JP2018193455A - Aqueous composition, aqueous coating, coating film, and coating product - Google Patents

Abstract

To provide an aqueous composition that can form a coating film which suppresses the circulation foaming properties of a coating and can maintain excellent coating properties and weather resistance.SOLUTION: An aqueous composition contains an inorganic oxide particle (B) having no catalytic activity, a silicone-based surfactant (C), water as a solvent, and monohydric alcohol (D), with a solid content of 0.5-5 mass%.SELECTED DRAWING: None

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 building exteriors, bridges, tanks, etc. are painted with paint, etc., but the surface of the coating film is dirt, smoke, sand, etc. in the air, and dirt components that are eluted from the sealing material. Contaminated by pollutants discharged from the building outlet. Such contamination of the paint film is usually dark and significantly impairs the aesthetics of buildings and outdoor structures.

Conventionally, as an aqueous top coating composition that suppresses contamination of the coating film as described above, an aqueous composition containing a polymer particle dispersion and inorganic oxide particles, the constituents contained in the polymer particle dispersion comprising: A prescribed aqueous composition has been proposed (see, for example, Patent Document 1).
Further, a technique for reducing the surface tension of a paint by adding a composition additive containing a specific amount of a hydrocarbon surfactant and a specific amount of a fluorocarbon surfactant is disclosed (for example, see Patent Document 2). .

JP 2014-114425 A JP 2012-219215 A

The technique described in Patent Document 1 is an excellent technique that provides sufficient contamination resistance and weather resistance, but is a requirement required when the paint is circulated and used, such as line coating in a factory. There is a problem that the foaming property which is one of the performances is not considered.
Further, in the technique described in Patent Document 2, the foaming property when the paint is shaken in a short time is improved, but the circulating foaming property when the paint is circulated for a long time is suppressed, and the coating is performed. However, there is a problem that an aqueous composition that achieves both high performance and weather resistance has not been obtained.

  Therefore, in view of the above-mentioned problems of the prior art, the present invention provides an aqueous composition capable of forming a coating film that can suppress the circulating foaming property of a paint and maintain good coating properties and weather resistance. Objective.

As a result of intensive studies, the present inventors have found that inorganic oxide particles (B) having no catalytic activity, a specific surfactant (C), water as a solvent, and a monovalent alcohol (D). It has been found that the aqueous composition having a specific solid content can solve the above-mentioned problems of the prior art, and has completed the present invention.
That is, the present invention is as follows.

[1]
Inorganic oxide particles (B) having no catalytic activity;
A silicone-based surfactant (C);
Water as solvent,
A monohydric alcohol (D),
Containing,
The aqueous composition whose solid content is 0.5-5 mass%.
[2]
The aqueous composition according to [1], further including an aqueous dispersion (AD) of the polymer (A).
[3]
The polymer (A) is
The aqueous composition according to [2], which is a polymer obtained by polymerizing a vinyl monomer and a hydrolyzable silicon compound in the presence of water and an emulsifier.
[4]
The aqueous composition according to any one of [1] to [3], wherein the inorganic oxide particles (B) having no catalytic activity are silicon dioxide.
[5]
The aqueous composition according to any one of [1] to [4], wherein the static surface tension at an alcohol concentration of 15% by mass in the aqueous composition is 20 to 40 mN / m.
[6]
The aqueous composition according to any one of [1] to [5], further including an inorganic oxide (E) having photocatalytic activity.
[7]
An aqueous paint containing the aqueous composition according to any one of [1] to [6].
[8]
A coating film obtained from the water-based paint described in [7].
[9]
A coated product comprising a substrate and the coating film according to [8] formed on at least a part of the surface of the substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the aqueous composition which can form the coating film which can suppress the circulating foaming property of a coating material and can maintain favorable coating property and a weather resistance can be provided.

  Hereinafter, modes for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

(Aqueous composition)
The aqueous composition of the present embodiment is
Inorganic oxide particles (B) having no catalytic activity;
A silicone-based surfactant (C);
Water as solvent,
A monohydric alcohol (D),
The solid content is 0.5 to 5% by mass.

(Components of aqueous composition)
<Aqueous dispersion (AD) of polymer (A)>
The aqueous composition of the present embodiment is added to the inorganic oxide particles (B), the silicone-based surfactant (C), water, and the monovalent alcohol (D) from the viewpoint of weather resistance and stain resistance. Furthermore, it is preferable to contain the aqueous dispersion (AD) of a polymer (A).
In the present specification, the polymer (A) may be described as the component (A).

As the polymer (A), a polymer obtained by a method such as emulsion polymerization can be used.
Specific examples include polymers obtained by performing any one of radical polymerization, anionic polymerization, and cationic polymerization in an aqueous medium.
The component (A) is not limited to the following, but for example, poly (meth) acrylate polymer, polyvinyl acetate polymer, vinyl acetate- (meth) acrylic polymer, ethylene vinyl acetate heavy polymer Polymer, silicone polymer, fluorine polymer, polybutadiene polymer, styrene butadiene polymer, NBR polymer, polyvinyl chloride polymer, chlorinated polypropylene polymer, polyethylene polymer, polystyrene polymer Homopolymers or copolymers represented by 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.
“(Meth) acrylate” means “acrylate” and “methacrylate” corresponding to it, and “(meth) acryl” means “acryl” and “methacryl” corresponding thereto.

Various homopolymers, copolymers, modified copolymers, etc. (hereinafter, these may be collectively referred to as “polymers”) as the polymer (A) are obtained in the state of an aqueous dispersion. It is preferable.
Suitable examples of these polymers include emulsions, and examples thereof include acrylic emulsions and acrylic silicon emulsions. These can be obtained, for example, by emulsion polymerization of a monomer such as (meth) acrylic acid ester or a hydrolyzable silicon compound described later.

It is preferable that (A) component contains the functional group which can interact with the inorganic oxide (B) which does not have the catalyst activity mentioned later. The interaction here may be a chemical interaction, and examples thereof include a hydrogen bond, a covalent bond, an ionic bond, and a van der Waals force.
Examples of the hydrogen bond include a hydrogen bond between a hydroxyl group possessed by metal oxide particles and a functional group possessed by polymer particles (for example, a hydroxyl group, an amino group, an amide group, etc.).
Examples of the covalent bond include a covalent bond generated by a condensation reaction (dehydration condensation reaction) between the hydroxyl group of the metal oxide particles and the hydroxyl group of the polymer particle.
Examples of the ionic bond include an ionic bond between a hydroxyl group of the metal oxide particle or the like and a cationic group (for example, amino group or imino group) in the polymer particle.

The functional group capable of interacting with the inorganic oxide (B) having no catalytic activity is not limited to the following, but examples thereof include an amide group, a hydroxyl group, a carboxyl group, a carbonyl group, a silanol group, A thiol group, an amino group, an imino group, a ureido group, etc. are mentioned.
These functional groups may contain only 1 type and may contain 2 or more types.

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

The component (A) preferably contains a polymer obtained by polymerizing a vinyl monomer and a hydrolyzable silicon compound described later in the presence of water and an emulsifier.
Thereby, the effect of the weather resistance improvement of a coating film is acquired.

When the component (A) is a polymer obtained by emulsion polymerization, it is obtained as a solvent dispersion of the polymer. The number average particle size of the polymer is preferably 10 to 300 nm, more preferably It is 50-200 nm, More preferably, it is 80-150 nm.
(A) The weather resistance of the coating film obtained further improves because the number average particle diameter of a component is the said range. Furthermore, when the number average particle diameter is 10 nm or more, the stain resistance of the coating film is further improved, and when the number average particle diameter is 300 nm or less, the transparency of the coating film is further improved.
In addition, the number average particle diameter here can be measured using a wet particle size analyzer.

  (A) As a vinyl monomer which can be used for manufacture of a component, although not limited to the following, for example, (meth) acrylic acid ester, aromatic vinyl compound, vinyl cyanide compound, carboxyl group containing Examples thereof include vinyl monomers containing functional groups such as vinyl compounds, hydroxyl group-containing vinyl compounds, glycidyl group-containing vinyl compounds, vinyl compounds having secondary and / or tertiary amide groups, and anionic vinyl compounds.

The (meth) acrylic acid ester is not limited to the following. For example, the (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 particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acrylic. Examples include methyl cyclohexyl acid, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, and the like.
Examples of (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, Examples include 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, α-chloroacrylonitrile, and the like.
Examples of the carboxyl group-containing vinyl compound include, but are not limited to, for example, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, or itaconic acid, maleic acid, fumaric acid. Examples thereof include half esters of dibasic acids such as acids. By using a vinyl monomer containing a carboxyl group, the carboxyl group can be introduced into the component (A). Thus, it is presumed that the stability as an emulsion can be further improved and a high resistance against an external dispersion breaking action can be imparted to the coating film (however, the action of the present embodiment is not limited thereto). 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 amount of the carboxyl group-containing vinyl monomer used in the total amount of the vinyl monomer 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, 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 or 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 (poly) oxyethylene mono (meth) acrylate include, but are not limited to, ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, methoxy Examples include (meth) acrylic acid diethylene glycol, (meth) acrylic acid tetraethylene glycol, and methoxy (meth) acrylic acid tetraethylene glycol.
Examples of (poly) oxypropylene mono (meth) acrylate include, but are not limited to, propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, dipropylene glycol (meth) acrylate Methoxy (meth) acrylic acid dipropylene glycol, (meth) acrylic acid tetrapropylene glycol, methoxy (meth) acrylic acid tetrapropylene glycol, and the like.
The proportion of the hydroxyl group-containing vinyl monomer in the total amount of the vinyl monomer is not limited to the following, but is preferably 0 to 80% by mass, more preferably from the viewpoint of the water resistance of the coating film. Is 0.1-50 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.
Among the vinyl monomers described above, when a glycidyl group-containing vinyl monomer is used, the reactivity of the component (A) is further improved. Therefore, a coating film with further excellent solvent resistance can be obtained by crosslinking using a hydrazine derivative, a carboxylic acid derivative, an isocyanate derivative, or the like. From this viewpoint, the total amount of the glycidyl group-containing vinyl monomer used in the total amount of the vinyl monomer is preferably 0 to 50% by mass.

The vinyl compound having a secondary and / or tertiary amide group is not limited to the following, and examples thereof include N-alkyl-substituted (meth) acrylamide and N-alkylene-substituted (meth) acrylamide.
Examples of N-alkyl-substituted (meth) acrylamides 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-Nn-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 Bis (meth) acrylamide, N-vinylacetamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide and the like.

Examples of vinyl monomers other than those described above include, but are not limited to, for example, olefins such as (meth) acrylamide, ethylene, propylene, and isobutylene; dienes such as butadiene; vinyl chloride and vinylidene chloride fluoride Haloolefins such as vinyl, tetrafluoroethylene and chlorotrifluoroethylene; vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, vinyl p-tert-butylbenzoate, vinyl pivalate, 2-ethylhexanoic acid Carboxylic acid vinyl esters such as vinyl, vinyl versatate and vinyl laurate; isopropenyl acetate such as isopropenyl acetate and isopropenyl propionate; ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, etc. Nyl ethers; 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, perfluoropropyl Examples include methyl (meth) acrylate, vinyl pyrrolidone, trimethylolpropane tri (meth) acrylate, and allyl (meth) acrylate.
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 the polymerization product of the vinyl monomer 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; 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, di (methylenetrimethylolpropane) xanthogen disulfide; thioglycol, α-methylstyrene dimer, etc. Examples include allyl compounds.
These may be used alone or in combination of two or more.
Although the usage-amount of a chain transfer agent with respect to the total amount of the above-mentioned vinyl monomer is not specifically limited, Preferably it is 0.001-30 mass%, More preferably, it is 0.05-10 mass%.

When the polymer (A) is produced by a polymerization reaction of a vinyl monomer and a hydrolyzable silicon compound, the hydrolyzable silicon compound used for producing the polymer (A) is limited to the following. Although it is not a thing, For example, the compound represented by following formula (1), a silane coupling agent, and these condensates are mentioned as a preferable thing.
SiWxRy (1)
In said formula (1), W is a C1-C20 alkoxy group, a hydroxyl group, a C1-C20 acetoxy group, a halogen atom, a hydrogen atom, a C1-C20 oxime group, an enoxy group, an aminoxy group. And at least one selected from the group consisting of amide groups.
R is 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, or a C 6 to 20 carbon atom substituted with a halogen atom. Represents at least one group selected from the group consisting of aryl groups.
x is an integer from 1 to 4, y is an integer from 0 to 3, and satisfies the relationship x + y = 4.
When W is plural or when R is plural, 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, and examples thereof include silicon alkoxide represented by the formula (1).
The silicon alkoxide is preferably a tetrafunctional silicon alkoxide from the viewpoint of hydrolysis rate.

Examples of the silane coupling agent include hydrolyzable groups (for example, alkoxy groups having 1 to 20 carbon atoms, hydroxyl groups, acetoxy groups having 1 to 20 carbon atoms, halogen atoms, hydrogen atoms, oxime groups having 1 to 20 carbon atoms, and enoxy groups. Functional group having reactivity with at least one selected from the group consisting of a group, an aminoxy group and an amide group) and other compounds (eg, vinyl polymerizable group, epoxy group, amino group, methacryl group, thiol group) And hydrolyzable silicon compounds (silane coupling agents) having an isocyanate group and the like.
By using such a silane coupling agent as the hydrolyzable silicon compound, the polycondensate of the hydrolyzable silicon compound and the vinyl monomer can be chemically bonded to each other. Thereby, compatibility improves further and the transparency of a coating film improves further.
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 above vinyl monomer, chemical bonds can be efficiently formed by copolymerization reaction or 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 combined with other components (for example, a vinyl monomer) constituting the component (A). By using such a component (A) in which a hydrolyzable silicon compound (or a polymerization product thereof) and / or a vinyl monomer (or a polymerization product thereof) is combined by a chemical bond, weather resistance is achieved. In addition, a coating film with further improved strength and the like can be obtained (however, the action of this embodiment is not limited thereto).

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

  Although it does not limit to the following as a silane coupling agent which has a thiol group, For example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc. are mentioned as a preferable thing.

The hydrolyzable silicon compound and the silane coupling agent represented by the formula (1) are not limited to the following, but examples include 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 Tiltrimethoxysilane, 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 Xylpropyltrimethoxysilane, 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) acryloyloxypropylto 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, 3- (meth) acryloyloxypropylmethyldimethoxysilane Silanes; monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane.
Among these, tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes are preferable, tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, dimethyldimethoxysilane. From the viewpoint that the hydrolysis rate is high, tetramethoxysilane and tetraethoxysilane which are tetrafunctional silicon alkoxides are more preferable.

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

  As for the silicon alkoxide and the silane coupling agent represented by the above formula (1), only one kind may be used alone, or two or more kinds may be used in combination. Among these, the silicon alkoxide represented by the formula (1) and the silane coupling agent may be used in combination from the viewpoint of improving the performance of the aqueous composition of the present embodiment and the coating film obtained from the aqueous composition. Preferably, at least one selected from the group consisting of tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane and dimethyldimethoxysilane and 3- (meth) acryloxypropyltrimethoxysilane are more preferably used in combination.

  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 component (A) is preferably 0.01 to 20 parts by mass from the viewpoint of polymerization stability. More preferably, it is 0.1-10 mass parts.

In the aqueous composition of the present embodiment, a cyclic siloxane oligomer can be used in combination with the hydrolyzable silicon compound used for producing the above-described polymer (A) in addition to the above-mentioned ones.
By using the cyclic siloxane oligomer in combination, a coating film with 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 said Formula (2), R 'is respectively independently a hydrogen atom, a linear or branched C1-C30 alkyl group, a C5-C20 cycloalkyl group, C1-C20. And at least one selected from the group consisting of 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, cyclic dimethylsiloxane oligomers such as octamethylcyclotetrasiloxane are preferable from the viewpoint of reactivity and the like.

  (A) When manufacturing a component, a titanium alkoxide, a zirconium alkoxide, those condensation products, or a chelate can also be used together with a hydrolyzable silicon compound. By using these compounds in combination, it is possible to obtain a coating film with better water resistance and the like.

Examples of the titanium alkoxide include, but are not limited to, tetramethoxy titanium, tetraethoxy titanium, tetra-i-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec- Examples include butoxy titanium and tetra-tert-butoxy titanium.
When the condensation product of titanium alkoxide is used, the polystyrene-reduced weight average molecular weight is not particularly limited, but is preferably 200 to 5000, more preferably 300 to 1000.

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, tetra-sec- Examples include butoxyzirconium and tetra-tert-butoxyzirconium.
When zirconium alkoxide is used as the condensation product, the weight average molecular weight in terms of polystyrene of the condensation product is not particularly limited, but is preferably 200 to 5000, and more preferably 300 to 1000.

  The mass ratio (hydrolyzable silicon compound / vinyl monomer) of the hydrolyzable silicon compound to the vinyl monomer used when polymerizing the polymer (A) is preferably 0.5 / 99.5 to 99.99. 5 / 0.5, more preferably 0.5 / 99.5 to 15/85.

When the component (A) is produced, a chelating agent that forms a chelate by coordinating with the free metal ion of the metal compound can be used in combination.
Preferred chelating agents include, but are not limited to, for example, alkanolamines such as diethanolamine and triethanolamine; glycols such as ethylene glycol, diethylene glycol and propylene glycol; acetylacetone; ethyl acetoacetate and the like It is done.
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 polymerization rate 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.
Although the compounding quantity of a chelating agent is not specifically limited, It is preferable that it is a ratio of 0.1 mol-2 mol with respect to 1 mol of free metal ions to coordinate.

The emulsifier that can be used for the production of the component (A) is not limited to the following. For example, alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylenealkylsulfuric acid, polyoxyethylenealkylaryl Acidic emulsifiers such as sulfuric acid and polyoxyethylene distyryl phenyl ether sulfonic acid; alkali metal (Li, Na, K etc.) salts of the acidic emulsifiers; ammonium salts of the acidic emulsifiers; anionic surfactants such as fatty acid soaps; For example, quaternary ammonium salts such as alkyltrimethylammonium bromides, alkylpyridinium bromides, imidazolinium laurates, pyridinium salts, imidazolinium salt type cationic surfactants; polyoxyethylene alkylaryl ethers, 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 water dispersion stability of the polymer (A) becomes very good, and the water resistance of the resulting coating film is further improved.

Examples of the anionic reactive emulsifier include, but are not limited to, ethylenically unsaturated monomers having a sulfonic acid group, a sulfonate group, or a sulfate ester group and salts thereof. A compound having an acid group or a group (ammonium sulfonate group or alkali metal sulfonate group) which is an ammonium salt or an alkali metal salt thereof is preferable.
Although not limited to the following, for example, alkylallylsulfosuccinate (for example, “Eleminol ™ JS-20” manufactured by Sanyo Chemical Co., Ltd., for example, “Latemul ™ S-120” manufactured by Kao Corporation) , “Latemul S-180A”, “Latemul S-180”, etc.), for example, polyoxyethylene alkylpropenyl phenyl ether sulfate ester salt (for example, “AQUALON ™ HS-produced by Daiichi Kogyo Seiyaku Co., Ltd.”). 10 "etc.)), for example, α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-polyoxyethylene sulfate ester salt (for example,“ ADEKA rear, manufactured by ADEKA) Soap (TM) SE-10N "), for example, ammonium- [alpha] -sulfonato- [omega] -1- (allyloxymethyl). ) Alkyloxypolyoxyethylene (for example, “AQUALON KH-1025” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), for example, styrene sulfonate (for example, “Spinomer (trademark) NaSS manufactured by Tosoh Organic Chemical Co., Ltd.) Etc.), for example, α- [2-[(allyloxy) -1- (alkyloxymethyl) ethyl] -ω-polyoxyethylene sulfate ester salt (for example, “ADEKA rear soap (trademark) manufactured by ADEKA) ) SR-1025 ", etc.), for example, a sulfate ester salt of polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (for example," Latemul (trademark) PD-104 "manufactured by Kao Corporation) Etc.) and the like.
Among these, ammonium-α-sulfonato-ω-1- (allyloxymethyl) alkyloxypolyoxyethylene, α- [2-[(allyloxy) -1- (alkyloxymethyl) ethyl] -ω-polyoxyethylene Sulfuric acid ester salts are preferred.

  Further, the nonionic reactive emulsifier is not limited to the following, and examples include α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene. (For example, (Adeka Soap NE-20, “Adekalia Soap NE-30”, “Adekalia Soap NE-40”, etc., manufactured by ADEKA Co., Ltd.) may be mentioned), 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.) can be mentioned. -[(Allyloxy) -1- (alkyloxymethyl) ethyl] -ω-hydroxypolyoxyethylene (for example, manufactured by ADEKA) For example, polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (for example, “Latemul ™ PD-” manufactured by Kao Corporation). 420 ”and the like.

  The use amount of the emulsifier is preferably 10 parts by mass or less, more preferably 100 parts by mass or less, more preferably 100 parts by mass of the total amount of the hydrolyzable silicon compound which is a raw material of the component (A) which is a polymer. 0.001 to 5 parts by mass. By making the usage-amount of an emulsifier into the said range, superposition | polymerization stability improves further and the water resistance of a coating film becomes much better.

The polymerization of the vinyl monomer and the hydrolyzable silicon compound is preferably carried out in the presence of a polymerization catalyst.
The polymerization catalyst for the vinyl monomer is not particularly limited, but a radical polymerization catalyst that causes addition polymerization of the vinyl monomer by radical decomposition itself by heat or a reducing substance is preferable.
Examples of such radical polymerization catalyst include, but are not limited to, persulfates, peroxides, azobis compounds, and the like. These may be water-soluble or oil-soluble.
Specific examples of the radical polymerization catalyst include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, and 2,2-azobisisobutyronitrile. 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile), and the like.
Although the compounding quantity of a radical polymerization catalyst is not specifically limited, Preferably it is 0.001-5 mass parts with respect to 100 mass parts of total amounts of a vinyl monomer.
In addition, when acceleration of the polymerization rate and efficient polymerization at a low temperature (for example, 70 ° C. or lower) are desired, for example, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, Rongalite is used as a radical polymerization catalyst. It is preferable to use together.

The polymerization catalyst for the hydrolyzable silicon compound is not limited to the following. For example, hydrogen halides such as hydrochloric acid and hydrofluoric acid; carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid and lactic acid; sulfuric acid Sulfonic acids such as p-toluenesulfonic acid; acidic emulsifiers such as alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, polyoxyethylenealkylarylsulfuric acid, polyoxyethylene distyrylphenyl ether sulfonic acid Acidic or weakly acidic inorganic salts; acidic compounds such as phthalic acid, phosphoric acid, nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine The Basic compounds such as zabicycloundecene, ethylenediamine, diethylenetriamine, ethanolamine, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane; dibutyltin octylate, dibutyltin dilaurate, etc. The tin compound is mentioned.
Among these, as the polymerization catalyst for the hydrolyzable silicon compound, acidic emulsifiers are preferable from the viewpoint of having a function as an emulsifier as well as a polymerization catalyst. As the acidic emulsifier, an alkylbenzene sulfonic acid having 5 to 30 carbon atoms (for example, dodecylbenzene sulfonic acid) is more preferable.

  The polymerization of the vinyl monomer and the hydrolyzable silicon compound can be carried out separately, but it is preferable because the polymerization can be efficiently achieved by carrying out the polymerization simultaneously.

A preferred method for obtaining the component (A) is, for example, so-called emulsion polymerization in which a vinyl monomer and a hydrolyzable silicon compound are polymerized in the presence of a sufficient amount of water for the emulsifier to form micelles. Can be mentioned.
The specific method of emulsion polymerization is not particularly limited. For example, the vinyl monomer and the hydrolyzable silicon compound are dropped into the reaction vessel as they are or in an emulsified state, all at once or in a divided manner or continuously. And a method of polymerizing at a reaction temperature of about 30 to 150 ° C. in the presence of a polymerization catalyst, preferably under a pressure of atmospheric pressure to 10 MPa.
The reaction temperature and reaction pressure are not limited to the above-mentioned conditions depending on the reaction conditions and the like, and arbitrary conditions can be appropriately selected.
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 further preferably 5 to 30% by mass. is there.
When it is desired to control the particle diameter more precisely during the emulsion polymerization, it is preferable to employ a seed polymerization method in which emulsion particles are preliminarily present in the aqueous phase for polymerization. The pH of the polymerization system in this case 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 (borax, etc.), sodium hydrogen carbonate, ammonia and the like.

  (A) As a method for producing the component, after polymerizing a hydrolyzable silicon compound and a vinyl monomer in the presence of a solvent, if necessary, in the presence of water and an emulsifier, water is added until the polymerization product becomes an emulsion. Further, a method of adding can also be adopted. However, emulsion polymerization is preferred from the viewpoint of easy control of the particle size of the obtained component (A).

The component (A) preferably has a core / shell structure in which polymer particles have a core and one or more shell layers.
Having a core / shell structure is preferable because the mechanical properties (balance of strength and flexibility, etc.) of the obtained coating film are further improved. The confirmation of the core / shell structure of the component (A) can be performed by, for example, morphological observation using a transmission electron microscope or the like, analysis by viscoelasticity measurement, or the like.
Although it does not specifically limit as a method to manufacture (A) component which has a core / shell structure, Multistage emulsion polymerization is mentioned as a preferable method.
Multistage emulsion polymerization here is a method of preparing two or more types of reaction solutions having different compositions containing a vinyl monomer and a hydrolyzable silicon compound, and polymerizing them in separate stages.
As an example of multi-stage emulsion polymerization, a method for synthesizing the component (A) having a core / shell structure by two-stage emulsion polymerization will be mainly described.
As the two-stage emulsion polymerization, for example, a step of obtaining seed particles by polymerizing a vinyl monomer and / or a hydrolyzable silicon compound in the presence of water and an emulsifier (first stage), and the obtained seed particles In the presence of, there may be mentioned a method having a step (second stage) of polymerizing a hydrolyzable silicon compound and a vinyl monomer.
The production of the component (A) by the two-stage emulsion polymerization is carried out by supplying the first series (vinyl monomer and / or hydrolyzable silicon compound) and emulsion polymerization to supply the first series, followed by the first stage. The second series (vinyl monomer and / or hydrolyzable silicon compound) is supplied, and this is carried out by a two-stage polymerization process consisting of a second stage polymerization which is further emulsion polymerized 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 preferably 9/1 to 1 / 9, more preferably 8/2 to 2/8.
By performing such multistage emulsion polymerization, polymer particles having a more uniform particle diameter can be obtained. As a method for adding the raw material in the multi-stage emulsion polymerization, a method of preparing seed particles (core) in the first stage polymerization and then adding another monomer or the like thereafter is preferable. This increases the particle diameter of the polymer particles obtained by the second stage polymerization without changing the ratio of the volume average particle diameter / number average particle diameter of the seed particles (core) obtained by the first stage polymerization. It is also possible to do.
When performing multistage emulsion polymerization of three or more stages, the number of stages of polymerization may be increased in the same manner as in the two-stage polymerization.

Although content of (A) component in the aqueous composition of this embodiment is not specifically limited, Preferably it is 0-4.0 mass%, More preferably, it is 0.025-4.0 mass%, More preferably, it is 0.1-3.75 mass%.
By making content of (A) component in an aqueous composition into the said range, the coating film which was further excellent in the weather resistance and stain resistance can be obtained.
Moreover, content of (A) component in the coating film obtained from the aqueous composition of this embodiment is although it does not specifically limit, Preferably it is 0.0-80.0 mass%, More preferably, it is 5.0. It is -80.0 mass%, More preferably, it is 20.0-75.0 mass%. By making content of (A) component in a coating film more than the said lower limit, the weather resistance of a coating film improves further, and the contamination resistance of a coating film improves further by making it below the said upper limit. .

<Inorganic oxide particles having no catalytic activity (B)>
The aqueous composition of the present embodiment contains inorganic oxide particles (B) having no catalytic activity (may be described as component (B) in the present specification).
The inorganic oxide particles (B) having no catalytic activity are inorganic oxide particles having no photocatalytic activity.
Here, having no photocatalytic activity means that neither an oxidation reaction nor a reduction reaction occurs due to light irradiation.
The component (B) is not limited to the following, but examples include silicon dioxide (silica), aluminum oxide (alumina), calcium silicate, magnesium oxide, antimony oxide, zirconium oxide, and complex oxides thereof. Can be mentioned. Among these, from the viewpoint that there are many surface hydroxyl groups, silicon dioxide, aluminum oxide, antimony oxide, and complex oxides thereof are preferable, and silicon dioxide is more preferable.

  The inorganic oxide particles used as the component (B) are preferably present as colloidal particles such as hydrates. That is, by using inorganic oxide colloidal particles, it is possible to further combine with other components such as the component (A) and the component (E) described later, and the stability as the aqueous composition of the present embodiment. Is further improved.

Silicon dioxide as the component (B) is preferably colloidal silica. Examples of the colloidal silica include colloidal silica which is a dispersion of silica water or a water-soluble solvent having silicon dioxide as a basic unit.
The manufacturing method of colloidal silica is not specifically limited, For example, it can also prepare with a sol-gel method. For preparation by the sol-gel method, Werner Stober et al .; Journal of Colloid And Interface Science, vol. 26, pp. 62-69 (1968) and Rickey D. Badley et al .; Langmuir 6, 792 -801 (1990), “Color Material Association Journal”, 61 [9] 488-493 (1988), and the like.

  Although the number average particle diameter of (B) component is not specifically limited, Preferably it is 1-400 nm, More preferably, it is 1-100 nm. By making the number average particle diameter of the component (B) 1 nm or more, the storage stability of the aqueous composition of the present embodiment is further improved. By setting the number average particle diameter of the component (B) to 400 nm or less, the transparency of the obtained coating film is further improved. The number average particle diameter can be measured using a wet particle size analyzer.

The colloidal silica as the component (B) may be acidic or basic in the state of an aqueous dispersion.
Commercially available products can also be used as the acidic colloidal silica using water as a dispersion medium. Examples of such commercially available products include “Snowtex (trademark) -OXS”, “Snowtex-OS”, “Snowtex-O”, “Snowtex-O-40”, “Snowtex-O-40” manufactured by Nissan Chemical Industries, Ltd. Snowtex-OL "and" Snowtex-OYL "," Adelite (trademark) AT-20Q "manufactured by Asahi Denka Kogyo Co., Ltd.," Clevosol (trademark) 20H12 "," Clevosol 30CAL25 "manufactured by Clariant Japan, etc. .
Examples of basic colloidal silica include colloidal silica stabilized by the addition of alkali metal ions, ammonium ions, amines and the like. A commercial item can also be used for these. Examples of such commercially available products include “Snowtex-XS”, “Snowtex-S”, “Snowtex-30”, “Snowtex-50”, and “Snowtex-20L” manufactured by Nissan Chemical Industries, Ltd. , "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”; “Adelite AT-20” manufactured by Asahi Denka Kogyo Co., Ltd. , “Adelite AT-30”, “Adelite AT-20N”, “Adelite AT-30N”, “Adelite AT-20A”, “Adelai “AT-30A”, “Adelite AT-40”, and “Adelite AT-50”; “Clevosol 30R9”, “Clevosol 30R50”, “Crebosol 50R50” manufactured by Clariant Japan, “Ludox ™ HS” manufactured by DuPont -40 "," Ludox HS-30 "," Ludox LS ", and" Ludox SM-30 ".

  Commercially available products can also be used as colloidal silica using a water-soluble solvent as a dispersion medium. Examples of such commercially available products include “MA-ST-M (methanol dispersion type with a particle size of 20 to 25 nm)” and “IPAST (isopropyl alcohol dispersion type with a particle size of 10 to 15 nm)” manufactured by Nissan Chemical Industries, Ltd. , “EG-ST (ethylene glycol dispersion type with a particle size of 10 to 15 nm)”, “EG-ST-ZL (ethylene glycol dispersion type with a particle size of 70 to 100 nm)”, “NPC-ST (with a particle size of 10 to 15 nm) Ethylene glycol monopropyl ether dispersion type) "and the like.

The said colloidal silica may be used individually by 1 type, and may use 2 or more types together.
Furthermore, alumina, sodium aluminate, or the like may be included as a minor component.
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.

Although content of (B) component in the aqueous composition of this embodiment is not specifically limited, Preferably it is 0.025-4.995 mass%, More preferably, it is 0.025-4.0 mass%. Yes, and more preferably 0.05 to 3.0% by mass. By making content of (B) component in an aqueous composition into the said range, the coating film which was further excellent in weather resistance and stain resistance can be obtained.
Although content of (B) component in the coating film obtained from the aqueous composition of this embodiment is not specifically limited, Preferably it is 5.0-99.9 mass%, More preferably, it is 5.0-80. It is 0.0 mass%, More preferably, it is 10.0-60.0 mass%. By making content of (B) component in a coating film more than the said lower limit, the stain resistance of a coating film improves further, and the weather resistance of a coating film improves further by making it below the said upper limit. .

<Silicone-based surfactant (C)>
The aqueous composition of this embodiment contains a silicone-based surfactant (C) (in this specification, it may be referred to as the component (C)). As a result, the wettability to the organic base material and the like when coating using the aqueous composition of the present embodiment and the aqueous paint containing the same is improved, and troubles in appearance such as repellency are suppressed. The uniformity is further improved, and the circulating foaming property can be suppressed to a certain level or less.

  As the silicone-based surfactant (C), a silicone-based surfactant, a modified silicone surfactant, or the like can be used. The modified silicone surfactant may be a modified silicone surfactant modified with a polyether, for example, or may be a modified silicone surfactant obtained by adding a polyether surfactant to a silicone surfactant, for example. .

As a silicone type surfactant (C), a conventionally well-known commercial item can also be used, for example. Examples of such commercially available products include, but are not limited to, “BYK-302”, “BYK-307”, “BYK-331”, “BYK-333”, manufactured by Big Chemie Japan, “BYK-342”, “BYK-345”, “BYK-346”, “BYK-347”, “BYK-348”, “BYK-349”, “BYK-378”, “BYK-3455”; “SN wet 125”, “SN wet 126”, “SN leveler S-906-10”, and the like are available.
These may be used alone or in combination of two or more.

Although content of (C) component in the aqueous composition of this embodiment is not specifically limited, Preferably it is 0.0005-1.0 mass%, More preferably, it is 0.0025-0.75 mass%. Yes, and more preferably 0.005 to 0.5 mass%. By making content of (C) component more than the said lower limit, the uniformity of the coating film obtained improves further. By making content of (C) component below the said upper limit, circulating foaming property and shaking foaming property are suppressed to below a fixed level, and the weather resistance of the coating film obtained further improves.
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 0.1 to 20.0% by mass, more preferably 0.5. It is -15.0 mass%, More preferably, it is 1.0-10.0 mass%. By making content of (C) component more than the said lower limit, the uniformity of a coating film improves further, and the weather resistance of a coating film improves further by setting it as the said upper limit or less.

<Monovalent alcohol (D)>
The aqueous composition of the present embodiment contains a monovalent alcohol (D) (in this specification, it may be referred to as the component (D)).
Although it does not specifically limit as monohydric alcohol (D), Methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, hexane alcohol, heptane alcohol, octane alcohol, 2 ethyl hexane alcohol, etc. are mentioned. It is done. Of these, ethyl alcohol, propyl alcohol, and isopropyl alcohol are preferable from the viewpoints of volatility, odor, wettability, and safety.
These monohydric alcohols may be used alone or in combination of two or more.
The content of the monohydric alcohol in the aqueous composition of the present embodiment is not particularly limited, but is preferably 1.0 to 50.0% by mass, more preferably 5.0 to 40.0% by mass, More preferably, it is 10.0-35.0 mass%.
By making content of (D) component more than the said minimum, coatability and drying property improve further. By making content of (D) component below the said upper limit, safety | security and the storage stability of a coating material further improve.

<Inorganic oxide particles having photocatalytic activity (E)>
It is preferable that the aqueous composition of the present embodiment further contains inorganic oxide particles (E) having photocatalytic activity (may be described as (E) component in the present specification). Thereby, photocatalytic activity and hydrophilicity can be expressed by irradiating light to a coating film.

The kind of inorganic oxide particles (E) having photocatalytic activity is not particularly limited.
As the component (E) include, but are not limited to, 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 a layered oxide having at least one element selected from the group consisting of V and V (for example, Japanese Patent Application Laid-Open Nos. 62-074552, 02-172535, 07-024329, and 08- JP 0897799, JP 08-089800, JP 08-089804, JP 08-198061, JP 09-248465, JP 10-099694. Distribution, JP-A-10-244165 Publication, etc.).

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

The component (E) is an inorganic oxide having photocatalytic activity, and is preferably a metal compound whose particle surface has been modified. By performing the modification treatment, the generation amount of active oxygen species such as H ₂ O ₂ and .OH can be suppressed, and damage to the base coating film can be further suppressed. The substance to be modified is not particularly limited, and examples thereof include silica, aluminum, copper oxide, and iron oxide. Among these, silica is preferable. The same effect can be obtained by modifying with a metal such as Fe, Cu, Al, or Pt, or a complex such as chloroplatinic acid.

The method for modifying the surface of the component (E) will be described using silica as an example. The method for modifying the surface of the silica is not particularly limited, and examples thereof include a method in which a silicon compound is added to a slurry of titanium oxide, and a hydrous oxide of silicon is precipitated through steps such as neutralization. .
It does not specifically limit as a silicon compound, For example, water-soluble alkali metal silicate salts, such as sodium silicate, can be used. Among these, sodium silicate is preferable from the viewpoint that it is colorless and the titanium oxide sol is not colored.
The treatment amount of the hydrous oxide of silicon is preferably 3 to 25% by mass, more preferably 5 to 20% by mass with respect to titanium oxide. Since the increase in the amount of active oxygen species can be suppressed when the amount of treatment is at least the above lower limit, damage to the underlying coating film can be prevented. Further, when the treatment amount is not more than the above upper limit value, the aggregation of titanium oxide can be suppressed and the increase in the viscosity of the sol can be suppressed, so that dispersibility and transparency are further improved.

Although content of (E) component in the aqueous composition of this embodiment is not specifically limited, Preferably it is 0.015-2.00 mass%, More preferably, it is 0.015-1.50 mass%. Yes, and more preferably 0.025 to 1.25% by mass. By making content of (E) component in an aqueous composition into the said range, the coating film which was further excellent in stain resistance and transparency can be obtained.
Moreover, content of (E) component in the coating film obtained from the aqueous composition of this embodiment is although it does not specifically limit, Preferably it is 3.0-40.0 mass%, More preferably, it is 3.0. It is -30.0 mass%, More preferably, it is 5.0-25.0 mass%. By setting the content of the component (E) in the coating film to the above lower limit value or more, the stain resistance of the coating film is further improved, and by setting the content to the upper limit value or less, the transparency of the coating film is further improved. .

<Solid content in aqueous composition>
The solid content (solid content) in the aqueous composition of the present embodiment is 0.5 to 5.0 mass%. Preferably it is 0.7-5.0 mass%, More preferably, it is 1.2-4.5 mass%.
By setting the content of the solid content in the aqueous composition to the lower limit value or more, the uniformity and stain resistance of the coating film are further improved. By setting the solid content in the aqueous composition to the upper limit or less, the transparency and weather resistance are further improved.
Solid content here can be calculated | required by the method as described in the Example mentioned later.
Furthermore, depending on the application of the coating film, it may be required that the coating film has a small film thickness. Even in such a case, when the solid content in the aqueous composition is less than or equal to the above upper limit value, it is possible to obtain a coating film having excellent physical properties such as weather resistance and contamination resistance while having a thin film thickness. it can. By setting the solid content in the aqueous composition to be equal to or higher than the lower limit, it is possible to shorten the drying time required for forming the coating film, and to further improve the work efficiency.
The solid content in the aqueous composition of the present embodiment can be controlled within the above numerical range by adding water as a solvent and a monohydric alcohol.

<Other ingredients>
The aqueous composition of the present embodiment may further contain other components other than those described above, if necessary, within the range where the effect can be obtained.
Examples of such other components include, but are not limited to, for example, antifoaming agents, fading dyes, freezing stabilizers, matting agents, crosslinking reaction catalysts, pigments, curing catalysts, crosslinking agents, and fillers. Agents, anti-skinning agents, dispersants, wetting agents, light stabilizers, antioxidants, UV absorbers, film-forming aids, rust inhibitors, plasticizers, lubricants, reducing agents, antiseptics, antifungal agents, A deodorant, a yellowing prevention agent, an antistatic agent, a charge control agent, etc. are mentioned.
These may be used alone or in combination of two or more.

(Physical properties of aqueous composition)
The aqueous composition of the present embodiment preferably has a static surface tension of 20 to 40 mN / m at an alcohol concentration of 15% by mass from the viewpoint of the circulating foamability and coating properties of the paint.
More preferably, it is 20 to 35 mN / m, and still more preferably 22 to 32 mN / m.
The static surface tension at an alcohol concentration of 15% by mass can be measured by the method described in Examples described later.
The static surface tension of the aqueous composition can be controlled within the above numerical range by the silicone surfactant (C).

[Water-based paint]
The aqueous paint of this embodiment contains the aqueous composition of this embodiment described above.
For the water-based paint of this embodiment, the water-based composition of this embodiment may be used alone, or any other additive or solvent may be blended.
The water-based paint can be applied by a suitable method depending on the application and the material to be applied.
The application method is not limited to the following, but for example, manual spraying method, automatic spraying method in line, flow coating method, roll coating method, brush coating method, dip coating method, spin coating Method, screen printing method, casting method, gravure printing method and flexographic printing method.

  After applying the water-based paint of the present embodiment, the coating film is obtained by drying to remove volatile components. Drying may be performed at normal temperature or may be performed at a temperature of about 40 to 120 ° C. Further, an ultraviolet irradiation treatment or the like may be performed.

[Coating]
Thus, a coating film is obtained with the aqueous coating material containing the aqueous composition of the present embodiment.
This coating film is obtained from an aqueous composition. For example, the above-described aqueous composition may be applied to the surface of various substrates and dried to form a coating film formed on the substrate. it can.

[Coated 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 substrate is not particularly limited as long as a coating film can be formed on the surface thereof, and either an organic substrate or an inorganic substrate may be used, but an organic substrate is preferable.
Examples of the material for the base material include, but are not limited to, synthetic resin, natural resin, metal, ceramics, glass, stone, cement, concrete, ceramic siding, and the like.
These may be used alone or in combination of two or more.

Examples of the synthetic resin include, but are not limited to, thermoplastic resins and curable resins (thermosetting resins, photocurable resins, moisture curable resins, and the like).
Specifically, silicone resin, acrylic resin, methacrylic resin, fluororesin, alkyd resin, aminoalkyd resin, vinyl resin, polyester resin, styrene-butadiene resin, 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 resin, melamine resin, epoxy resin, urethane resin, Examples thereof include silicone-acrylic resin.
Examples of natural resins include, but are not limited to, cellulose resins, isoprene resins such as natural rubber, and protein resins such as casein.
When the base material is a resin base material using the above-described synthetic resin, natural resin, or the like, surface treatment such as corona discharge treatment, flame treatment, or plasma treatment may be performed as necessary.

  The coated product of the present embodiment includes a base material and a coating film formed on the base material, and the coating film is also useful as a coating or the like.

  Since the coating film obtained by this embodiment can maintain an external appearance and antifouling property at a high level over a long period of time, it can be suitably used in an environment that has been difficult to use. From this point of view, the coated product of the present embodiment is not limited to the following, for example, building materials, building exterior, building interior, window frame, window glass, various lenses, structural members, building equipment such as houses, Covers and window glass for vehicular lamps, exteriors of machinery and equipment, dust covers and coatings, display devices, covers, traffic signs, various display devices, display objects such as advertising towers, sound insulation walls for roads and railways, etc. , Exteriors and paintings of bridges, guardrails, tunnel interiors and paintings, insulators, solar battery covers, solar water heater heat collection covers, etc., exterior parts of electronic and electrical equipment used outside, especially transparent materials, plastic houses, greenhouses, etc. Is mentioned.

  As a manufacturing method of the coated product of the present embodiment, for example, the above-described aqueous composition of the present embodiment is applied to at least a part of the surface of the base material, and drying or the like is performed as necessary. Although the method of forming is mentioned, it is not limited to this. For example, after applying the coating film of this embodiment on a base material, the coating film may be peeled off from the base material and adhered to another base material. Or after apply | coating the coating film of this embodiment on a base material, you may adhere | attach to another base material in the state closely_contact | adhered with the base material.

  You may mix | blend the aqueous composition of this embodiment with various aqueous coating materials. Such a water-based paint can form a coating film excellent in appearance, stain resistance, transparency, weather resistance and the like. As described above, the coating film of the present embodiment is excellent in appearance, stain resistance, transparency, weather resistance, and the like, and can be used in a wide range of applications including exterior paints for buildings.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to a following example.
In Examples and Comparative Examples, various physical properties were measured by the following methods.

〔Base material〕
Exterior wall material (ceramic siding; with a clear coating on a single color coating; water contact angle 82 °; dark (brown): lightness L * = 31; light color (beige): L * = 68)

[Content of each component and solid content]
A 2 g sample was placed in an aluminum pan and heated at 130 ° C. for 1 hour. The mass of the sample before and after heating was measured, and the solid content (mass%) was calculated from the difference.
[Solid content in aqueous composition]
A 2 g sample was placed in an aluminum pan and heated at 130 ° C. for 1 hour. The mass of the sample before and after heating was measured, and the solid content (mass%) was calculated from the difference.
[Composition in aqueous composition and composition of coating film]
The solid content of each component was measured in accordance with [content of each component and solid content]. The composition in the aqueous composition and the composition of the coating film were calculated from the blending amount and the solid content described in the examples.

[Number average particle diameter]
The polymer (A) or inorganic oxide (E) having photocatalytic activity is diluted by adding ion-exchanged water so that the loading index is 1.5 to 3.0, and a wet particle size analyzer (manufactured by Nikkiso, “ Microtrack UPA-9230 ").
The measurement conditions are shown below.
-Loading index: 1.5-3.0
・ Measurement time: 60 seconds ・ Number of measurements: 3 times

[Static surface tension at alcohol concentration of 15% by mass]
The static surface tension of the aqueous compositions obtained in Examples and Comparative Examples at an alcohol concentration of 15% by mass was measured using an automatic surface tension meter “CBVP-Z” manufactured by Kyowa Interface Science Co., Ltd. Method), and the measurement was performed under the measurement conditions of a liquid temperature of 23 ° C.

[Physical properties]
(Circulating foaming property)
As the circulating foaming property, the foaming ratio after 30 minutes of circulation of the aqueous composition was determined as follows.
It was evaluated that the smaller the foaming ratio, the better the circulating foaming property.
Place the aqueous composition (300 mL) in a stainless steel container with a scale of 13.5 cm in diameter and 15 cm in height (capacity 2 L), and drop the liquid at a discharge rate of 230 g / min from a height of 20 cm from the liquid level with a circulation pump. Circulated.
Circulating foaming property = (volume of aqueous composition containing generated foam after circulation for 30 minutes / volume of aqueous composition before circulation (300 mL))
2 times: Foaming magnification is 2 times or more and less than 3 times 3 times: Foaming magnification is 3 times or more and less than 4 times 4 times: Foaming magnification is 4 times or more and less than 5 times 5 times: Foaming magnification is 5 times or more and less than 6 times 6 times Above: Foaming ratio is 6 times or more

(Shaking foaming)
The foaming ratio of the aqueous composition was determined as follows as shaking foaming property.
It was evaluated that the smaller the expansion ratio, the better the foaming property.
Operation A: The steps of reversing the top and bottom were repeated 10 times by putting the aqueous compositions (30 mL) obtained in Examples and Comparative Examples into 250 mL graduated cylinders and sealing them.
Foaming factor = (volume of aqueous composition containing generated foam after operation A / volume of aqueous composition before operation A (30 mL))
Less than 2 times: Foaming factor is less than 2 times 2 times: Foaming factor is 2 times to less than 3 times 3 times: Foaming factor is 3 times to less than 4 times 4 times: Foaming factor is 4 times to less than 5 times 5 times: Foaming Multiple is more than 5 times

(Coating property)
In the examples and comparative examples, the surface of the coating film obtained using the light-colored base material is a reflection electron stereoscopic image (acceleration voltage 10 kV, magnification 500 times) of a scanning electron microscope (manufactured by JEOL; JSM-6390LV). I took a picture.
With the image analysis software (manufactured by Asahi Kasei Engineering Co., Ltd .; “A image kun”), the portion covered with the coating film obtained from the aqueous composition and the coating film obtained from the aqueous composition are absent. The area ratio of the part covered with the coating film obtained from the aqueous composition was determined.
The larger the area ratio value, the better the coverage.
The degree of coverage was evaluated according to the following criteria.
◎: Area ratio 90% or more ○: Area ratio 75% or more △: Area ratio 60% or more ×: Area ratio 60% or less

(Color difference before and after painting)
Using a spray so that the coating amount of the aqueous composition becomes a ratio of 33 g / m ^{2 on} the black background portion (L * value 7) of the JISK5600 paint general test method concealment rate test paper (manufactured by Nippon Test Panel Co., Ltd.). Painted.
The coated test paper was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux to obtain a test plate.
The color difference before and after coating was measured using a “color guide” manufactured by BYK Gardner.
If the color difference is 3.0 or less, it indicates that the change in color difference on the dark color background is small and good.
Preferably it is less than 2.0.
Further, it was visually confirmed whether or not local white unevenness was generated on the test plate.
It is preferable that there is no local white unevenness.
As described above, the color difference and the result of visual confirmation were evaluated according to the following criteria.
A: The color difference was less than 2.0 and there was no local white unevenness.
○: The color difference was 2.0 or more and 3.0 or less, and there was no local white unevenness.
○ to Δ: The color difference was 2.0 or more and 3.0 or less, and some white unevenness was locally observed.
Δ: Color difference was 2.0 or more and 3.0 or less, and local white unevenness was observed.
×: Color difference over 3.0

(Drying)
The dark base material was previously heated to 80 ° C., and was applied using a spray so that the coating amount of the aqueous composition was 33 g / m ² .
The coated substrate was kept horizontal, the surface dryness 30 seconds after painting was visually observed and evaluated according to the following criteria.
<Evaluation criteria>
○: It was almost dry.
Δ: There was some drying unevenness.
X: There was an undried portion enough to cause dripping.

(Weather resistance test: gloss retention after 2500 hours)
An exposure test using a “Sunshine Weather Meter” manufactured by Suga Test Instruments Co., Ltd. (black panel temperature 63 ° C., rainfall 18 minutes / 2 hours) Went.
The glossiness at 60 ° after 2500 hours of exposure was measured using a gloss meter (manufactured by BYK Gardner, “Micro Trigloss μ”).
And gloss retention was computed based on the following formula.
In addition, the result evaluated only with the base material shows a gloss retention of 80% after 2500 hours of exposure. When the gloss retention is larger than these values, the weather resistance is good.
Gloss retention (%) = 60 ° gloss after exposure test / 60 ° gloss before exposure test × 100

(Contamination resistance)
The coating film obtained by using the light-colored base material in Examples and Comparative Examples is attached to a fence facing a general road (truck traffic volume of about 500 to 1000 units / day) and left for 6 months or 1 year. did.
The degree of contamination of the test plate after standing was visually evaluated according to the following criteria.
In addition, the result evaluated only with the base material was “△” for 6 months and “×” for 1 year.
○: Dirt was hardly confirmed.
Δ: Some contamination was confirmed.
X: A large amount of dirt was confirmed.

[Production Example 1]
<Synthesis of aqueous dispersion (AD-1) of polymer (A-1)>
A reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device was charged with 850 g of ion-exchanged water and 5.6 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution, and then the temperature in the reactor was adjusted to 80 under stirring. Warmed to ° C.
In this reactor, a mixed solution consisting of 93.9 g of dimethyldimethoxysilane, 73.0 g of phenyltrimethoxysilane, and 29.4 g of methyltrimethoxysilane was added for about 2 hours while maintaining the temperature in the reactor at 80 ° C. It was dripped over. Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 30 minutes.
Next, 5.6 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution was added, and then the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 4 hours. Thereto, 6.6 g of a 2% by mass aqueous ammonium persulfate solution was added, then 22.5 g of methyl methacrylate, 11.2 g of n-butyl acrylate, 12.3 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, -A mixed solution composed of 1.1 g of methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, 1.2 g of reactive emulsifier (manufactured by ADEKA, "ADEKA rear soap SR-1025"; 25 mass% solid content aqueous solution), Reactive emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., “Aqualon KH-1025”; solid content 25% by weight aqueous solution) 1.2 g, mixed solution of ammonium persulfate 2.0% by weight aqueous solution 30 g, ion-exchanged water 286.4 g Were simultaneously added dropwise over about 2 hours while maintaining the temperature in the reactor at 80 ° C.
Further, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for about 1 hour, followed by cooling to room temperature, adjusting the pH to 8 by adding 25% aqueous ammonia solution to the reaction solution, and then adding 100 mesh. Filtered through a wire mesh. The solid content was adjusted to 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion (AD-1) of polymer particles (A-1) having a number average particle size of 148 nm.

[Production Example 2]
<Synthesis of aqueous dispersion (AD-2) of polymer (A-2)>
A reactor having a reflux condenser, a dropping tank, a thermometer, and a stirrer was charged with 560 g of ion-exchanged water and 15.0 g of a 10% by mass aqueous dodecylbenzenesulfonic acid solution, and then the temperature in the reactor was changed to 80 under stirring. Warmed to ° C. Into this reactor, a mixed liquid consisting of 125.9 g of dimethyldimethoxysilane and 39.4 g of methyltrimethoxysilane was dropped over about 2 hours while keeping 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, 16.8 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution was added, and then the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 2 hours.
A mixed solution composed of 36.8 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, and 1.1 g of 3-methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, a reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap” SR-1025 "; solid content 25 mass% aqueous solution) 1.5 g, reactive emulsifier (Daiichi Kogyo Seiyaku Co., Ltd.," Aqualon KH-1025 "; solid content 25 mass% aqueous solution) 3.0 g, ammonium persulfate 0. A mixed liquid consisting of 146.4 g of a 5% by mass aqueous solution and 256.4 g of ion-exchanged water was simultaneously added dropwise over about 2 hours while maintaining the temperature in the reactor at 80 ° C.
After completion of the dropwise addition, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for about 1 hour.
After cooling to room temperature, the hydrogen ion concentration of the reaction solution in the reactor was measured and found to be pH 1.9. A 25% aqueous ammonia solution was added to the reaction solution to adjust the pH of the solution to 8, and then the reaction solution was filtered through a 100 mesh wire net.
Furthermore, it adjusted so that solid content might be 10.0 mass% with ion-exchange water, and obtained the water dispersion (AD-2) of the polymer (A-2) whose number average particle diameter is 100 nm.

[Production Example 3]
<Synthesis of inorganic oxide (E-1) having photocatalytic activity>
Silica-modified rutile titanium oxide 700 mL of 200 g / L titanium tetrachloride aqueous solution as TiO ₂ and 100 g / L sodium hydroxide aqueous solution as Na ₂ O while maintaining the pH of the reaction solution at 5-9 Added.
Then, after adjusting the pH of the reaction liquid to 7, it was filtered and washed until the electric conductivity of the filtrate became 100 μS / cm to obtain a titanium oxide wet cake 1 having a solid content of 28.3 mass%.
This titanium oxide wet cake 1 contained fine particles having a rutile structure, and the number average particle diameter of the primary particles thereof 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 was charged into a 3 L flask, and 1N nitric acid was added so that the molar ratio of titanium oxide / nitric acid was 1/1, and the mixture was heated to a temperature of 95 ° C. and maintained at this temperature for 2 hours. Then, acid heat treatment was performed. The slurry after the acid heat treatment was cooled to room temperature, neutralized to pH 6.7 using 28% aqueous ammonia, and filtered. Then, it wash | cleaned until the electrical conductivity of a filtrate was set to 100 microsiemens / cm, and obtained the titanium oxide wet cake 2 whose solid content is 25 mass%.
The obtained titanium oxide wet cake 2 is repulped by adding an aqueous solution of sodium hydroxide having a concentration of 10%, and then dispersed for 3 hours with an ultrasonic cleaner to obtain an alkaline solution having a pH of 10.5 and a solid content of 10% by mass. A titanium oxide sol was obtained. 2 L of this alkaline titanium oxide sol was charged into a 3 L flask, heated to a temperature of 70 ° C., 69.4 mL of a sodium silicate aqueous solution having a concentration of 432 g / L was added as SiO ₂ , and then heated to 90 ° C. to 1 After maintaining the time, the pH was adjusted to 6 by adding 10% sulfuric acid to obtain a titanium oxide sol whose surface was treated with a hydrous 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 and concentrating device, pH 7.3, solid content 29 mass%, conductivity A neutral rutile type titanium oxide sol of 1.18 mS / cm was obtained. The neutral rutile titanium oxide sol contained 15 mass% of silicon hydrous oxide of SiO ₂ basis relative to TiO _2. The number average particle diameter of the primary particles of titanium oxide in the sol was 9 nm.

[Production Example 4]
<Synthesis of inorganic oxide (E-2) having photocatalytic activity>
Silica-modified anatase-type titanium oxide Aggregated metatitanic acid produced by heating and hydrolyzing a titanium sulfate solution obtained by reacting titanium ore with sulfuric acid was made into an aqueous slurry of 30% by mass in terms of TiO ₂ .
Aqueous ammonia was added to the aqueous slurry to neutralize to pH 7, and then sulfate ions were removed by filtration and washing to obtain a dehydrated cake.
The resulting dehydrated cake was peptized by adding nitric acid to obtain an acidic titanium oxide sol having a pH of 1.5 comprising titanium oxide fine particles having an anatase type crystal structure (number average particle diameter of primary particles: 7 nm).
The obtained acidic titanium oxide sol is diluted with pure water to make 600 mL of titanium oxide sol having a TiO ₂ equivalent concentration of 200 g / L, then heated to 70 ° C., and sodium silicate having a SiO ₂ equivalent concentration of 432 g / L. 20.8 mL of an aqueous solution was added simultaneously with 20% sulfuric acid.
Thereafter, it was aged for 30 minutes. Subsequently, 10% sodium hydroxide aqueous solution was added to adjust pH to 8, and then pH was adjusted to 6 with 2% sulfuric acid aqueous solution, followed by filtration and washing to obtain a wet cake. This wet cake was repulped into pure water and then ultrasonically dispersed to obtain anatase-type titanium oxide sol (solid content 20% by mass, pH 7.5) stable in the neutral range.
In this sample, the aggregated silica was deposited on the surface of the titanium oxide fine particles in a porous state, and the content thereof was 7 parts by mass in terms of SiO _{2 with} respect to 100 parts by mass of TiO ₂ .

[Example 1]
Water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, “Snowtex OS”; solid content 20% by mass) 25.0 g, silicone surfactant (C-1) ( San Nopco's “SN Wet 126”; 5.0 g previously diluted to 10.0% by mass with ethanol, 70.5 g ethanol, and antifoaming agent (San Nopco's “SN Deformer 323”; The aqueous composition (G-1) having a solid content of 1.1% by mass was obtained by mixing and stirring 5.0g) and 394.5g of ion-exchanged water.
The surface tension of this aqueous composition (G-1) was 24 mN / m.
Next, the aqueous composition (G-1) was applied to a 15 cm × 15 cm dark and light-colored substrate previously heated to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-1) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of the aqueous composition (G-1), the coating film, and the test plate (H-1).

[Example 2]
Water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, “Snowtex OS”; solid content 20% by mass) 75.0 g, silicone surfactant (C-2) ( “BYK-348” manufactured by Big Chemie Japan Co., Ltd., 1.0 g previously diluted to 10.0% by mass with ethanol, 74.1 g ethanol, and an antifoaming agent (manufactured by San Nopco, “SN deformer 323”; Aqueous composition (G-2) having a solid content of 3.0% by mass was obtained by mixing 5.0 g of the product diluted in advance with water to 1.0% by mass) and 344.9 g of ion-exchanged water and stirring. It was.
The surface tension of this aqueous composition (G-2) was 40 mN / m.
Next, the aqueous composition (G-2) was applied to a 15 cm × 15 cm dark and light-colored substrate heated to a plate temperature of 80 ° C. in advance using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-2) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of the aqueous composition (G-2), the coating film, and the test plate (H-2).

Example 3
110.0 g of an aqueous dispersion (AD-1) of polymer particles (A-1) and an aqueous dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, “Snowtex OS”); 20.0 g of solid content (20% by mass) and silicone surfactant (C-1) (manufactured by San Nopco, “SN Wet 126”; previously diluted to 10.0% by mass with ethanol), 5.0 g, 70.5 g of ethanol, 5.0 g of an antifoaming agent (manufactured by San Nopco, “SN deformer 323”; previously diluted to 1.0 mass% with water) and 289.5 g of ion-exchanged water are mixed and stirred. Thus, an aqueous composition (G-3) having a solid content of 3.1% by mass was obtained.
The surface tension of this aqueous composition (G-1) was 30 mN / m.
Next, the aqueous composition (G-3) was applied to a 15 cm × 15 cm dark and light-colored substrate previously heated to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-3) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of the aqueous composition (G-3), the coating film, and the test plate (H-3).

Example 4
110.0 g of an aqueous dispersion (AD-1) of polymer particles (A-1) and an aqueous dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, “Snowtex OS”); 20.0 g of a solid content (20% by mass) and 20.0 g of a silicone-based surfactant (C-1) (manufactured by San Nopco, “SN wet 126”; previously diluted to 10.0% by mass with ethanol), Mixing and stirring 57.0 g of ethanol, 5.0 g of antifoaming agent (manufactured by San Nopco, “SN deformer 323”; previously diluted to 1.0 mass% with water) and 288.0 g of ion-exchanged water As a result, an aqueous composition (G-4) having a solid content of 3.4% by mass was obtained.
The surface tension of this aqueous composition (G-4) was 28 mN / m.
Next, the aqueous composition (G-4) was applied to a 15 cm × 15 cm dark and light-colored substrate previously heated to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-4) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of the aqueous composition (G-4), the coating film, and the test plate (H-4).

Example 5
107.25 g of an aqueous dispersion (AD-1) of polymer particles (A-1) and an aqueous dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”); (Solid content 20% by mass) 10.15 g, Silicone surfactant (C-1) (manufactured by Sannopco, “SN wet 126”; previously diluted to 10.0% by mass with ethanol), 5.0 g, 70.5 g of ethanol, 7.75 g of inorganic oxide (E-1) having a photocatalytic activity (solid content 29% by mass), an antifoaming agent (manufactured by San Nopco, “SN deformer 323”; 1.0 with water in advance) The aqueous composition (G-5) having a solid content of 3.1% by mass was obtained by mixing 5.0 g of the product diluted to mass%) and 294.35 g of ion-exchanged water and stirring.
The surface tension of this aqueous composition (G-5) was 30 mN / m.
Next, the aqueous composition (G-5) was applied to a 15 cm × 15 cm dark and light-colored substrate previously heated to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-5) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of the aqueous composition (G-5), the coating film, and the test plate (H-5).

Example 6
107.25 g of an aqueous dispersion (AD-1) of polymer particles (A-1) and an aqueous dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”); 12.65 g of solid content 20% by mass), 5.0 g of silicone surfactant (C-1) (manufactured by San Nopco, “SN Wet 126”; previously diluted to 10.0% by mass with ethanol), 70.5 g of isopropyl alcohol, 5.15 g of inorganic oxide (E-1) having a photocatalytic activity (solid content 29% by mass), an antifoaming agent (manufactured by San Nopco, “SN deformer 323”); The aqueous composition (G-6) having a solid content of 3.1% by mass was obtained by mixing and stirring 5.0 g) (diluted to 0% by mass) and 294.45 g of ion-exchanged water.
The surface tension of this aqueous composition (G-6) was 30 mN / m.
Next, the aqueous composition (G-6) was applied to a 15 cm × 15 cm dark and light-colored substrate heated to a plate temperature of 80 ° C. in advance using a spray so as to have a coating amount of 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-6) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of the aqueous composition (G-6), the coating film, and the test plate (H-6).

Example 7
111.75 g of an aqueous dispersion (AD-1) of polymer particles (A-1) and an aqueous dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”); Solid content 20 mass%) 11.65 g, silicone surfactant (C-1) (manufactured by San Nopco, “SN wet 126”; previously diluted to 10.0 mass% with ethanol), 5.0 g, 70.5 g of ethanol, 5.15 g of inorganic oxide (E-1) having a photocatalytic activity (solid content 29% by mass), an antifoaming agent (manufactured by San Nopco, “SN deformer 323”; 1.0 with water in advance) The aqueous composition (G-7) having a solid content of 3.1% by mass was obtained by mixing 5.0 g of the product (diluted to mass%) and 290.95 g of ion-exchanged water and stirring.
The surface tension of this aqueous composition (G-7) was 30 mN / m.
Next, the aqueous composition (G-7) was applied to a 15 cm × 15 cm dark and light-colored substrate previously heated to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-7) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of the aqueous composition (G-7), the coating film, and the test plate (H-7).

Example 8
90.0 g of an aqueous dispersion (AD-1) of polymer particles (A-1) and an aqueous dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”); 18.75 g of solid content 20 mass%) and silicone surfactant (C-1) (manufactured by San Nopco, “SN Wet 126”; previously diluted to 10.0 mass% with ethanol) 5.0 g, 70.5 g of ethanol, 7.75 g of inorganic oxide (E-1) having a photocatalytic activity (solid content 29% by mass), an antifoaming agent (manufactured by San Nopco, “SN deformer 323”; 1.0 with water in advance) The aqueous composition (G-8) having a solid content of 3.1% by mass was obtained by mixing and stirring 5.0 g) (diluted to mass%) and 303.0 g of ion-exchanged water.
The surface tension of this aqueous composition (G-8) was 31 mN / m.
Next, the aqueous composition (G-8) was applied to a 15 cm × 15 cm dark and light-colored substrate previously heated to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-8) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of this aqueous composition (G-8), coating film and test plate (H-8).

Example 9
35.5 g of an aqueous dispersion (AD-2) of polymer particles (A-2) and water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”); 39.0 g of solid content 20% by mass), zirconia aqueous sol (B-2) (manufactured by Nissan Chemical Industries, Ltd .; “Nanouse ZR-30BS”; solid content 30%) 4.5 g, and silicone surfactant (C -1) (San Nopco, "SN wet 126"; previously diluted to 10.0% by mass with ethanol) 5.0 g, ethanol 70.5 g, and inorganic oxide (E-1) having photocatalytic activity 7.95 g (solid content 29% by mass), antifoaming agent (manufactured by San Nopco, “SN Deformer 323”; 5.0 g previously diluted with water) 5.0 g, and ion exchanged water 332.55 g Mix and stir Gave a solid content 3.1% by weight of the aqueous composition (G-9).
The surface tension of this aqueous composition (G-9) was 30 mN / m.
Next, the aqueous composition (G-9) was applied to a 15 cm × 15 cm dark and light-colored substrate previously heated to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-9) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of the aqueous composition (G-9), the coating film, and the test plate (H-9).

Example 10
67.0 g of an aqueous dispersion (AD-1) of polymer particles (A-1) and an aqueous dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”); 7.0 g of a solid content (20% by mass) and 5.0 g of a silicone surfactant (C-1) (manufactured by San Nopco, “SN Wet 126”; previously diluted to 10.0% by mass with ethanol), 145.5 g of ethanol, 3.1 g of inorganic oxide (E-1) having a photocatalytic activity (solid content 29% by mass), an antifoaming agent (manufactured by San Nopco, “SN deformer 323”; 1.0 with water in advance) The aqueous composition (G-10) having a solid content of 1.9% by mass was obtained by mixing and stirring 5.0 g) (diluted to mass%) and 267.4 g of ion-exchanged water.
Of this aqueous composition (G-10), the surface tension of the aqueous composition (G-10 ′) prepared by replacing 75.0 g of ethanol with 75.0 g of ion-exchanged water was 30 mN / m.
Next, the aqueous composition (G-10) was applied on a 15 cm × 15 cm dark and light-colored substrate previously heated to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-10) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of the aqueous compositions (G-10) and (G-10 ′), the coating film, and the test plate (H-10).

Example 11
107.25 g of an aqueous dispersion (AD-1) of polymer particles (A-1) and an aqueous dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”); (Solid content 20% by mass) 10.15 g, Silicone surfactant (C-1) (manufactured by Sannopco, “SN wet 126”; previously diluted to 10.0% by mass with ethanol), 5.0 g, 70.5 g of ethanol, 7.75 g of an inorganic oxide (E-2) having a photocatalytic activity (solid content 29% by mass), an antifoaming agent (manufactured by San Nopco, “SN deformer 323”; 1.0 with water in advance) The aqueous composition (G-11) having a solid content of 3.1% by mass was obtained by mixing and stirring 5.0 g of the product (diluted to mass%) and 294.35 g of ion-exchanged water.
The surface tension of this aqueous composition (G-11) was 30 mN / m.
Next, the aqueous composition (G-11) was applied on a 15 cm × 15 cm dark and light-colored substrate heated in advance to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-11) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of the aqueous composition (G-11), the coating film, and the test plate (H-11).

[Comparative Example 1]
Water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, “Snowtex OS”; solid content 20% by mass) 5.0 g, silicone surfactant (C-1) ( “SN Wet 126” manufactured by San Nopco, 2.5 g previously diluted to 10.0% by mass with ethanol, 72.75 g ethanol, and antifoam (“SN Deformer 323” manufactured by San Nopco; previously water The aqueous composition (G-12) having a solid content of 0.3% by mass was obtained by mixing and stirring 5.0 g) and 414.75 g of ion-exchanged water.
The surface tension of this aqueous composition (G-12) was 24 mN / m.
Next, the aqueous composition (G-12) was applied to a 15 cm × 15 cm dark and light-colored substrate previously heated to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-12) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of the aqueous composition (G-12), the coating film, and the test plate (H-12).

[Comparative Example 2]
150.0 g of water-dispersed colloidal silica (B-1) (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20 mass%) having a number average particle size of 8 nm, and a silicone surfactant (C-1) ( San Nopco's “SN Wet 126”; 5.0 g previously diluted to 10.0% by mass with ethanol, 70.5 g ethanol, and antifoaming agent (San Nopco's “SN Deformer 323”; The aqueous composition (G-13) having a solid content of 6.1% by mass was obtained by mixing and stirring 5.0g) and 269.5g of ion-exchanged water.
The surface tension of this aqueous composition (G-13) was 24 mN / m.
Next, the aqueous composition (G-13) was applied on a 15 cm × 15 cm dark and light-colored substrate heated in advance to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-13) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of the aqueous composition (G-13), the coating film, and the test plate (H-13).

[Comparative Example 3]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries Ltd., “Snowtex OS”; solid content 20% by mass) 75.0 g, ethanol 75.0 g, and defoamer (San Nopco) "SN deformer 323" manufactured by the company, which was previously diluted to 1.0 mass% with water) 5.0 g and 345.0 g of ion-exchanged water were mixed and stirred to obtain an aqueous solution with a solid content of 3.0 mass% A composition (G-14) was obtained.
The surface tension of this aqueous composition (G-14) was 41 mN / m.
Next, the aqueous composition (G-14) was applied to a 15 cm × 15 cm dark and light-colored substrate previously heated to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-14) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of the aqueous composition (G-14), the coating film, and the test plate (H-14).

[Comparative Example 4]
Water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, “Snowtex OS”; solid content 20 mass%) 75.0 g, fluorocarbon surfactant (manufactured by AGC Seimi Chemical Co., Ltd.) "Surflon S-232"; solid content 30% by mass) 1.0g, ethanol 75.0g, antifoam (San Nopco, "SN deformer 323"; previously diluted to 1.0% by mass with water ) 5.0 g and 344.0 g of ion-exchanged water were mixed and stirred to obtain an aqueous composition (G-15) having a solid content of 3.1% by mass.
The surface tension of this aqueous composition (G-15) was 16 mN / m.
Next, the aqueous composition (G-15) was applied to a 15 cm × 15 cm dark and light-colored substrate previously heated to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-15) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of the aqueous composition (G-15), the coating film, and the test plate (H-15).

[Comparative Example 5]
75.0 g of water-dispersed colloidal silica (B-1) (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20% by mass) having a number average particle size of 8 nm, and a hydrocarbon surfactant (Lion Specialty) “Lipon LH-200” manufactured by Chemicals Co., Ltd. 5.0 g previously diluted to 10.0% by mass with ion-exchanged water, 75.0 g ethanol, and an antifoaming agent (San Nopco, “SN Deformer 323”) A solution previously diluted to 1.0% by mass with water) and 340.0 g of ion-exchanged water were mixed and stirred to obtain an aqueous composition (G-16) having a solid content of 3.1% by mass. Obtained.
The surface tension of this aqueous composition (G-16) was 38 mN / m.
Next, the aqueous composition (G-16) was applied to a 15 cm × 15 cm dark and light-colored substrate previously heated to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-16) having a coating film formed on the substrate.
Table 1 shows the various physical properties and evaluation results of this aqueous composition (G-16), coating film and test plate (H-16).

[Comparative Example 6]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, “Snowtex OS”; solid content 20% by mass) 75.0 g, silicone surfactant (C-1) ( “SN Wet 126” manufactured by San Nopco, 5.0 g previously diluted with ion-exchanged water to 10.0% by mass) and an antifoaming agent (“SN Deformer 323” manufactured by San Nopco; previously 1.0 with water The aqueous composition (G-17) having a solid content of 3.1% by mass was obtained by mixing and stirring 5.0 g) (diluted to mass%) and 415.0 g of ion-exchanged water.
The surface tension of this aqueous composition (G-17) was 24 mN / m.
Next, the aqueous composition (G-17) was applied to a 15 cm × 15 cm dark and light-colored substrate previously heated to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-17) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of this aqueous composition (G-17), coating film and test plate (H-17).

[Comparative Example 7]
35.5 g of an aqueous dispersion (AD-2) of polymer particles (A-2) and water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”); 39.0 g of solid content 20% by mass), 4.5 g of zirconia aqueous sol (B-2) (manufactured by Nissan Chemical Industries, Ltd .; “Nanouse ZR-30BS”; solid content 30%), and fluorocarbon surfactant (AGC Seimi) “Surflon S-232” manufactured by Chemical Co., Ltd .: 1.0 g, solid content 30% by mass), ethanol 75.0 g, and photocatalytic activity inorganic oxide (E-1) 7.95 g (solid content 29% by mass) And 5.0 g of defoaming agent (manufactured by San Nopco, “SN deformer 323”; previously diluted to 1.0 mass% with water) and 332.05 g of ion-exchanged water, and stirring, 3 1% by weight of the aqueous composition of (G-18) was obtained.
The surface tension of this aqueous composition (G-18) was 18 mN / m.
Next, the aqueous composition (G-18) was applied to a 15 cm × 15 cm dark and light-colored substrate previously heated to a plate temperature of 80 ° C. using a spray so that the coating amount was 33 g / m ² .
The coated substrate was kept horizontal and allowed to stand at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a test plate (H-18) having a coating film formed on the substrate.
Table 1 shows various physical properties and evaluation results of this aqueous composition (G-18), coating film and test plate (H-18).

  It was confirmed that any of the aqueous compositions of the examples of the present invention can form a coating film that suppresses the circulating foaming property of the paint and can maintain good coating properties and weather resistance at a high level. .

  The water-based composition, water-based paint, coating film, and coated product of the present invention are industrially applicable as various parts such as architectural exterior use, exterior display use, automotive parts, and optical parts such as displays and lenses. have.

Claims (9)

Inorganic oxide particles (B) having no catalytic activity;
A silicone-based surfactant (C);
Water as solvent,
A monohydric alcohol (D),
Containing,
The aqueous composition whose solid content is 0.5-5 mass%.   The aqueous composition according to claim 1, further comprising an aqueous dispersion (AD) of the polymer (A). The polymer (A) is
The aqueous composition according to claim 2, which is a polymer obtained by polymerizing a vinyl monomer and a hydrolyzable silicon compound in the presence of water and an emulsifier.   The aqueous composition according to any one of claims 1 to 3, wherein the inorganic oxide particles (B) having no catalytic activity are silicon dioxide.   The aqueous composition according to any one of claims 1 to 4, wherein the static surface tension at an alcohol concentration of 15% by mass in the aqueous composition is 20 to 40 mN / m.   The aqueous composition according to any one of claims 1 to 5, further comprising an inorganic oxide (E) having photocatalytic activity.   An aqueous paint containing the aqueous composition according to any one of claims 1 to 6.   A coating film obtained from the water-based paint according to claim 7.   A coated product comprising a substrate and the coating film according to claim 8 formed on at least a part of the surface of the substrate.