JP6086879B2 - Water-based coating agent composition, water-based paint, coating film, and painted product - Google Patents

Description

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

  Conventionally, the surfaces of outdoor structures such as building exteriors, bridges, and tanks have been painted with paint, etc., but the surface of the coating film is dirt, smoke, sand, etc. in the air, and dirt that elutes from the sealing material. Contaminated by components and 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, various technical proposals regarding such a coating film have been made.
For example, Patent Document 1 includes an organic resin and silica at a solid content weight ratio of 100: 50 to 100: 500, and the silica contained in the coating layer is derived from a silica sol having an average primary particle diameter of 1 to 200 nm. A coating layer laminate is disclosed in which the coating amount of the coating layer is 0.1 to 50 g / m ² in terms of solid content.

JP 2007-118567 A

  However, the paint described in Patent Document 1 causes dripping when forming a coating film on the exterior of a building to be painted on a vertical surface. Further, the thickness of the coating film is thickened in the reservoir of the paint due to dripping. Therefore, cracking occurs. This cracked portion has a problem that dust, soot, sand, etc. adhere to it and cause contamination.

  Then, this invention is made | formed in view of the said situation, and it aims at providing the aqueous coating agent composition which can form the coating film which can maintain an external appearance and stain | pollution resistance at a high level over a long period of time. .

As a result of intensive studies, the present inventors have found that the aqueous coating agent composition has a solid content of 0.5 to 2% by mass, and includes an aqueous dispersion (AD) of the polymer (A) and an inorganic oxide (B ), A hydroxyethylcellulose thickener (C), and a (meth) acrylic acid thickener (D). The present invention has been reached.
That is, the present invention is as follows.

[1]
An aqueous coating agent composition having a solid content of 0.5 to 2% by mass,
An aqueous dispersion (AD) of the polymer (A);
Inorganic oxide (B);
Hydroxyethyl cellulose thickener (C);
(Meth) acrylic acid thickener (D);
An aqueous coating agent composition containing
[2]
The aqueous coating agent composition according to [1] above, which contains a polymer obtained by polymerizing a vinyl monomer and a hydrolyzable silicon compound in the presence of water and an emulsifier as the component (A). .
[3]
The aqueous coating agent composition according to [1] or [2], wherein the component (B) is silicon dioxide.
[4]
The aqueous coating agent composition according to any one of [1] to [3], further including an inorganic oxide (E) having photocatalytic activity.
[5]
The aqueous coating agent composition according to any one of [1] to [4], further comprising a fluorocarbon surfactant (F).
[6]
The aqueous coating agent composition according to any one of [1] to [5], further including a fading dye (G).
[7]
An aqueous paint containing the aqueous coating agent composition according to any one of [1] to [6].
[8]
A coating film obtained from the water-based paint described in [7].
[9]
A substrate;
The coating film according to [8], formed on at least a part of the surface of the substrate;
, Painted products containing.
[10]
The coated product according to [9], wherein the substrate is an organic substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the aqueous coating agent composition which can form the coating film which can maintain an external appearance and stain | pollution resistance at a high level over a long term 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 coating agent composition]
The aqueous coating agent composition of the present embodiment is
An aqueous coating agent composition having a solid content of 0.5 to 2% by mass,
An aqueous dispersion (AD) of the polymer (A);
Inorganic oxide (B);
Hydroxyethyl cellulose thickener (C);
(Meth) acrylic acid thickener (D);
Containing.
The coating film obtained from the aqueous coating agent composition of the present embodiment can maintain the appearance and stain resistance at a high level over a long period of time.

(Solid content of aqueous coating agent composition)
The aqueous coating agent composition of this embodiment has a solid content (solid content) of 0.5 to 2% by mass.
When the solid content in the aqueous coating agent composition is 0.5% by mass or more, dripping during application of the aqueous coating agent composition can be prevented, and when it is 2% by mass or less, the transparency of the coating film is good. It will be something.
The lower limit of the solid content in the aqueous coating agent composition is 0.5% by mass or more, preferably 0.7% by mass or more, and more preferably 0.9% by mass or more.
The upper limit of the solid content in the aqueous coating agent is 2% by mass or less, preferably 1.5% by mass or less, and more preferably 1.4% by mass or less.

As a coating film, there exists a case where the film thickness is requested | required thin, and an application. In order to form such a thin coating film, conventionally, a method of reducing the solid content in the aqueous coating agent composition has been attempted.
However, when the solid content is lowered, the dripping of the aqueous coating agent composition (or aqueous paint) cannot be sufficiently prevented, and there may be a problem that the appearance of the coating film is deteriorated.
On the other hand, in order to prevent dripping of the aqueous coating agent composition (or aqueous paint), if the solid content in the aqueous coating agent composition is increased, the coating film becomes too thick and the film thickness becomes non-uniform. And the problem of deteriorating the physical properties of the coating film may occur.
In the aqueous coating agent composition of this embodiment, dripping can be prevented and the coating film which has the outstanding physical property can be formed by containing the above-mentioned specific component composition. Furthermore, it is possible to form a thin coating film sufficiently. Furthermore, these effects can be further improved by setting the solid content in the aqueous coating agent composition of the present embodiment within the above range.

(Components of aqueous coating agent composition)
<Aqueous dispersion (AD) of polymer (A)>
The aqueous coating agent composition of this embodiment contains an aqueous dispersion (AD) of the 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 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.

  The above-mentioned polymer (A) homopolymer, copolymer, modified copolymer, etc. (hereinafter may be collectively referred to as “polymer”) may be obtained in the state of an aqueous dispersion. preferable. Preferred examples of these polymers include emulsions, and specific 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.

  The component (A) preferably contains a functional group capable of interacting with the inorganic oxide (B) described 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) is not limited to the following, and examples thereof include an amide group, a hydroxyl group, a carboxyl group, a carbonyl group, a silanol group, a thiol group, and an amino group. , Imino group, ureido group and the like. These functional groups may contain only 1 type and may contain 2 or more types.

  In addition to the component (A), the aqueous coating agent composition of the present embodiment may further include a compound having a functional group that reacts with the functional group contained in the polymer (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 in the presence of water and an emulsifier.
Thereby, the effect of the weather resistance improvement of a coating film is acquired.

Although the number average particle diameter of (A) component is not specifically limited, Preferably it is 10-300 nm, More preferably, it is 50-200 nm, More preferably, it is 80-150 nm.
By using the component (A) having a number average particle diameter in the above range, the weather resistance of the obtained coating film is further improved. 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.

SiW _x R _y (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 there are a plurality of Ws, and when there are a plurality of Rs, each W and R may be the same as or different from each other.

  As a compound represented by Formula (1), although not limited to the following, the silicon alkoxide represented by Formula (1) etc. are mentioned, for example. 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 vinyl monomer described above, 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 silane coupling agent represented by the formula (1) are not limited to the following, but examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisosilane. Tetraalkoxysilanes such as propoxysilane and tetra-n-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyl Trimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octy Trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloro Propyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxy Ethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltri Toxisilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acrylic Oxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltrii Trialkoxysilanes such as sopropoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxy Silane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyl Diethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di Dialkoxysilanes such as n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane 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) The weight average molecular weight in terms of polystyrene of the condensate of the silane coupling agent is not particularly limited, but is preferably 200 to 5000, more preferably 300 to 1000. By using a condensate having a weight average molecular weight within the above range, the polymerization stability is further improved.

  These silicon alkoxides and silane coupling agents represented by the formula (1) may be used alone or in combination of two or more. Among these, from the viewpoint of improving the performance of the aqueous coating agent composition and the resulting coating film, it is preferable to use a silicon alkoxide represented by the formula (1) and a silane coupling agent in combination, such as tetraethoxysilane, methyltrimethoxy. More preferably, at least one selected from the group consisting of silane, phenyltrimethoxysilane and dimethyldimethoxysilane and 3- (meth) acryloxypropyltrimethoxysilane are 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 present embodiment, a cyclic siloxane oligomer can be used in combination with the hydrolyzable silicon compound in addition to the above-described compounds. 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 condensate of titanium alkoxide is used, the weight average molecular weight in terms of polystyrene 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 condensate, the weight average molecular weight in terms of polystyrene of the condensate is not particularly limited, but is preferably 200 to 5000, more preferably 300 to 1000.

  The mass ratio of the hydrolyzable silicon compound to the vinyl monomer used when polymerizing the polymer (A) is preferably 0.5 / 99.5 to 99.5 / 0.5, more preferably 0. 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, for example, alkanolamines such as diethanolamine and triethanolamine; glycols such as ethylene glycol, diethylene glycol and propylene glycol; acetylacetone; ethyl acetoacetate and the like.
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.
For example, alkylallylsulfosuccinate (for example, “Eleminol ™ JS-20” manufactured by Sanyo Chemical Co., Ltd., for example, “Latemul ™ S-120”, “Latemul S-180A”, “Latemul” manufactured by Kao Corporation S-180 "etc.)), for example, polyoxyethylene alkylpropenyl phenyl ether sulfate ester salt (for example," Aqualon (trademark) HS-10 "manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), etc. , Α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-polyoxyethylene sulfate ester salt (for example, “ADEKA rear soap (trademark) SE-10N” manufactured by ADEKA) For example, ammonium-α-sulfonato-ω-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) SR-1025” manufactured by ADEKA) For example, sulfate ester salt of polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (for example, “Latemul ™ PD-104” manufactured by Kao Corporation). ) 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.

  Nonionic reactive emulsifiers include, for example, α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene (for example, “ADEKA,“ ADEKA Rear soap NE-20 "," ADEKA rear soap NE-30 "," ADEKA rear soap NE-40 ", etc.), for example, polyoxyethylene alkyl propenyl phenyl ether (for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “AQUALON RN-10”, “AQUALON RN-20”, “AQUALON RN-30”, “AQUALON RN-50” and the like.), For example, α- [2-[(allyloxy) -1- (alkyl Oxymethyl) ethyl] -ω-hydroxypolyoxyethylene (for example, “ADEKA rear soap (trademark) ER, manufactured by ADEKA) 10 "etc.), for example, polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (for example," Latemul (trademark) PD-420 "manufactured by Kao Corporation), etc. Can be mentioned.

  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.

  Examples of the radical polymerization catalyst include, but are not limited to, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, 2, 2 -Azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) 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, acidic emulsifiers are preferable as the polymerization catalyst for the hydrolyzable silicon compound 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 may not be the above-mentioned conditions depending on the reaction conditions and the like.
The solid content in the emulsion obtained by emulsion polymerization is not particularly limited, but is preferably 0.1 to 70% by mass, more preferably 1 to 55% by mass, and further preferably 5 to 30% by mass. is there.

  When it is desired to further control the particle size during 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 having 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 an example of 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 obtained Examples thereof include a method having a step (second stage) of polymerizing a hydrolyzable silicon compound and a vinyl monomer in the presence of seed particles.

  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 coating agent composition of this embodiment is not specifically limited, Preferably it is 0.4-1.2 mass%, More preferably, it is 0.4-0.6 mass. %. By making content of (A) component in an aqueous coating agent composition into the said range, the coating film which was further excellent in weather resistance and stain resistance can be obtained.

  Although content of (A) component in the coating film obtained from the aqueous coating agent composition of this embodiment is not specifically limited, Preferably it is 30.0-80.0 mass%, More preferably, it is 40.0. It is -70.0 mass%, More preferably, it is 45-65.0 mass%. By setting the content of the component (A) in the coating film to the above lower limit value or more, the weather resistance of the coating film is further improved, and by setting the content to the upper limit value or less, the stain resistance of the coating film is further improved. .

<Inorganic oxide (B)>
The aqueous coating agent composition of this embodiment contains an inorganic oxide (B).
In the present specification, the inorganic oxide (B) may be simply referred to as the component (B).
The inorganic oxide (B) is an inorganic oxide 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 (B) is preferably present as colloidal particles such as a hydrate. That is, the inorganic oxide colloidal particles can be further combined with other components such as the component (A) and the component (C), and the stability as the aqueous coating agent composition is further improved.

  Silicon dioxide as the inorganic oxide (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 .; Lang muir 6, 792-801 (1990), “Color Material Association Journal”, 61 [9] 488-493 (1988), and the like can be referred to.

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, More preferably, it is 5-30 nm.
By making the number average particle diameter of the component (B) 1 nm or more, the storage stability of the aqueous coating agent composition 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.

  Colloidal silica 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, but are not limited to, “Snowtex (trademark) -OXS”, “Snowtex-OS”, “Snowtex-O” manufactured by Nissan Chemical Industries, Ltd. “Snowtex-O-40”, “Snowtex-OL” and “Snowtex-OYL”, “Adelite ™ AT-20Q” manufactured by ADEKA, “Crebosol ™ 20H12” manufactured by Clariant Japan, and “Clevozole 30CAL25” and the like.

  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, but are not limited to, “Snowtex-XS”, “Snowtex-S”, “Snowtex-30”, “Snowtex” manufactured by Nissan Chemical Industries, Ltd. -50 "," Snowtex-20L "," Snowtex-XL "," Snowtex-YL "," Snowtex-ZL "," Snowtex-NXS "," Snowtex-NS "," Snowtex- "N", "Snowtex-N40", "Snowtex-CXS", "Snowtex-C", "Snowtex-CM", "Snowtex-PS-S" and "Snowtex PS-M"; manufactured by ADEKA “Adelite AT-20”, “Adelite AT-30”, “Adelite AT-20N”, “Adelite AT-30N”, “Adela” "AT-20A", "Adelite AT-30A", "Adelite AT-40" and "Adelite AT-50"; "Clevosol 30R9", "Clebosol 30R50", "Crebosol 50R50" manufactured by Clariant Japan, DuPont "Ludox (trademark) HS-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, but are not limited to, “MA-ST-M (methanol dispersion type with a particle size of 20 to 25 nm)”, “IPAST (particle size) manufactured by Nissan Chemical Industries, Ltd. “10-15 nm isopropyl alcohol dispersion type)”, “EG-ST (ethylene glycol dispersion type with particle diameter of 10-15 nm)”, “EG-ST-ZL (ethylene glycol dispersion type with particle diameter of 70-100 nm)”, “ NPC-ST (ethylene glycol monopropyl ether dispersion type having a particle diameter of 10 to 15 nm) ”and the like.

  The above colloidal silica may be used alone or in combination of two or more. 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 coating agent composition of this embodiment is not specifically limited, Preferably it is 0.05-1.0 mass%, More preferably, it is 0.1-0.9 mass. %.
By making content of (B) component in an aqueous coating agent 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 coating agent composition of this embodiment is not specifically limited, Preferably it is 3.0-70 mass%, More preferably, it is 3.0-60. It is 0.0 mass%, More preferably, it is 5.0-50.0 mass%. By setting the content of the component (B) 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 weather resistance of the coating film is further improved. .

<Hydroxyethylcellulose thickener (C)>
The aqueous coating agent composition of the present embodiment contains a hydroxyethyl cellulose thickener (C). In the present specification, the hydroxyethyl cellulose thickener (C) may be simply referred to as the component (C).
Examples of the hydroxyethyl cellulose thickener (C) include hydroxyethyl cellulose and modified products thereof.
A commercial item can also be used as a hydroxyethylcellulose type | system | group thickener (C). Examples of such commercially available products include, but are not limited to, “HEC Daicel SP200”, “HEC Daicel SP400”, “HEC Daicel SP500”, “HEC Daicel SP550”, “ "HEC Daicel SP600", "HEC Daicel SP800", "HEC Daicel SP850" and "HEC Daicel SP900", "San Heck (trademark) HH", "San Heck H", "San Heck M" and "San Heck G &L" manufactured by Sansho And “HECSZ-25F” manufactured by Sumitomo Seika Co., Ltd.
These hydroxyethyl cellulose-based thickeners (C) may be used alone or in combination of two or more.

  Although the weight average molecular weight of a hydroxyethyl cellulose type | system | group thickener (C) is not specifically limited, Preferably it is 700,000-2 million, More preferably, it is 1 million-1,600,000. When the weight average molecular weight is 700,000 or more, dripping of the aqueous coating agent composition can be further suppressed. When the weight average molecular weight is 2 million or less, the transparency of the coating film obtained from the aqueous coating agent composition is further improved. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

  Although content of (C) component in the aqueous coating agent composition of this embodiment is not specifically limited, Preferably it is 0.05-0.1 mass%, More preferably, it is 0.07-0.09 mass. %. By making content of (C) component in an aqueous coating agent composition into the said range, the coating film which was further excellent in transparency and a weather resistance can be obtained.

  Although content of (C) component in the coating film obtained from the aqueous coating agent composition of this embodiment is not specifically limited, Preferably it is 2.0-10.0 mass%, More preferably, it is 4.0. It is -9.0 mass%. By making content of (C) component in a coating film more than the said lower limit, transparency of a coating film improves further, and the weather resistance of a coating film improves further by making it into the said upper limit or less.

<(Meth) acrylic acid thickener (D)>
The aqueous coating agent composition of this embodiment contains a (meth) acrylic acid thickener (D). In the present specification, the (meth) acrylic acid thickener (D) may be simply referred to as the component (D).
The (meth) acrylic acid thickener (D) contains at least (meth) acrylic acid of (meth) acrylic acid and (meth) acrylic acid ester, and these (meth) acrylic acid and / or (meta) ) It is made of a copolymer mainly composed of an acrylate ester.
The “main component” means that the copolymer contains 50% by mass or more of (meth) acrylic acid and / or (meth) acrylic acid ester.
Examples of the (meth) acrylic acid include, but are not limited to, acrylic acid and methacrylic acid. Moreover, as (meth) acrylic acid ester, although not limited to the following, for example, methyl methacrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Examples include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Further, other monomers such as crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, allylonitrile, (meth) acrylic acid amide, N-methylolacrylamide, glycidyl methacrylate, etc. It may be copolymerized.

  The (meth) acrylic acid thickener (D) is usually used in the form of an aqueous solution after neutralizing with a basic substance. Examples of basic substances include, but are not limited to, alkanolamines such as triethanolamine and monoethanolamine, inorganic bases such as ammonia, sodium hydroxide, and potassium hydroxide, and basic substances such as arginine. An amino acid etc. are illustrated. Moreover, the addition amount of a basic substance should just be sufficient quantity to neutralize an above-described copolymer, and should just mix | blend suitably according to the kind and usage-amount of these components.

The (meth) acrylic acid thickener (D) may be any of powder, aqueous solution, and emulsion.
A commercial item can also be used as a powdered (meth) acrylic-acid type | system | group thickener (D). Examples of such commercially available products include, but are not limited to, "Aron (trademark) A-20P-X", "Aronbis (trademark) MX", "Jurimer (trademark)" manufactured by Toa Gosei Co., Ltd. “AC-10LHP”, “Julimar AC-10SHP”, “Reosic ™ 260H”, “Leosic 262L”, “Leosic 845H”, “Junron ™ PW-120”, “Junron PW-121” and “Junron PW” -160 "and the like.
A commercial item can also be used as (meth) acrylic-acid type | system | group thickener (D) of aqueous solution. Examples of such commercially available products include, but are not limited to, "Aron A-20L", "Aron A-7100", "Aron A-10H", "Aron A-" manufactured by Toa Gosei Co., Ltd. 30 "," Aron A-7255 "," Aron A-7185 "," Aron A-7195 "and the like.

A commercially available product can also be used as the (meth) acrylic acid thickener (D) for the emulsion. Examples of such commercially available products include, but are not limited to, "Aron A-7075", "Aron A-7055", "Aron B-300K" and "Aron B-" manufactured by Toa Gosei Co., Ltd. 500 ”,“ SN thickener (trademark) 630 ”,“ SN thickener 634 ”,“ SN thickener 636 ”and“ SN thickener 640 ”manufactured by San Nopco.
These (meth) acrylic acid thickeners (D) may be used alone or in combination of two or more.

  Although the weight average molecular weight of (meth) acrylic-acid type | system | group thickener (D) is not specifically limited, Preferably it is 100,000-6 million, More preferably, it is 500,000-5 million. When the weight average molecular weight is 100,000 or more, dripping of the aqueous coating agent composition can be further suppressed. When the weight average molecular weight is 6 million or less, the transparency of the coating film obtained from the aqueous coating agent composition is further improved. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

  Although content of (D) component in the aqueous coating agent composition of this embodiment is not specifically limited, Preferably it is 0.005-0.1 mass%, More preferably, it is 0.01-0.07 mass. %. By making content of (D) component in an aqueous coating agent composition into the said range, the coating film which was further excellent in transparency and a weather resistance can be obtained.

Although content of (D) component in the coating film obtained from the aqueous coating agent composition of this embodiment is not specifically limited, Preferably it is 0.5-8.0 mass%, More preferably, it is 1.0. -6.0 mass%.
By making content of (D) component in a coating film more than the said lower limit, transparency of a coating film improves further, and the weather resistance of a coating film improves further by making it into the said upper limit or less.

Furthermore, within the range in which the effect of this embodiment can be obtained, the aqueous coating agent composition of this embodiment may be used in combination with other thickeners.
Examples of other thickeners include, but are not limited to, polysaccharide thickeners, vinyl ether thickeners, and the like.

<Inorganic oxide (E) having photocatalytic activity>
The aqueous coating agent composition of the present embodiment preferably further contains an inorganic oxide (E) having photocatalytic activity. Thereby, photocatalytic activity and hydrophilicity can be expressed by irradiating light to a coating film.
In the present specification, the inorganic oxide (E) may be simply referred to as the (E) component.

As an inorganic oxide (E), what is necessary is just an inorganic oxide which has photocatalytic activity, The kind is not specifically 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 Layered oxides having at least one element selected from the group consisting of V (for example, JP-A-62-074452, JP-A-02-172535, JP-A-07-024329, JP-A-08-089799) , JP 08-089800, JP 08-089804, JP 09-248465, JP 10-099694, JP 10-244165 Etc.) and the like.

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 is modified. By modifying the particle surface, the generation amount of active oxygen species such as H ₂ O ₂ and .OH can be suppressed, and damage to the underlying coating film can be further suppressed.
Examples of the substance that modifies the particle surface include, but are not limited to, silica, aluminum, copper oxide, iron oxide, and the like. Among these, silica is preferable. The same effect can be obtained by modifying the particle surface with a metal such as Fe, Cu, Al or Pt, or a complex such as chloroplatinic acid.

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

  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 treatment amount is equal to or more than the above lower limit value, damage to the base 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 coating agent composition of this embodiment is not specifically limited, Preferably it is 0.1-0.3 mass%, More preferably, it is 0.15-0.20 mass. %. By making content of (E) component of an aqueous coating agent into the said range, the coating film which was further excellent in stain resistance and transparency can be obtained.

  Although content of (E) component in the coating film obtained from the aqueous coating agent composition of this embodiment is not specifically limited, Preferably it is 10.0-25.0 mass%, More preferably, it is 15.0. -20.0 mass%. By setting the content of the component (E) in the coating film to the above lower limit value or more, the contamination 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. .

<Fluorocarbon surfactant (F)>
The aqueous coating agent composition of the present embodiment preferably further contains a fluorocarbon surfactant (F). In the present specification, the fluorocarbon surfactant (F) is sometimes simply referred to as the component (F).
When the aqueous coating agent composition of the present embodiment contains the component (F), it can be applied to an organic base material or the like when applied using the aqueous coating agent composition of the present embodiment or an aqueous paint containing the same. The wettability is further improved, and troubles in appearance such as repellency can be further suppressed. Furthermore, the uniformity of the coating film is further improved. Although it is not certain as these reasons, it is presumed that by containing the component (F), the surface strength of the aqueous coating agent composition can be reduced (however, the action of the present embodiment is not limited to these). Not limited.)

The component (F) is not particularly limited, and examples thereof include a nonionic amphoteric surfactant, an anionic amphoteric surfactant, and a cationic amphoteric surfactant. Among these, nonionic amphoteric surfactants are preferable, and amphoteric surfactants having a C 3-20 perfluoroalkyl group are more preferable.
Examples of amphoteric surfactants having a C 3-20 perfluoroalkyl group include, but are not limited to, perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl ethylene oxide additions. Thing etc. are mentioned. Among these, perfluoroalkylethylene oxide adducts are preferable from the viewpoint of lowering the surface tension of the paint. As a perfluoroalkyl ethylene oxide adduct, a commercial item can also be used, for example. Examples of such commercially available products include, but are not limited to, for example, “Megafac (trademark) F-444” manufactured by DIC, and “Surflon (trademark) S-242” manufactured by AGC Seimi Chemical Co., Ltd. Etc. These may be used alone or in combination of two or more.

  Although content of (F) component in the aqueous coating agent composition of this embodiment is not specifically limited, Preferably it is 0.01-0.1 mass%, More preferably, it is 0.02-0.05 mass. %. By making content of (F) component more than the said lower limit, the uniformity of the coating film obtained improves further. By making content of (F) component below the said upper limit, the weather resistance of the coating film obtained further improves.

<Discoloring dye (G)>
It is preferable that the aqueous coating agent composition of the present embodiment further contains a fading dye (G). In the present specification, the fading dye (G) may be simply referred to as the (G) component.
When the aqueous coating agent composition of this embodiment contains a fading dye (G), troubles such as forgetting to paint, overlapping painting, and uneven coating can be prevented.

  (G) As a component, the thing which loses color by irradiation of sunlight and does not impair the design of the ground is preferable. Although the time until decoloration varies depending on the season, irradiation direction, etc., it is usually preferable that the period until the decoloration is confirmed visually is 20 days or less, more preferably 10 days or less, and even more preferably 3 Less than a day.

  The component (G) is not particularly limited as long as it has the property of being decolored by irradiation with sunlight. Preferred examples include methylene blue, crystal violet, malachite green, brilliant blue FCF, erythrosin, new Examples thereof include one selected from the group consisting of coccin, phloxine, rose bengal, acid red, and first green FCF. Among these, methylene blue is more preferable from the viewpoint of good color developability and fast decolorization rate. These may be used alone or in combination of two or more.

  Although content of (G) component in the aqueous coating agent composition of this embodiment is not specifically limited, Preferably it is 0.0005-0.01 mass%, More preferably, it is 0.001-0.003 mass. %. By making content of (G) component in an aqueous coating agent composition into the said range, the color development property and fading property of a coating film improve further. Color development here refers to the property of coloring to the extent that the painted and unpainted surfaces are visually distinguished from the difference in color, and fading is the color that does not impair the design of the base material. Refers to the nature of

  Although content of (G) component in the coating film obtained from the aqueous coating agent composition of this embodiment is not specifically limited, Preferably it is 0.01-0.5 mass%, More preferably, it is 0.05. It is -0.2 mass%, More preferably, it is 0.1-0.2 mass%. By making content of (G) component more than the said lower limit, the coloring property of a coating film improves further, and the fading property of a coating film improves further by setting it as the said upper limit or less.

<Other ingredients>
The aqueous coating agent composition of the present embodiment may further contain other components than the above as necessary within the range in which the effect is obtained. Examples of such other components include, but are not limited to, for example, antifoaming agents, freeze stabilizers, matting agents, crosslinking reaction catalysts, pigments, curing catalysts, crosslinking agents, fillers, and skinning. Inhibitors, dispersants, wetting agents, light stabilizers, antioxidants, ultraviolet absorbers, film-forming aids, rust inhibitors, plasticizers, lubricants, reducing agents, antiseptics, antifungal agents, anti-algae 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.

[Water-based paint]
The above-mentioned aqueous coating agent composition can be suitably used as an aqueous paint.
That is, the water-based paint of this embodiment contains the above-described water-based coating agent composition.
The water-based paint is obtained by mixing other components with the water-based coating agent composition of the present embodiment as necessary.
Examples of the other components include, but are not limited to, antifoaming agents, freeze stabilizers, matting agents, crosslinking reaction catalysts, pigments, curing catalysts, crosslinking agents, fillers, and anti-skinning agents. , Dispersants, wetting agents, light stabilizers, antioxidants, UV absorbers, film-forming aids, rust inhibitors, plasticizers, lubricants, reducing agents, antiseptics, antifungal agents, anti-algae agents, deodorants Agents, yellowing inhibitors, antistatic agents, charge control agents and the like.

  The water-based paint of the present embodiment can be applied by a suitable method depending on the application and the material to be applied. Examples of the application method include, but are not limited to, spray spraying method, flow coating method, roll coating method, brush coating method, dip coating method, spin coating method, screen printing method, casting method, and gravure printing. Method and flexographic printing method.

[Coating]
The coating film of this embodiment is obtained by applying the water-based paint to a predetermined application target and then drying to remove volatile components. Under the present circumstances, you may further perform the heat processing by the temperature of about 40-120 degreeC, an ultraviolet irradiation process, etc. as needed.

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

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

Examples of the synthetic resin include, but are not limited to, thermoplastic resins and curable resins (thermosetting resins, photocurable resins, moisture curable resins, and the like).
Specific examples of the synthetic resin include, but are not limited to, for example, silicone resins, acrylic resins, methacrylic resins, fluororesins, alkyd resins, aminoalkyd resins, vinyl resins, polyester resins, styrene-butadiene resins, 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, Examples include urea resins, phenol resins, melamine resins, epoxy resins, urethane resins, and silicone-acrylic resins.

  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 the coating film formed on the base material, and the coating film is useful as a coating or the like.

Since the coating film obtained by the aqueous coating composition of the present embodiment can maintain the appearance and antifouling property at a high level for a long period of time, it can be suitably used in an environment that has been difficult to use in the past.
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, by applying the aqueous paint (or aqueous coating agent composition) described above to at least a part of the surface of the substrate, and performing drying or the like as necessary, Although the method of forming a coating film 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 make it adhere | attach on another base material in the state closely_contact | adhered with the base material.

  You may mix | blend the water-based coating agent composition of this embodiment with various water-based paints. 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.

The measuring method of the physical property in the Example and comparative example which are mentioned later is described below.
(Measurement method of physical properties)
<1. Solid content>
A 2 g sample was placed in an aluminum pan and heated at 150 ° C. for 1 hour. The mass of the sample before and after heating was measured, and the solid content (% by mass) was calculated from the difference.

<2. Number average particle diameter>
Ion exchange water was added and diluted so that the loading index was 1.5 to 3.0, and measurement was performed using a wet particle size analyzer (manufactured by Nikkiso Co., Ltd., “Microtrac UPA-9230”). The measurement conditions are shown below.
-Loading index; 1.5-3.0
・ Measurement time: 60 seconds ・ Number of measurements: 3 times

<3. Viscosity>
Measurement was performed using a BM viscometer (manufactured by Toki Sangyo Co., Ltd.). The measurement conditions are shown below.
・ Temperature: 23 ℃
・ Rotor: No1
・ Rotation speed: 60rpm

<4. Glass transition temperature>
Using a “DCS 6220” manufactured by Seiko Instruments Inc., the glass transition temperature was determined from the inflection point of the DSC curve obtained by measuring under a measuring condition of a heating rate of 10 ° C./min. Measurement conditions are shown below.
Measurement cell: aluminum container Preparation of measurement sample: 40 mg of polymer emulsion as a measurement sample was put in an aluminum container and dried at 130 ° C. for 1 hour.

<5. Appearance of coating film (drip)>
Using a spray so that the coating amount of the aqueous coating composition is 25 g / m ^{2 on} one side of the 7 cm × 15 cm substrate (the surface previously coated with the enamel coating) previously coated with the enamel coating described later Painted. The coated substrate was kept vertical, and the degree of dripping after standing for 10 minutes under the conditions of a temperature of 23 ° C. and a relative humidity of 50% was evaluated visually. The coating appearance (drip) was evaluated according to the following criteria.
○: Almost no dripping was confirmed.
Δ: Some dripping was confirmed.
X: A lot of liquid dripping was confirmed.

<6. Gloss>
Using a gloss meter (manufactured by BYK Gardner, “Micro Trigloss μ”), the 60 ° glossiness of the measurement sample was measured.

<7. Gloss retention after painting aqueous coating agent composition>
Using a spray so that the coating amount of the aqueous coating composition is 25 g / m ^{2 on} one side of the 7 cm × 15 cm substrate (the surface previously coated with the enamel coating) previously coated with the enamel coating described later The first painting was done. The coated substrate was kept vertical and allowed to stand for 2 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%, and then the second coating was performed in the same manner as the first coating. Gloss meter (BYK Gardner, “Micro Trigloss μ”) is used to measure the 60 ° gloss after standing for 24 hours under conditions of 23 ° C. and 50% relative humidity. And measured. Moreover, the 60 degree glossiness of the substrate surface before applying the aqueous coating agent composition was also measured in advance using a gloss meter.
And gloss retention was computed based on the following formula.
The higher the gloss retention value, the better the transparency and the better the design of the substrate.

Gloss retention (%) = 60 ° gloss after application of aqueous coating agent composition / 60 ° gloss before application of aqueous coating agent composition × 100

<8. Gloss retention after 3000 hours of weather resistance test>
Using a spray so that the coating amount of the aqueous coating composition is 25 g / m ^{2 on} one side of the 7 cm × 15 cm substrate (the surface previously coated with the enamel coating) previously coated with the enamel coating described later The first painting was done. The coated substrate was kept vertical and allowed to stand for 2 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%, and then the second coating was performed in the same manner as the first coating. The coated substrate was kept vertical and allowed to stand for 24 hours under the conditions of a temperature of 23 ° C. and a relative humidity of 50% to obtain a test plate.
Using an “Sunshine weather meter” manufactured by Suga Test Instruments Co., Ltd., an exposure test (black panel temperature 63 ° C., rainfall 18 minutes / 2 hours) was performed on the test plate. The 60 ° glossiness before and after the exposure test was measured using a gloss meter (manufactured by BYK Gardner, “Microtrigloss μ”).
And gloss retention was computed based on the following formula. The higher the gloss retention value, the better the weather resistance.
Note that the 60 ° gloss retention rate of only the base material previously coated with the enamel paint was 95%.

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

<9. Contamination resistance>
Using a spray so that the coating amount of the aqueous coating composition is 25 g / m ^{2 on} one side of the 7 cm × 15 cm substrate (the surface previously coated with the enamel coating) previously coated with the enamel coating described later The first painting was done. The coated substrate was kept vertical and allowed to stand for 2 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%, and then the second coating was performed in the same manner as the first coating.
The coated substrate was kept vertical and allowed to stand for 24 hours under the conditions of a temperature of 23 ° C. and a relative humidity of 50% to obtain a test plate.
The test plate was affixed to a fence facing a general road (traffic volume of about 500 to 1000 vehicles / day) and allowed to stand for 6 months or 1 year.
The degree of contamination of the test plate after standing was visually evaluated according to the following criteria.
In addition, the result evaluated only with the base material previously coated with the enamel paint was an evaluation of “x” for 6 months and 1 year.

○: Dirt was hardly confirmed.
Δ: Some contamination was confirmed.
X: A large amount of dirt was confirmed.

<10. Wet decomposition performance>
Using a spray so that the coating amount of the aqueous coating composition is 25 g / m ^{2 on} one side of the 7 cm × 15 cm substrate (the surface previously coated with the enamel coating) previously coated with the enamel coating described later The first painting was done.
The coated substrate was kept vertical and allowed to stand for 2 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%, and then the second coating was performed in the same manner as the first coating.
The coated substrate was kept vertical and allowed to stand for 24 hours under the conditions of a temperature of 23 ° C. and a relative humidity of 50% to obtain a test plate.
The test plate was tested in accordance with JIS R1703-2 (Fine ceramics-Test method for self-cleaning performance of photocatalytic material-Part 2: wet decomposition performance) to obtain a decomposition activity index.
The higher the decomposition activity index, the better the self-cleaning property.

The manufacturing method of the base material of the measurement sample used in the method for measuring physical properties is described below.
<Preparation of 7 cm × 15 cm base material pre-coated with enamel paint>
-Preparation of pigment dispersion Dispersant (BASF Japan, "Pig. Disperser MD20") 5.35g, ammonia water 0.50g, propylene glycol 23.50g, water 147.50g, titanium oxide (chlorine method rutile type oxidation) Titanium; manufactured by Ishihara Sangyo Co., Ltd., “Taipeku CR-97”) 333.50 g, antifoaming agent (modified silicone type; manufactured by San Nopco, “SN Deformer 1310”) 2.85 g , A batch type tabletop sand mill) for 20 minutes to obtain a pigment dispersion.

-Preparation of enamel paint 10.0 g of 2,2,4-trimethyl-1,3-butanediol isobutyrate (manufactured by Chisso Corporation, "CS-12") was added to 109.0 g of the polymer emulsion of Production Example 1, ethylene glycol 10.0 g of a mixed solution of 50 parts by mass of monobutyl ether and 50 parts by mass of water, 51.4 g of the pigment dispersion obtained above, and 0.5 g of a 10% aqueous solution of a thickener (manufactured by ADEKA, “Adecanol UH-438”) Was added and mixed for 1 hour to obtain an enamel paint.

-Preparation of 7 cm x 15 cm base material pre-coated with enamel paint Apply the enamel paint obtained above on a 7 cm x 15 cm sulfate alumite plate using wire coater No50, temperature 23 ° C, relative humidity 50% for 48 hours. It was dried to obtain a 7 cm × 15 cm base material previously coated with an enamel paint. The glossiness of the obtained base material was 75.

The polymer aqueous dispersions (Production Examples 1 to 5) and methods for producing the inorganic oxides (Production Examples 6 to 7) having photocatalytic activity used in Examples and Comparative Examples described below are described below.
[Production Example 1]
<Synthesis of polymer emulsion>
In a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirrer, 290 g of ion-exchanged water and 8.0 g of a reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; aqueous solution with a solid content of 25 mass%) are added. After charging, the temperature in the reactor was heated to 80 ° C. with stirring. Into this reactor, 10 g of a 2% by mass aqueous solution of ammonium persulfate was added. After 5 minutes, 25 g of methyl methacrylate, 50 g of cyclohexyl methacrylate, 15 g of butyl acrylate, 5 g of methacrylic acid, 10 g of 2-hydroxyethyl methacrylate, reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; solid A 25 wt% aqueous solution) 4.0 g, an ammonium persulfate 2 wt% aqueous solution 15 g and ion-exchanged water 48 g were added dropwise over 40 minutes from the dropping tank. During the dropping, the temperature of the reaction vessel was maintained at 80 ° C. Even after completion of the dropwise addition, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 30 minutes.
Next, 109 g of methyl methacrylate, 160 g of cyclohexyl methacrylate, 123 g of butyl acrylate and 8 g of methacrylic acid, and a reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; aqueous solution with a solid content of 25% by mass) 16.0 g, an emulsified mixed solution composed of 60 g of a 2% by weight aqueous solution of ammonium persulfate and 192 g of ion-exchanged water, and a mixed solution composed of 1 g of 3-methacryloxypropyltrimethoxysilane, 20 g of dimethyldimethoxysilane and 20 g of methyltrimethoxysilane. From a separate dropping tank, the reactor was dropped over 160 minutes while maintaining the temperature in the reactor at 80 ° C. Furthermore, even after completion of the dropping, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 2 hours. After cooling to room temperature, a 25% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8, and then the reaction solution was filtered through a 100-mesh wire mesh to obtain a polymer emulsion. The obtained polymer emulsion had a solid content of 44.5% by mass.
About the polymer contained in this polymer emulsion, the glass transition temperature calculated | required from the inflection point of the DSC curve based on the above-mentioned method was 40 degreeC.

[Production Example 2]
<Synthesis of aqueous dispersion (AD-1) of polymer (A-1)>
In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 500 g of ion-exchanged water, reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; solid content 25% by mass aqueous solution) 8.0 g Then, 15 g of a 2% by weight aqueous solution of ammonium persulfate was added, and the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, 400 g of methyl methacrylate, 250 g of cyclohexyl methacrylate, 300 g of n-butyl acrylate, 20 g of 2-hydroxyethyl methacrylate, 30 g of methacrylic acid, a reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025” A solid content of 25% by weight aqueous solution) 40 g, an ammonium persulfate 2% by weight aqueous solution 50 g, and ion-exchanged water 700 g of an emulsified mixed solution was added dropwise over about 4 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 2 hours.
After cooling to room temperature, the hydrogen ion concentration of the reaction solution in the reactor was measured and found to be pH 2.1.
A 25% aqueous ammonia solution was added to the reaction solution to adjust the pH 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-1) of the polymer (A-1) whose number average particle diameter is 130 nm.

[Production Example 3]
<Synthesis of aqueous dispersion (AD-2) of polymer (A-2)>
In a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirrer, 609 g of ion exchange water, 10 g of a 25% aqueous solution of a reactive emulsifier (manufactured by Kao Corporation, “Latemul S-180A”), 26 g of cyclohexyl methacrylate, methacrylic acid After charging 8 g of n-butyl acid, 14 g of methyl methacrylate, 2.5 g of n-butyl acrylate, 0.8 g of methacrylic acid, 0.8 g of acrylic acid, and 0.4 g of acrylamide, the temperature in the reactor was adjusted with stirring. Warmed to 80 ° C. Into this reactor, 5 g of a 2% by weight aqueous solution of ammonium persulfate, 1 g of 3-methacryloxypropyltrimethoxysilane, 68 g of methyltrimethoxysilane, and 27 g of dimethyldimethoxysilane were charged. Then, after confirming the exotherm due to the initiation of polymerization, the temperature in the reactor was heated to 85 ° C. and held for 30 minutes.
Next, with the temperature in the reactor lowered and maintained at 80 ° C., 45 g of ion-exchanged water, 10 g of a 25% aqueous solution of a reactive emulsifier (manufactured by Kao Corporation, “Latemul S-180A”), 26 g of cyclohexyl methacrylate, Emulsified mixture consisting of 8 g of n-butyl methacrylate, 14 g of methyl methacrylate, 2.5 g of n-butyl acrylate, 0.8 g of methacrylic acid, 0.8 g of acrylic acid, 0.4 g of acrylamide, and 5 g of 2% by weight aqueous solution of ammonium persulfate. The liquid and a mixed liquid consisting of 46 g of methyltrimethoxysilane and 18 g of dimethyldimethoxysilane were poured into the reactor from separate dropping tanks over 30 minutes and further maintained at 80 ° C. for 2 hours.
Next, with the temperature in the reactor maintained at 80 ° C., 130 g of ion-exchanged water, 50 g of a 25% aqueous solution of a reactive emulsifier (manufactured by Kao Corporation, “Latemul S-180A”), 123 g of cyclohexyl methacrylate, methacrylic acid An emulsified mixture composed of 37 g of n-butyl, 4 g of methyl methacrylate, 79 g of n-butyl acrylate, 4 g of methacrylic acid, and 12 g of a 2% by weight aqueous solution of ammonium persulfate, 2 g of 3-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane A mixed solution composed of 170 g and dimethyldimethoxysilane 68 g was poured into the reactor from a separate dropping tank over 2 hours, and further maintained at 80 ° C. for 1.5 hours.
After cooling to room temperature, the hydrogen ion concentration of the reaction solution in the reactor was measured and found to be pH 2.8.
Next, a 25% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8, followed by filtration 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 127 nm.

[Production Example 4]
<Synthesis of aqueous dispersion (AD-3) of polymer (A-3)>
A reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device was charged with 880 g of ion-exchanged water and 10.0 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution, and the temperature in the reactor was adjusted to 80 with stirring. Warmed to ° C. In this reactor, a mixed solution consisting of 83.4 g of dimethyldimethoxysilane, 73.0 g of phenyltrimethoxysilane, and 42.6 g of methyltrimethoxysilane was maintained for about 2 hours while maintaining the temperature in the reactor at 80 ° C. It was dripped at the same time.
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 2 hours. Next, a mixed liquid consisting of 22.5 g of methyl methacrylate, 11.2 g of n-butyl acrylate, 12.3 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, and 1.1 g of 3-methacryloxypropyltrimethoxysilane 0.9 g of acrylic acid, reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; solid content 25% by mass aqueous solution) 1.5 g, reactive emulsifier (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “AQUALON KH- 1025 "; solid content 25 mass% aqueous solution) 0.8 g, ammonium persulfate 0.5 mass% aqueous solution 146.4 g, and ion-exchanged water 256.4 g mixed liquid maintained at 80 ° C in the reactor. In this state, the solution was simultaneously added dropwise over about 2 hours.
Further, 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 liquid in the reactor was measured to be pH 2.0.
Next, a 25% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8, followed by filtration 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-3) of the polymer (A-3) with a number average particle diameter of 80 nm.

[Production Example 5]
<Synthesis of aqueous dispersion (AD-4) of polymer (A-4)>
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 solution of dodecylbenzenesulfonic acid, 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 simultaneously added dropwise over about 2 hours while maintaining the temperature in the reactor at 80 ° C. Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 30 minutes.
Next, 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-4) of the polymer (A-4) whose number average particle diameter is 100 nm.

[Production Example 6]
<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 7]
<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 .

In the following [Examples 1 to 24] and [Comparative Examples 1 to 5], an aqueous coating agent composition and a coating film were prepared.
[Example 1]
51.6 g of the aqueous dispersion (AD-1) of polymer (A-1) (solid content: 10.0% by mass) and water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by “Snowtex OS”; solid content 20.0% by mass) 17.2 g and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by ion-exchanged water 80.0 g of “HEC Daicel SP900”), 25% aqueous ammonia solution was added to adjust the pH of the solution to 8, and then the solid content was 1.0% by mass with ion-exchanged water. 60.0 g of (meth) acrylic acid-based thickener (D-1) (manufactured by San Nopco, “SN thickener 636”), 150 g of ethanol, and 641.2 g of ion-exchanged water were mixed and stirred. More, to give a solid content 1.0 wt% of the aqueous coating agent composition (H-1). The viscosity of the aqueous coating agent composition (H-1) was 30 mPa · s.
Next, the aqueous coating agent composition (H-1) is applied on one side of the 7 cm × 15 cm base material (the surface on which the enamel paint has been previously applied) on which the enamel paint has been applied in advance by the above method. A test plate (I-1) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-1) are shown in Table 1.

[Example 2]
Instead of 60.0 g of (meth) acrylic acid thickener (D-1) adjusted to have a solid content of 1.0% by mass with ion-exchanged water, the solid content is 1.0 mass with ion-exchanged water. % (Meth) acrylic acid thickener (D-2) (manufactured by San Nopco, “SN thickener 640”) 60.0 g was used. Other conditions were the same as in Example 1 to obtain an aqueous coating agent composition (H-2) having a solid content of 1.0% by mass. The viscosity of this aqueous coating agent composition (H-2) was 25 mPa · s.
Next, the aqueous coating agent composition (H-2) is applied on one side of the 7 cm × 15 cm base material (the surface on which the enamel paint has been previously applied) on which the enamel paint has been applied in advance by the above method. A test plate (I-2) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-2) are shown in Table 1.

Example 3
51.6 g of polymer (A-3) in water dispersion (AD-3) (solid content: 10.0% by mass) and water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by “Snowtex OS”; solid content 20.0% by mass) 17.2 g and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by ion-exchanged water 80.0 g of “HEC Daicel SP900”), 25% aqueous ammonia solution was added to adjust the pH of the solution to 8, and then the solid content was 1.0% by mass with ion-exchanged water. 60.0 g of (meth) acrylic acid-based thickener (D-2) (San Nopco, “SN thickener 640”), 150 g of ethanol, and 641.2 g of ion-exchanged water were mixed and stirred. More, to give a solid content 1.0 wt% of the aqueous coating composition of the (H-3). This aqueous coating agent composition (H-3) had a viscosity of 25 mPa · s.
Next, the aqueous coating agent composition (H-3) is applied to one side of the 7 cm × 15 cm base material (the surface pre-coated with the enamel paint) previously coated with the enamel paint by the above-described method. A test plate (I-3) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-3) are shown in Table 1.

Example 4
Instead of 60.0 g of (meth) acrylic acid thickener (D-2) adjusted to have a solid content of 1.0 mass% with ion-exchanged water, the solid content was 1.0 mass with ion-exchanged water. % (Meth) acrylic acid thickener (D-3) (manufactured by Toa Gosei Co., Ltd., “Aron A-7055”) 60.0 g was used in the same manner as in Example 3, An aqueous coating agent composition (H-4) having a solid content of 1.0% by mass was obtained. The viscosity of the aqueous coating agent composition (H-4) was 30 mPa · s.
Next, the aqueous coating agent composition (H-4) is applied on one side of the 7 cm × 15 cm base material (the surface on which the enamel paint has been previously applied), which has been previously applied with the enamel paint, on the base material. A test plate (I-4) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-4) are shown in Table 1.

Example 5
A water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd.) was added to 54.0 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-3) of the polymer (A-3). Manufactured by “Snowtex OS”; solid content 20.0% by mass) 18.0 g, and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by mass with ion-exchanged water (HEC Daicel SP900)) and 80.0 g of (meth) acrylic acid thickener (D-4) (Toa Gosei Co., Ltd.) adjusted to have a solid content of 1.0% by mass with ion-exchanged water. Manufactured by “Aron A-20P-X”), 150 g of ethanol, and 678.0 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-5 having a solid content of 1.0 mass%). ) The viscosity of the aqueous coating agent composition (H-5) was 35 mPa · s.
Next, the aqueous coating agent composition (H-5) is applied to one side of the 7 cm × 15 cm base (pre-coated) with the enamel paint in advance by the above method. A test plate (I-5) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-5) are shown in Table 1.

Example 6
A water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (Nissan Chemical Industry Co., Ltd.) was added to 54.6 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-3) of the polymer (A-3). “Snowtex OS”; 18.2 g of solid content 20.0 mass%) and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0 mass% with ion-exchanged water (HEC Daicel SP900)) and 80.0 g of (meth) acrylic acid thickener (D-4) (Toa Gosei Co., Ltd.) adjusted to have a solid content of 1.0% by mass with ion-exchanged water. Manufactured by “Aron A-20P-X”), 150 g of ethanol, and 687.2 g of ion-exchanged water, and stirred to obtain an aqueous coating composition (H-6 having a solid content of 1.0 mass%). ) The viscosity of the aqueous coating agent composition (H-6) was 25 mPa · s.
Next, the aqueous coating agent composition (H-6) is applied on one side of the 7 cm × 15 cm base material (the surface on which the enamel paint has been previously applied) on which the enamel paint has been applied in advance by the above method. A test plate (I-6) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-6) are shown in Table 1.

Example 7
An aqueous dispersion colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd.) was added to 54.0 g (solid content: 10.0% by mass) of the aqueous dispersion (AD-2) of the polymer (A-2). Manufactured by “Snowtex OS”; solid content 20.0% by mass) 18.0 g, and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by mass with ion-exchanged water (HEC Daicel SP900)) and 80.0 g of (meth) acrylic acid thickener (D-4) (Toa Gosei Co., Ltd.) adjusted to have a solid content of 1.0% by mass with ion-exchanged water. Manufactured by “Aron A-20P-X”), 150 g of ethanol, and 678.0 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-7 having a solid content of 1.0 mass%). ) The viscosity of the aqueous coating agent composition (H-7) was 33 mPa · s.
Next, the aqueous coating agent composition (H-7) is applied on one side of the 7 cm × 15 cm base material (the surface on which the enamel paint has been previously applied) on which the enamel paint has been applied in advance by the above method. A test plate (I-7) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-7) are shown in Table 1.

Example 8
Instead of 54.0 g of the aqueous dispersion (AD-2) of the polymer (A-2) (solid content: 10.0% by mass), the aqueous dispersion (AD-4) of the polymer (A-4) 54. 0 g (solid content 10.0% by mass) was used. Other conditions were the same as in Example 7 to obtain an aqueous coating agent composition (H-8) having a solid content of 1.0% by mass. This aqueous coating agent composition (H-8) had a viscosity of 32 mPa · s.
Next, the aqueous coating agent composition (H-8) is applied on one side of the 7 cm × 15 cm base material (the surface on which the enamel paint has been previously applied) on which the enamel paint has been applied in advance by the above method. A test plate (I-8) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-8) are shown in Table 1.

Example 9
A water-dispersed colloidal silica (B-2) having a number average particle diameter of 8 nm (Nissan Chemical Industries, Ltd.) was added to 54.0 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-3) of the polymer (A-3). “Snowtex S”, solid content 30% by mass) 12.0 g, and hydroxyethyl cellulose thickener (C-1) (made by Daicel Finechem) with solid content adjusted to 1.0% by mass with ion-exchanged water , “HEC Daicel SP900”), and (meth) acrylic acid thickener (D-4) (manufactured by Toa Gosei Co., Ltd.) adjusted to have a solid content of 1.0% by mass with ion-exchanged water. “Aron A-20P-X”) 20.0 g, ethanol 150 g, and ion-exchanged water 684.0 g were mixed and stirred to obtain an aqueous coating agent composition (H-9) having a solid content of 1.0 mass%. Obtained. This aqueous coating agent composition (H-9) had a viscosity of 36 mPa · s.
Next, the aqueous coating agent composition (H-9) is applied to one side of the 7 cm × 15 cm base material (the surface pre-coated with the enamel paint) previously coated with the enamel paint by the above-described method. A test plate (I-9) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-9) are shown in Table 1.

Example 10
A water-dispersed colloidal silica (B-3) having a number average particle size of 22 nm (Nissan Chemical Industries, Ltd.) was added to 54.0 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-3) of the polymer (A-3). "Snowtex OL", solid content 20.0% by mass) 18.0g, and hydroxyethyl cellulose thickener (C-1) (Daicel FineChem) whose solid content was adjusted to 1.0% by mass with ion-exchanged water (HEC Daicel SP900)) and 80.0 g of (meth) acrylic acid thickener (D-4) (Toa Gosei Co., Ltd.) adjusted to have a solid content of 1.0% by mass with ion-exchanged water. Manufactured by “Aron A-20P-X”), 150 g of ethanol, and 678.0 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-10 having a solid content of 1.0 mass%). ) The viscosity of the aqueous coating agent composition (H-10) was 30 mPa · s.
Next, the aqueous coating agent composition (H-10) is applied on one side of the 7 cm × 15 cm base material (the surface on which the enamel paint has been previously applied), which has been previously applied with the enamel paint, on the base material by the above method. A test plate (I-10) on which a coating film was formed was obtained.
The various evaluation results of this test plate (I-10) are shown in Table 1.

Example 11
The aqueous dispersion colloidal silica (B-1) having a number average particle size of 8 nm (Nissan Chemical Industry Co., Ltd.) was added to 52.2 g (solid content: 10.0% by mass) of the aqueous dispersion (AD-1) of the polymer (A-1). Manufactured by “Snowtex OS”; solid content 20.0% by mass) 17.4 g and hydroxyethyl cellulose thickener (C-2) whose solid content is adjusted to 1.0% by mass with ion-exchanged water (Sumitomo Sumitomo (Chemical company, "HECSZ-25F") is mixed with 70.0 g, and after adding a 25% aqueous ammonia solution to adjust the pH of the solution to 8, the solid content is 1.0% by mass with ion-exchanged water. 60.0 g of (meth) acrylic acid thickener (D-1) (manufactured by San Nopco, “SN thickener 636”), 150 g of ethanol, and 650.4 g of ion-exchanged water, which were adjusted to be mixed, were stirred. The solid content is 1 0% by weight of the aqueous coating agent composition (H-11) was obtained. This aqueous coating agent composition (H-11) had a viscosity of 29 mPa · s.
Next, the aqueous coating agent composition (H-11) is applied on one side of the 7 cm × 15 cm base (pre-painted with enamel paint) previously coated with the enamel paint by the above method. A test plate (I-11) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-11) are shown in Table 1.

Example 12
51.6 g of the aqueous dispersion (AD-1) of polymer (A-1) (solid content: 10.0% by mass) and water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) “Snowtex OS” (solid content 20.0% by mass) 17.2 g, and hydroxyethyl cellulose thickener (C-3) (Sansho) whose solid content was adjusted to 1.0% by ion-exchanged water 90.0 g of “San Heck HH” manufactured by the company, and 25% aqueous ammonia solution was added to adjust the pH of the solution to 8, and then the solid content was 1.0% by mass with ion-exchanged water. By mixing and stirring 50.0 g of (meth) acrylic acid-based thickener (D-1) (manufactured by San Nopco, “SN thickener 636”), ethanol 150 g, and ion-exchanged water 641.2 g. , Solid content 1.0 mass To give the aqueous coating composition of the (H-12). The viscosity of the aqueous coating agent composition (H-12) was 31 mPa · s.
Next, the aqueous coating agent composition (H-12) is applied to one side of the 7 cm × 15 cm base (previously coated with the enamel paint) previously coated with the enamel paint by the above-described method. A test plate (I-12) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-12) are shown in Table 1.

Example 13
45.0 g of the aqueous dispersion (AD-4) of the polymer (A-4) (solid content: 10.0% by mass) and water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by “Snowtex OS, solid content 20.0% by mass) 22.5 g, and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by mass with ion-exchanged water (HEC Daicel SP900)) and 80.0 g of (meth) acrylic acid thickener (D-4) (Toa Gosei Co., Ltd.) adjusted to have a solid content of 1.0% by mass with ion-exchanged water. Manufactured by "Aron A-20P-X"), 150 g of ethanol, and 682.5 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating agent composition (H-13 having a solid content of 1.0 mass%). ) The viscosity of the aqueous coating agent composition (H-13) was 35 mPa · s.
Next, the aqueous coating agent composition (H-13) is applied to one side of the 7 cm × 15 cm base material (the surface pre-coated with the enamel paint) previously coated with the enamel paint by the above-described method. A test plate (I-13) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-13) are shown in Table 2.

Example 14
63.0 g of polymer (A-4) in water dispersion (AD-4) (solid content: 10.0% by mass) and water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by “Snowtex OS”, solid content 20.0% by mass) and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by mass with ion-exchanged water (HEC Daicel SP900)) and 80.0 g of (meth) acrylic acid thickener (D-4) (Toa Gosei Co., Ltd.) adjusted to have a solid content of 1.0% by mass with ion-exchanged water. Manufactured by “Aron A-20P-X”), 150 g of ethanol, and 673.5 g of ion-exchanged water, and stirred to obtain an aqueous coating composition having a solid content of 1.0 mass% (H-14). ) This aqueous coating agent composition (H-14) had a viscosity of 29 mPa · s.
Next, the aqueous coating agent composition (H-14) is applied on one side of the 7 cm × 15 cm base material (the surface on which the enamel paint has been previously applied) on which the enamel paint has been applied in advance by the above method. A test plate (I-14) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-14) are shown in Table 2.

Example 15
57.0 g of polymer (A-4) in water dispersion (AD-4) (solid content: 10.0% by mass) and water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by “Snowtex OS”, solid content 20.0% by mass) 19.0 g, and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by mass with ion-exchanged water ("HEC Daicel SP900") 40.0g, and (meth) acrylic acid thickener (D-4) (Toa Gosei Co., Ltd.) adjusted with ion-exchanged water to a solid content of 1.0% by mass Manufactured by "Aron A-20P-X"), 75 g of ethanol, and 299.0 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating agent composition (H-15 having a solid content of 2.0% by mass). ) The viscosity of the aqueous coating agent composition (H-15) was 30 mPa · s.
Next, the aqueous coating agent composition (H-15) is applied to one side of the 7 cm × 15 cm base material (previously coated with the enamel paint) previously coated with the enamel paint by the above-described method. A test plate (I-15) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-15) are shown in Table 2.

Example 16
62.0 g of polymer (A-4) in water dispersion (AD-4) (solid content: 10.0% by mass) and water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by "Snowtex OS", solid content 20.0% by mass) and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by mass with ion-exchanged water (HEC Daicel SP900)) and 80.0 g of (meth) acrylic acid thickener (D-4) (Toa Gosei Co., Ltd.) adjusted to have a solid content of 1.0% by mass with ion-exchanged water. Manufactured by "Aron A-20P-X"), 6.2 g of inorganic oxide (E-1) having photocatalytic activity, 150 g of ethanol, and 676.8 g of ion-exchanged water, and stirring. , Solid content 1.0 mass To give the aqueous coating composition of the (H-16). This aqueous coating agent composition (H-16) had a viscosity of 33 mPa · s.
Next, the aqueous coating agent composition (H-16) is applied on one side of the 7 cm × 15 cm base material (the surface on which the enamel paint has been previously applied) on which the enamel paint has been applied in advance by the above method. A test plate (I-16) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-16) are shown in Table 2.

Example 17
59.2 g of polymer (A-4) in water dispersion (AD-4) (solid content: 10.0% by mass) and water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) "Snowtex OS", solid content 20.0% by mass) 4.8g, and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) with solid content adjusted to 1.0% by mass with ion-exchanged water (HEC Daicel SP900)) and 80.0 g of (meth) acrylic acid thickener (D-4) (Toa Gosei Co., Ltd.) adjusted to have a solid content of 1.0% by mass with ion-exchanged water. Manufactured by "Aron A-20P-X"), 5.9 g of inorganic oxide (E-1) having photocatalytic activity, and fluorocarbon surfactant (F-1) (manufactured by DIC, "Megafuck" F-444 ") 0.4g And Nord 150 g, by mixing and stirring the ion exchange water 679.7g, was obtained solid content 1.0 wt% of the aqueous coating composition of the (H-17). The viscosity of this aqueous coating composition (H-17) was 31 mPa · s.
Next, the aqueous coating agent composition (H-17) is applied on one side of the 7 cm × 15 cm base (pre-painted with enamel paint) previously coated with the enamel paint by the above method on the base. A test plate (I-17) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-17) are shown in Table 2.

Example 18
58.0 g of polymer (A-4) in water dispersion (AD-4) (solid content: 10.0% by mass) and water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by "Snowtex OS", solid content 20.0% by mass) and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by mass with ion-exchanged water (HEC Daicel SP900)) and 80.0 g of (meth) acrylic acid thickener (D-4) (Toa Gosei Co., Ltd.) adjusted to have a solid content of 1.0% by mass with ion-exchanged water. Manufactured by "Aron A-20P-X") 10.0 g, 6.6 g of an inorganic oxide (E-1) having photocatalytic activity, and fluorocarbon surfactant (F-1) (manufactured by DIC, "Megafuck" F-444 ") 0.4g And Nord 150 g, by mixing and stirring the ion exchange water 690.0g, was obtained solid content 1.0 wt% of the aqueous coating composition of the (H-18). This aqueous coating agent composition (H-18) had a viscosity of 23 mPa · s.
Next, the aqueous coating agent composition (H-18) is applied on one side of the 7 cm × 15 cm base material (the surface pre-coated with the enamel paint), which has been previously applied with the enamel paint, on the base material by the above method. A test plate (I-18) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-18) are shown in Table 2.

Example 19
A water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd.) was added to 56.0 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-4) of the polymer (A-4). Manufactured by "Snowtex OS", solid content 20.0% by mass) and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by mass with ion-exchanged water After adjusting the pH of the solution to 8 by adding 80.0 g of a “HEC Daicel SP900”) and 25% aqueous ammonia solution to a solid content of 1.0% by mass with ion-exchanged water. 60.0 g of adjusted (meth) acrylic acid thickener (D-1) (manufactured by San Nopco, “SN thickener 636”), 5.5 g of inorganic oxide (E-1) having photocatalytic activity, and fluorocarbon Surface activity (F-1) (manufactured by DIC, “Megafac F-444”) 0.4 g, ethanol 150 g, and ion-exchanged water 643.1 g are mixed and stirred to obtain an aqueous solution having a solid content of 1.0 mass%. A coating agent composition (H-19) was obtained. The viscosity of this aqueous coating agent composition (H-19) was 29 mPa · s.
Next, the aqueous coating agent composition (H-19) is applied on one side of the 7 cm × 15 cm base material (the surface on which the enamel paint has been previously applied) on which the enamel paint has been applied in advance by the above method. A test plate (I-19) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-19) are shown in Table 2.

Example 20
A water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd.) was added to 56.0 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-4) of the polymer (A-4). Manufactured by "Snowtex OS", solid content 20.0% by mass) and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by mass with ion-exchanged water 80.0 g of “HEC Daicel SP900”), 25% aqueous ammonia solution was added to adjust the pH of the solution to 8, and then the solid content was 1.0% by mass with ion-exchanged water. 60.0 g of (meth) acrylic acid thickener (D-1) (manufactured by San Nopco, “SN thickener 636”) and 8.0 g of inorganic oxide (E-2) having photocatalytic activity And fluorocarbon Surfactant (F-1) (manufactured by DIC, “Megafac F-444”) 0.4 g, ethanol 150 g, and ion-exchanged water 640.6 g are mixed and stirred to obtain a solid content of 1.0 mass. % Aqueous coating agent composition (H-20) was obtained. This aqueous coating agent composition (H-20) had a viscosity of 28 mPa · s.
Next, the aqueous coating agent composition (H-20) is applied on one side of the 7 cm × 15 cm base material (the surface on which the enamel paint has been previously applied) on which the enamel paint has been applied in advance by the above method. A test plate (I-20) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-20) are shown in Table 2.

Example 21
A water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Industry Co., Ltd.) was added to 56.0 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-4) of the polymer (A-4). Manufactured by "Snowtex OS", solid content 20.0% by mass) and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) with solid content adjusted to 1.0% by mass with ion-exchanged water 80.0 g of “HEC Daicel SP900”), 25% aqueous ammonia solution was added to adjust the pH of the solution to 8, and then the solid content was 1.0% by mass with ion-exchanged water. 60.0 g of (meth) acrylic acid thickener (D-1) (manufactured by San Nopco, “SN thickener 636”) and 10.0 g of inorganic oxide (E-2) having photocatalytic activity And fluorocarbon Surfactant (F-1) (manufactured by DIC, “Megafac F-444”) 0.4 g, ethanol 150 g, and ion-exchanged water 640.6 g are mixed and stirred to obtain a solid content of 1.0 mass. % Aqueous coating agent composition (H-21) was obtained. This aqueous coating agent composition (H-21) had a viscosity of 27 mPa · s.
Next, the aqueous coating agent composition (H-21) is applied to one side of the 7 cm × 15 cm base (previously coated with the enamel paint) previously coated with the enamel paint by the above-described method. A test plate (I-21) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-21) are shown in Table 2.

[Example 22]
58.0 g of polymer (A-4) in water dispersion (AD-4) (solid content: 10.0% by mass) and water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by "Snowtex OS", solid content 20.0% by mass) and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by mass with ion-exchanged water (HEC Daicel SP900)) and 80.0 g of (meth) acrylic acid thickener (D-4) (Toa Gosei Co., Ltd.) adjusted to have a solid content of 1.0% by mass with ion-exchanged water. Manufactured by "Aron A-20P-X") 10.0 g, 6.6 g of an inorganic oxide (E-1) having photocatalytic activity, and fluorocarbon surfactant (F-1) (manufactured by DIC, "Megafuck" F-444 ") 0.4 g 1.0 g of a fading dye (G-1) ("Acid Red" manufactured by Hodogaya Chemical Co., Ltd.), whose solid content was adjusted to 1.0 mass% with ion-exchanged water, 150 g of ethanol, and 689.0 g of ion-exchanged water. Were mixed and stirred to obtain an aqueous coating agent composition (H-22) having a solid content of 1.0% by mass. The viscosity of the aqueous coating agent composition (H-22) was 23 mPa · s.
Next, the aqueous coating agent composition (H-22) is applied to one side of the 7 cm × 15 cm base (previously coated with the enamel paint) that has been pre-coated with the enamel paint by the above-described method. A test plate (I-22) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-22) are shown in Table 2.

Example 23
A fading dye (G-) having a solid content adjusted to 1.0 mass% with ion-exchanged water instead of 1.0 g of the fading dye (G-1) having a solid content adjusted to 1.0 mass% with ion-exchange water. 2) 1.0 g (“Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) was used. Other conditions were the same as in Example 22 to obtain an aqueous coating agent composition (H-23) having a solid content of 1.0% by mass. The viscosity of the aqueous coating agent composition (H-23) was 24 mPa · s.
Next, the aqueous coating agent composition (H-23) is applied on one side of the 7 cm × 15 cm base material (the surface pre-coated with the enamel paint) previously coated with the enamel paint by the above-described method. A test plate (I-23) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-23) are shown in Table 2.

Example 24
58.0 g of polymer (A-4) in water dispersion (AD-4) (solid content: 10.0% by mass) and water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by "Snowtex OS", solid content 20.0% by mass) and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by mass with ion-exchanged water (HEC Daicel SP900)) and 80.0 g of (meth) acrylic acid thickener (D-4) (Toa Gosei Co., Ltd.) adjusted to have a solid content of 1.0% by mass with ion-exchanged water. Manufactured by "Aron A-20P-X") 10.0 g, 6.6 g of an inorganic oxide (E-1) having photocatalytic activity, and fluorocarbon surfactant (F-1) (manufactured by DIC, "Megafuck" F-444 ") 0.4 g 2.0 g of a fading dye (G-2) (“Methylene Blue”, manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0% by mass with ion exchange water, 150 g of ethanol, and 688.0 g of ion exchange water were mixed. By stirring the mixture, an aqueous coating agent composition (H-24) having a solid content of 1.0% by mass was obtained. The viscosity of the aqueous coating agent composition (H-24) was 25 mPa · s.
Next, the aqueous coating agent composition (H-24) is applied to one side of the 7 cm × 15 cm base material (the surface pre-coated with the enamel paint) previously coated with the enamel paint by the above-described method. A test plate (I-24) on which a coating film was formed was obtained. Various evaluation results of this test plate (I-24) are shown in Table 2.

[Comparative Example 1]
60.0 g of polymer (A-3) in water dispersion (AD-3) (solid content: 10.0% by mass) and water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by “Snowtex OS”; solid content 20.0 g) 20.0 g, ethanol 150 g, and ion-exchanged water 770.0 g are mixed and stirred to obtain a solid content 1.0 wt% aqueous coating agent. A composition (H-25) was obtained. The viscosity of the aqueous coating agent composition (H-25) was 2 mPa · s.
Next, the aqueous coating agent composition (H-25) is applied on one side of the 7 cm × 15 cm base material (the surface on which the enamel paint has been previously applied) on which the enamel paint has been applied in advance by the above method. A coating film was formed to obtain a test plate (I-25), and the coating film appearance (drip) was evaluated. Evaluation was x. The gloss retention after painting the aqueous coating composition, the gloss retention after 3000 hours, and the stain resistance were not evaluated.

[Comparative Example 2]
51.6 g of polymer (A-3) in water dispersion (AD-3) (solid content: 10.0% by mass) and water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by “Snowtex OS”; solid content 20.0% by mass) 17.2 g and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by ion-exchanged water "HEC Daicel SP900") 140.0g, ethanol 150g, and ion-exchanged water 641.2g were mixed and stirred to obtain an aqueous coating agent composition (H-26) having a solid content of 1.0 mass%. Got. The viscosity of the aqueous coating agent composition (H-26) was 10 mPa · s.
Next, the aqueous coating agent composition (H-26) is applied on one side of the 7 cm × 15 cm base material (the surface on which the enamel paint has been previously applied) on which the enamel paint has been applied in advance by the above method. A coating film was formed to obtain a test plate (I-26), and the coating film appearance (drip) was evaluated. Evaluation was x. The gloss retention after painting the aqueous coating composition, the gloss retention after 3000 hours, and the stain resistance were not evaluated.

[Comparative Example 3]
48.0 g of polymer (A-3) in water dispersion (AD-3) (solid content: 10.0% by mass) and water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by “Snowtex OS”; solid content 20.0% by mass) 16.0 g, and hydroxyethyl cellulose thickener (C-1) (Daicel Finechem) whose solid content was adjusted to 1.0% by mass with ion-exchanged water "HEC Daicel SP900") 200.0g, ethanol 150g, and ion-exchanged water 586.0g were mixed and stirred to obtain an aqueous coating agent composition (H-27) having a solid content of 1.0 mass%. Got. This aqueous coating agent composition (H-27) had a viscosity of 30 mPa · s.
Next, the aqueous coating agent composition (H-27) is applied on one side of the 7 cm × 15 cm base material (the surface pre-coated with the enamel paint) previously coated with the enamel paint by the above method. A test plate (I-27) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-27) are shown in Table 3.

[Comparative Example 4]
A water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (Nissan Chemical Industry Co., Ltd.) was added to 57.6 g (solid content: 10.0% by mass) of an aqueous dispersion (AD-3) of the polymer (A-3). “Snowtex OS” (solid content 20.0% by mass) 19.2 g, and (meth) acrylic acid thickener (D-4) (solid content adjusted to 1.0% by mass) ( Toa Gosei Co., Ltd. “Aron A-20P-X”) 40.0 g, ethanol 150 g, and ion-exchanged water 733.2 g were mixed and stirred to obtain an aqueous coating agent composition having a solid content of 1.0 mass%. (H-28) was obtained. This aqueous coating agent composition (H-28) had a viscosity of 32 mPa · s.
Next, the aqueous coating agent composition (H-28) is applied to one side of the 7 cm × 15 cm base material (the surface pre-coated with the enamel paint) previously coated with the enamel paint by the above-described method. A test plate (I-28) on which a coating film was formed was obtained.
Table 3 shows various evaluation results of this test plate (I-28).

[Comparative Example 5]
A water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Industries, Ltd.) Manufactured by “Snowtex OS”; solid content 20.0% by mass) 18.8 g, and xanthan gum thickener (S-1) (CP Kelco A) adjusted to 1.0% by mass with ion-exchanged water. By mixing and stirring 60.0 g of “KELZAN ST” (manufactured by Huber Company), 150 g of ethanol and 714.8 g of ion-exchanged water, an aqueous coating agent composition (H-29 having a solid content of 1.0 mass%) ) The viscosity of the aqueous coating agent composition (H-29) was 35 mPa · s.
Next, the aqueous coating agent composition (H-29) is applied on one side of the 7 cm × 15 cm base material (the surface on which the enamel paint has been previously applied) on which the enamel paint has been applied in advance by the above method. A test plate (I-29) on which a coating film was formed was obtained.
Various evaluation results of this test plate (I-29) are shown in Table 3.

  As mentioned above, according to the aqueous coating agent composition of a present Example, it was confirmed that the coating film which can maintain an external appearance and stain | pollution resistance at a high level can be formed over a long period of time.

  The aqueous coating agent composition, coating film, and coated product of the present invention can be used as various members such as architectural exterior applications, exterior display applications, automotive parts, and optical parts such as displays and lenses.

Claims (10)

An aqueous coating agent composition having a solid content of 0.5 to 2% by mass,
An aqueous dispersion (AD) of the polymer (A);
Inorganic oxide (B);
Hydroxyethyl cellulose thickener (C);
(Meth) acrylic acid thickener (D);
An aqueous coating agent composition containing   The aqueous coating agent composition according to claim 1, comprising a polymer obtained by polymerizing a vinyl monomer and a hydrolyzable silicon compound in the presence of water and an emulsifier as the component (A).   The aqueous coating agent composition according to claim 1 or 2, wherein the component (B) is silicon dioxide.   The aqueous coating agent composition according to any one of claims 1 to 3, further comprising an inorganic oxide (E) having photocatalytic activity.   The aqueous coating agent composition according to any one of claims 1 to 4, further comprising a fluorocarbon surfactant (F).   The aqueous coating agent composition according to any one of claims 1 to 5, further comprising a fading dye (G).   An aqueous paint containing the aqueous coating agent composition according to any one of claims 1 to 6.   A coating film obtained from the water-based paint according to claim 7. A substrate;
The coating film according to claim 8 formed on at least a part of the surface of the substrate;
, Painted products containing.   The coated product according to claim 9, wherein the substrate is an organic substrate.