), water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Industries, Ltd.) (Snowtex OS; solid content 20% by mass), 14.8 g, inorganic oxide (C-1) having photocatalytic activity 1.6 g (solid content 29% by mass), and ethanol with a solid content of 10. 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass and the bleaching property adjusted to 1.0% by mass of a solid content with ion-exchanged water An aqueous composition having a solid content of 4.0% by mass was prepared by mixing and stirring 1.2 g of the dye (E-1) (manufactured by Kishida Chemical Co., Inc., "methylene blue"), 10.0 g of ethanol, and 66.8 g of ion-exchanged water. Compound (F-12) was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-12) was applied using a spray so as to have a coating amount of 17 g / m ² .
The coated base material was kept horizontal, left at a temperature of 23 ° C., a relative humidity of 50% and an illuminance of 20,000 lux for 48 hours, and a test paper (G-12) having a coating film formed on a black background portion of the opacity test paper And a test plate (H-12) having a coating film formed on a substrate.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-12), the coating film and the test paper (G-12), and the coating film and the test plate (H-12).

[Example 13]
Water-dispersed colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 1.6 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industries, Ltd.) (Snowtex NS; solid content 20% by mass), 15.4 g, inorganic oxide (C-1) having photocatalytic activity 2.3 g (solid content 29% by mass), and ethanol with a solid content of 10. 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass and the bleaching property adjusted to 1.0% by mass of a solid content with ion-exchanged water An aqueous composition having a solid content of 4.0% by mass was prepared by mixing and stirring 1.2 g of the dye (E-1) (manufactured by Kishida Chemical Co., Inc., "methylene blue"), 10.0 g of ethanol, and 68.6 g of ion-exchanged water. Compound (F-13) was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-13) was applied using a spray so as to give a coating amount of 17 g / m ² .
A test paper (G-13) having a coating film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50% and an illuminance of 20,000 lux for 48 hours. And a test plate (H-13) having a coating film formed on a substrate.
Table 1 shows various physical properties and characteristics of the aqueous composition (F-13), the coating film and the test paper (G-13), and the coating film and the test plate (H-13).

[Example 14]
To 5.1 g (solid content 10.0 mass%) of an aqueous dispersion (AD-4) of the polymer (A-4), water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Industries, Ltd.) 12.8 g of “Snowtex OS”; solid content 20% by mass); 2.8 g of inorganic oxide (C-1) having photocatalytic activity (solid content 29% by mass); 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass and the bleaching property adjusted to 1.0% by mass of a solid content with ion-exchanged water An aqueous composition having a solid content of 4.0% by mass was obtained by mixing and stirring 1.2 g of the dye (E-1) (manufactured by Kishida Chemical Co., Inc., "methylene blue"), 10.0 g of ethanol, and 67.1 g of ion-exchanged water. Compound (F-14) was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-14) was applied using a spray so as to have a coating amount of 17 g / m ² .
Test paper (G-14) having a coated film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-14) having a coating film formed on a substrate.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-14), the coating film and the test paper (G-14), and the coating film and the test plate (H-14).

[Example 15]
5.5 g (solid content: 10.0 mass%) of an aqueous dispersion (AD-4) of the polymer (A-4) was added to an aqueous dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Industries, Ltd.) 13.5 g of "Snowtex OS"; solid content of 20 mass%); 2.3 g of inorganic oxide (C-1) having photocatalytic activity (solid content of 29 mass%); 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass, 10.0 g of ethanol, and 67.8 g of ion-exchanged water are mixed and stirred. Thereby, an aqueous composition (F-15) having a solid content of 4.0% by mass was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-15) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-15) having a coating film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-15) having a coating film formed on a substrate.
Table 1 shows the physical properties and characteristic evaluation results of the aqueous composition (F-15), the coating film and the test paper (G-15), and the coating film and the test plate (H-15).

[Example 16]
Water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm was added to 3.9 g (solid content 10.0 mass%) of an aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industries, Ltd.) Manufactured by "Snowtex OS"; solids content 20% by mass), 14.2 g of photocatalytically active inorganic oxide (C-2) 3.3 g (solids content 20% by mass), and fluorocarbon surfactant (D- 2) 0.3 g of (Surflon S-232, manufactured by AGC Seimi Chemical Co .; solid content 30% by mass) and a fading dye (E-2) whose solid content was adjusted to 1.0% by mass with ion-exchanged water. (Acid Red, manufactured by Hodogaya Chemical Co., Ltd.) 1.2 g, 10.0 g of ethanol, and 7.4 g of ion-exchanged water were mixed and stirred to obtain an aqueous composition (F- 16) was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-16) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-16) in which a coated film was formed on a black background portion of an opacity test paper while the coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-16) having a coating film formed on a substrate.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-16), the coating film and the test paper (G-16), and the coating film and the test plate (H-16).

[Example 17]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm was added to 3.0 g (solid content: 10.0 mass%) of an aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industries, Ltd.) Manufactured by "Snowtex OS"; solid content 20% by mass), 14.5 g of inorganic oxide (C-1) having photocatalytic activity (solid content 29% by mass), and fluorocarbon surfactant (D- 2) 0.7 g of "Surflon S-232" (manufactured by AGC Seimi Chemical Co., Ltd .; solid content 30% by mass) and a fading dye (E-2) whose solid content was adjusted to 1.0% by mass with ion-exchanged water. An aqueous composition (F-) having a solid content of 4.0% by mass was prepared by mixing 2.4 g of ethanol (“Acid Red” manufactured by Hodogaya Chemical Industry Co., Ltd.), 10.0 g of ethanol, and 67.4 g of ion-exchanged water and stirring the mixture. 17) was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-17) was applied using a spray so as to give a coating amount of 17 g / m ² .
A test paper (G-17) having a coated film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-17) having a coating film formed on a substrate.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-17), the coating film and the test paper (G-17), and the coating film and the test plate (H-17).

[Example 18]
4.3 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-4) of the polymer (A-4) was added to an aqueous dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm (Nissan Chemical Industries, Ltd.). (Snowtex NS; solid content 20% by mass), 14.8 g, inorganic oxide (C-3) having photocatalytic activity (C-3) 25.3 g (solid content 2% by mass), and ethanol with a solid content of 10. 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass and the bleaching property adjusted to 1.0% by mass of a solid content with ion-exchanged water An aqueous composition having a solid content of 4.0% by mass was prepared by mixing and stirring 1.2 g of the dye (E-1) (manufactured by Kishida Chemical Co., "methylene blue"), 10.0 g of ethanol, and 43.5 g of ion-exchanged water. Compound (F-18) was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-18) was applied using a spray so as to have a coating amount of 17 g / m ² .
A coated test paper (G-18) having a coated film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and standing at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. Then, a test plate (H-18) having a coating film formed on a substrate was obtained.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-18), the coating film and the test paper (G-18), and the coating film and the test plate (H-18).

[Example 19]
To 3.1 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-4) of the polymer (A-4), water-dispersed colloidal silica (B-2) having a number average particle diameter of 8 nm (Nissan Chemical Industries, Ltd.) 15.0 g of “Snowtex NS” (solid content: 20% by mass), 29.2 g of inorganic oxide (C-4) having photocatalytic activity (solid content: 2% by mass), and ethanol with a solid content of 10. 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass and the bleaching property adjusted to 1.0% by mass of a solid content with ion-exchanged water An aqueous composition having a solid content of 4.0% by mass was prepared by mixing and stirring 1.2 g of the dye (E-1) (manufactured by Kishida Chemical Co., "methylene blue"), 10.0 g of ethanol, and 43.5 g of ion-exchanged water. Compound (F-19) was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-19) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-19) having a coating film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50% and an illuminance of 20,000 lux for 48 hours. And a test plate (H-19) having a coating film formed on a substrate.
Table 1 shows the physical properties and characteristic evaluation results of the aqueous composition (F-19), the coating film and the test paper (G-19), and the coating film and the test plate (H-19).

[Example 20]
Water-dispersed colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 2.7 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industries, Ltd.) (“Snowtex NS”; solid content 20% by mass); 14.8 g; inorganic oxide (C-5) having photocatalytic activity 33.0 g (solid content 2% by mass); 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass and the bleaching property adjusted to 1.0% by mass of a solid content with ion-exchanged water An aqueous composition having a solid content of 4.0% by mass was prepared by mixing and stirring 1.2 g of dye (E-1) (manufactured by Kishida Chemical Co., Inc., "methylene blue"), 10.0 g of ethanol, and 37.3 g of ion-exchanged water. Compound (F-20) was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-20) was applied using a spray at an application amount of 17 g / m ² .
The coated base material was kept horizontal, and allowed to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-20) having a coating film formed on a substrate.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-20), the coating film and the test paper (G-20), and the coating film and the test plate (H-20).

[Example 21]
Water-dispersed colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 3.9 g (solid content 10.0 mass%) of an aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industries, Ltd.) (Snowtex NS; solid content 20% by mass), 14.2 g of inorganic oxide (C-6) having photocatalytic activity (2% by mass of solid content), and ethanol with solid content of 10. 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass and the bleaching property adjusted to 1.0% by mass of a solid content with ion-exchanged water An aqueous composition having a solid content of 4.0% by mass was prepared by mixing and stirring 1.2 g of the dye (E-1) (manufactured by Kishida Chemical Co., Inc., "methylene blue"), 10.0 g of ethanol, and 36.7 g of ion-exchanged water. Compound (F-21) was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-21) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-21) having a coated film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-21) having a coating film formed on a substrate.
Table 1 shows the physical properties and characteristic evaluation results of the aqueous composition (F-21), the coating film and the test paper (G-21), and the coating film and the test plate (H-21).

[Example 22]
To 4.7 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-4) of the polymer (A-4), water-dispersed colloidal silica (B-2) having a number average particle diameter of 8 nm (Nissan Chemical Industries, Ltd.) 14.0 g of “Snowtex NS” (solid content: 20% by mass), 31.1 g of inorganic oxide (C-7) having photocatalytic activity (solid content: 2% by mass), and ethanol with a solid content of 10. 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass and the bleaching property adjusted to 1.0% by mass of a solid content with ion-exchanged water An aqueous composition having a solid content of 4.0% by mass was prepared by mixing and stirring 1.2 g of the dye (E-1) (manufactured by Kishida Chemical Co., Inc., "methylene blue"), 10.0 g of ethanol, and 38.0 g of ion-exchanged water. Compound (F-22) was obtained.
Next, a water-based material was applied to the black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side of a 7 cm × 15 cm base material previously coated with the enamel paint (the surface previously coated with the enamel paint). The composition (F-22) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-22) having a coating film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. Then, a test plate (H-22) having a coating film formed on a substrate was obtained.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-22), the coating film and the test paper (G-22), and the coating film and the test plate (H-22).

[Example 23]
Water-dispersed colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 2.7 g (solid content: 10.0 mass%) of an aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industries, Ltd.) (Snowtex NS; solid content 20% by mass), 14.8 g, inorganic oxide (C-1) having photocatalytic activity 2.0 g (solid content 29% by mass), and ethanol with solid content of 10. 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass and the bleaching property adjusted to 1.0% by mass of a solid content with ion-exchanged water 1.2 g of dye (E-1) (manufactured by Kishida Chemical Co., "methylene blue"), 10.0 g of ethanol, and 0.7 g of a copper oxide alcohol dispersion (manufactured by CIK Nanotech, "CUAP15WT% -G180") Volume 15. Mass%), by stirring a mixture of ion-exchanged water 67.7 g, was obtained solid content 4.0% by weight of the aqueous composition (F-23).
Next, a water-based material was applied to the black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side of a 7 cm × 15 cm base material previously coated with the enamel paint (the surface previously coated with the enamel paint). The composition (F-23) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-23) having a coated film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-23) having a coating film formed on a substrate.
Table 1 shows the physical properties and characteristic evaluation results of the aqueous composition (F-23), the coating film and the test paper (G-23), and the coating film and the test plate (H-23).

[Example 24]
Water-dispersed colloidal silica (B-2) having a number average particle diameter of 8 nm was added to 2.3 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industries, Ltd.) (Snowtex NS; solid content 20% by mass), 15.9 g, inorganic oxide (C-3) having photocatalytic activity 18.9 g (solid content 2% by mass), and ethanol with a solid content of 10. 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") adjusted to 0% by mass and the bleaching property adjusted to 1.0% by mass of a solid content with ion-exchanged water 1.2 g of dye (E-1) (manufactured by Kishida Chemical Co., "methylene blue"), 10.0 g of ethanol, and 0.7 g of a copper oxide alcohol dispersion (manufactured by CIK Nanotech, "CUAP15WT% -G180") Volume 15. Mass%), by stirring a mixture of ion-exchanged water 67.7 g, was obtained solid content 4.0% by weight of the aqueous composition (F-24).
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-24) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-24) having a coating film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-24) having a coating film formed on a substrate.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-24), the coating film and the test paper (G-24), and the coating film and the test plate (H-24).

[Comparative Example 1]
5.5 g (solid content: 10.0% by mass) of an aqueous dispersion (A'D-6) of the polymer (A'-6) was added to water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan). 13.3 g of "Snowtex OS" (manufactured by Kagaku Kogyo KK; solid content: 20% by mass), 2.4 g of inorganic oxide (C-1) having photocatalytic activity (29% by mass of solid content), and solid content by ethanol Of fluorocarbon surfactant (D-1) (manufactured by DIC, "MegaFac F-444") adjusted to 10.0% by mass, 10.0 g of ethanol, and 67.9 g of ion-exchanged water. The resulting mixture was stirred to obtain an aqueous composition (F-25) having a solid content of 4.0% by mass.
Next, a water-based material was applied to the black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side of a 7 cm × 15 cm base material previously coated with the enamel paint (the surface previously coated with the enamel paint). The composition (F-25) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-25) in which a coated film was formed on a black background portion of an opacity test paper while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-25) having a coating film formed on a substrate.
Table 2 shows the physical properties and characteristic evaluation results of the aqueous composition (F-25), the coating film and the test paper (G-25), and the coating film and the test plate (H-25).

[Comparative Example 2]
To 5.1 g (solid content: 10.0% by mass) of an aqueous dispersion (A'D-7) of the polymer (A'-7), water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan) 12.9 g of "Snowtex OS" (manufactured by Chemical Industry Co., Ltd .; solid content: 20% by mass), 2.8 g of inorganic oxide (C-1) having photocatalytic activity (29 mass% of solid content), and solid content by ethanol Of fluorocarbon surfactant (D-1) (manufactured by DIC, "MegaFac F-444") adjusted to 10.0% by mass, 10.0 g of ethanol, and 68.2 g of ion-exchanged water. The resulting mixture was stirred to obtain an aqueous composition (F-26) having a solid content of 4.0% by mass.
Next, a water-based material was applied to the black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side of a 7 cm × 15 cm base material previously coated with the enamel paint (the surface previously coated with the enamel paint). The composition (F-26) was applied using a spray so as to have a coating amount of 17 g / m ² .
A coated test paper (G-26) with a coating film formed on a black background portion of the test paper with the coated base material kept horizontal and left at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-26) having a coating film formed on a substrate.
Table 2 shows the physical properties and characteristic evaluation results of the aqueous composition (F-26), the coating film and the test paper (G-26), and the coating film and the test plate (H-26).

[Comparative Example 3]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm was added to 1.1 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-1) of the polymer (A-1) (Nissan Chemical Industries, Ltd.) 13.2 g of "Snowtex OS"; solid content of 20 mass%); 4.0 g of inorganic oxide (C-1) having photocatalytic activity (solid content of 29 mass%); 1.0 g of fluorocarbon surfactant (D-1) (manufactured by DIC, "MegaFac F-444") adjusted to 0% by mass, 10.0 g of ethanol, and 70.8 g of ion-exchanged water are mixed and stirred. Thus, an aqueous composition (F-27) having a solid content of 4.0% by mass was obtained.
Next, a water-based material was applied to the black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side of a 7 cm × 15 cm base material previously coated with the enamel paint (the surface previously coated with the enamel paint). The composition (F-27) was applied using a spray so as to have a coating amount of 17 g / m ² .
Test paper (G-27) having a coated film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. And a test plate (H-27) having a coating film formed on a substrate.
Table 2 shows various physical properties and characteristics evaluation results of the aqueous composition (F-27), the coating film and the test paper (G-27), and the coating film and the test plate (H-27).

[Comparative Example 4]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm was added to 6.6 g (solid content 10.0 mass%) of an aqueous dispersion (AD-1) of the polymer (A-1) (Nissan Chemical Industries, Ltd.) 16.7 g, ethanol 10.0 g, and ion-exchanged water 66.7 g are mixed and stirred to obtain an aqueous composition having a solid content of 4.0 mass%. (F-28) was obtained.
Next, a water-based material was applied to the black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one side of a 7 cm × 15 cm base material previously coated with the enamel paint (the surface previously coated with the enamel paint). The composition (F-28) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-28) in which a coated film was formed on a black background portion of an opacity test paper while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50% and an illuminance of 20,000 lux for 48 hours. And a test plate (H-28) having a coating film formed on a substrate.
Table 2 shows various physical properties and property evaluation results of the aqueous composition (F-28), the coating film and the test paper (G-28), and the coating film and the test plate (H-28).

[Comparative Example 5]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm was added to 6.5 g of an aqueous dispersion (AD-5) of the polymer (A-5) (solid content: 10.0% by mass) (Nissan Chemical Industries, Ltd.) 12.9 g of “Snowtex OS”; solid content 20% by mass); 2.3 g of inorganic oxide (C-1) having photocatalytic activity (solid content 29% by mass); 1.0 g of a fluorocarbon surfactant (D-1) (manufactured by DIC, "MegaFac F-444") adjusted to 0% by mass, 10.0 g of ethanol, and 67.3 g of ion-exchanged water are mixed and stirred. Thereby, an aqueous composition (F-29) having a solid content of 4.0% by mass was obtained.
Next, a water-based material was applied to a black background portion (L * value 7) of the opacity test paper (manufactured by Nippon Test Panel Co., Ltd.) and one surface of a 7 cm × 15 cm base material pre-coated with enamel paint (surface pre-coated with enamel paint). The composition (F-29) was applied using a spray so as to have a coating amount of 17 g / m ² .
A test paper (G-29) having a coated film formed on a black background portion of an opacity test paper, while keeping the coated substrate horizontal and allowing it to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20,000 lux for 48 hours. Then, a test plate (H-29) having a coating film formed on a substrate was obtained.
Table 2 shows various physical properties and characteristics evaluation results of the aqueous composition (F-29), the coating film and the test paper (G-29), and the coating film and the test plate (H-29).

  Each of the aqueous compositions of the examples does not impair the appearance even with a dark-colored substrate, and forms a coating film that can maintain a high level of appearance, stain resistance, sealing stain resistance, and biological stain resistance over a long period of time. It was confirmed that it was possible.

  The water-based composition, water-based paint, coating film, and painted product of the present invention have industrial applicability as various members such as architectural exterior applications, exterior display applications, automotive parts, and optical components such as displays and lenses. have.

Claims (8)

An aqueous dispersion (AD) of the polymer (A) having a number average particle diameter of 10 to 40 nm,
Silicon dioxide (B),
An inorganic oxide (C) having photocatalytic activity;
, Containing
The polymer (A) is a poly (meth) acrylate-based polymer, and is a shea recone modified (meth) any one or more selected from an acrylic polymer or Ranaru group,
The mass ratio of the polymer (A) and the silicon dioxide (B) (polymer (A) / silicon dioxide (
B)) is 1/22 or more and less than 1/4. The aqueous composition according to claim 1, wherein the polymer (A) contains a structural unit derived from dimethyldimethoxysilane (a) in an amount of from 20 to 70% by mass in terms of a hydrolyzed condensate. The aqueous composition according to claim 1 or 2, further comprising a fluorocarbon surfactant (D). The aqueous composition according to any one of claims 1 to 3, further comprising a fading dye (E).   An aqueous paint containing the aqueous composition according to any one of claims 1 to 4.   A coating film formed from the water-based paint according to claim 5. A substrate,
The coating film according to claim 6, which is formed on at least a part of the surface of the substrate,
, Including, painted products.   The coated product according to claim 7, wherein the substrate is an organic substrate.