TW201544532A - Aqueous coating agent composition, aqueous coating material, coating film and coated article - Google Patents

Abstract

Provided is an aqueous coating agent composition capable of forming a coating film maintaining the appearance and stain resistance at a high level during a long period. This aqueous coating agent composition contains: an aqueous dispersion (AD) of polymer (A), an inorganic oxide (B), a hydroxyethylcellulose thickener (C) and a (meth)acrylic acid-based thickener (D), and the solid content of this aqueous coating agent composition is 0.5 to 2% by mass.

Description

Aqueous coating composition, water-based paint, coating film, and coated product

The present invention relates to aqueous coating composition, aqueous coating, coating film and coated article.

In the past, the surface of exterior structures such as building exteriors, bridges, and storage tanks was coated with paint or the like, but the surface of the coating film was dissolved by dust, soot, sand, or the like in the air. It is contaminated by dirty components or pollutants discharged from the discharge port of a building. The contamination of such coatings is usually thinner and significantly impairs the aesthetics of the building or the structure outside the building.

There have been proposals for various techniques for such coating films.

For example, the coating film laminate disclosed in Patent Document 1 contains an organic resin and cerium oxide at a solid content ratio of 100:50 to 100:500, and the cerium oxide contained in the coating layer is derived from the average primary granule. The aggregate of the cerium sol having a diameter of 1 to 200 nm, and the coating amount of the coating layer is 0.1 to 50 g/m ² in terms of solid content.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-118567

However, in the coating material described in Patent Document 1, when a coating film is formed in a building exterior or the like coated on a vertical surface, droplets are generated, and the accumulated portion of the coating due to the droplets causes the coating film to be formed. The film thickness becomes thicker and cracks occur. On this cracked portion, there is a problem that contamination occurs due to adhesion of dust, soot, sand, and the like.

Accordingly, the present invention has been made in view of the above problems, and an object thereof is to provide an aqueous coating composition which can form a coating film which maintains a high level of appearance and stain resistance for a long period of time.

As a result of intensive investigation by the present inventors, it has been found that the above problem can be attained by using an aqueous coating composition which is an aqueous coating having a solid content of 0.5 to 2% by mass. a coating composition comprising an aqueous dispersion (AD) of a polymer (A), an inorganic oxide (B), a hydroxyethyl cellulose-based tackifier (C), and a (meth)acrylic tackifier ( D).

That is, the present invention is as follows.

[1] An aqueous coating composition having a solid content of 0.5 to 2% by mass An aqueous coating composition comprising an aqueous dispersion (AD) of a polymer (A), an inorganic oxide (B), a hydroxyethyl cellulose-based tackifier (C) and a (meth)acrylic acid Adhesive (D).

[2] The aqueous coating composition according to the above [1], wherein the component (A) is obtained by polymerizing a vinyl monomer and a hydrolyzable hydrazine compound in the presence of water and an emulsifier. polymer.

[3] The aqueous coating composition according to the above [1] or [2] wherein the component (B) is cerium oxide.

[4] The aqueous coating composition according to any one of [1] to [3] above which further contains an inorganic oxide (E) having photocatalytic activity.

[5] The aqueous coating composition according to any one of [1] to [4] above which further contains a fluorocarbon surfactant (F).

[6] The aqueous coating composition according to any one of [1] to [5] above which further contains a fading dye (G).

[7] An aqueous coating composition comprising the aqueous coating composition according to any one of the above [1] to [6].

[8] A coating film obtained from the aqueous coating material according to the above [7].

[9] A coated article comprising a substrate and a coating film according to the above [8] formed on at least a part of a surface of the substrate.

[10] The coated article according to the above [9], wherein the substrate is an organic substrate.

According to the present invention, an aqueous coating agent group can be provided The product can form a coating film which maintains a high level of appearance and stain resistance for a long period of time.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described. The following embodiments are illustrative of the present invention, and the present invention is not limited to the following. The present invention can be carried out with appropriate modifications within the scope of the gist of the invention.

[Aqueous coating composition]

The aqueous coating composition of the present embodiment is an aqueous coating composition having a solid content of 0.5 to 2% by mass, which contains an aqueous dispersion (AD) of an polymer (A), an inorganic oxide (B), A hydroxyethyl cellulose-based tackifier (C) and a (meth)acrylic tackifier (D).

The coating film obtained from the aqueous coating composition of the present embodiment can maintain a high level of appearance and stain resistance for a long period of time.

(Amount of solid content of aqueous coating composition)

The aqueous coating composition of the present embodiment has a solid content (content of solid content) of 0.5 to 2% by mass.

The amount of the solid matter in the aqueous coating composition is 0.5% by mass or more In this case, it is possible to prevent droplets when the aqueous coating composition is applied; and when it is 2% by mass or less, the transparency of the coating film can be improved.

The lower limit of the amount of the solid matter in the aqueous coating composition is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and still more preferably 0.9% by mass or more.

The upper limit of the amount 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.

The coating film is required to have a thin film thickness or use. In order to form a film having such a thin film thickness, a method of lowering the amount of solid matter in the aqueous coating composition has been tried in the past.

However, when the amount of the solid matter is lowered, the droplets of the aqueous coating composition (or the aqueous coating material) are not sufficiently prevented, so that the appearance of the coating film or the like is deteriorated.

On the other hand, in order to prevent the droplets of the aqueous coating composition (or aqueous coating) from increasing the amount of solids in the aqueous coating composition, the film thickness of the coating film is made too thick, so that a film is produced. The problem of uneven thickness or the problem of deteriorating the physical properties of the coating film.

Since the aqueous coating composition of the present embodiment contains the above-described specific component composition, it is possible to prevent droplets and form a coating film having excellent physical properties. Further, a thin coating film can be sufficiently formed. Further, since the amount of the solid matter in the aqueous coating composition of the present embodiment is in the above range, these effects can be further enhanced.

(component of aqueous coating composition) <Aqueous dispersion of polymer (A) (AD)>

The aqueous coating composition of the present embodiment contains an aqueous dispersion (AD) of the polymer (A). In the present specification, the polymer (A) may be referred to as the component (A).

As the polymer (A), a polymer obtained by a method such as emulsion polymerization can be used. Specifically, a polymer obtained by performing any polymerization reaction of radical polymerization, anionic polymerization, or cationic polymerization in an aqueous medium can be mentioned.

The component (A) is not limited to the following, and examples thereof include a poly(meth)acrylate polymer, a polyvinyl acetate polymer, a vinyl acetate-(meth)acrylic polymer, and ethylene/vinyl acetate. Ester polymer, polyoxynene polymer, fluorine polymer, polybutadiene polymer, styrene-butadiene polymer, NBR polymer, polyvinyl chloride polymer, chlorinated poly Propylene polymer, polyethylene polymer, polystyrene polymer, vinylidene chloride polymer, polystyrene-(meth)acrylate polymer, styrene-maleic anhydride polymerization a homopolymer or a copolymer represented by the substance; a polyoxymethylene-modified (meth)acrylic polymer, a fluorine-(meth)acrylic polymer, a (meth)acrylic acid-ruthenium polymer, a ring A modified co-polymer represented by an oxygen-(meth)acrylic polymer or the like.

These polymers may be used alone or in combination of two or more.

Further, "(meth)acrylate" means "acrylate" and "methacrylate" corresponding thereto, and "(meth)acrylic acid" means "acrylic acid" and "methyl" corresponding thereto. acrylic acid".

The homopolymer, the copolymer, the modified copolymer, and the like of the above polymer (A) (hereinafter, collectively referred to as "polymer") are preferably dispersed in water. The state of the body is obtained. An appropriate form of such a polymer is an emulsion, and specific examples thereof include an acrylic emulsion and an acrylic emulsion. These emulsions can be obtained, for example, by emulsion polymerization of a monomer such as (meth) acrylate or a hydrolyzable hydrazine compound described later.

The component (A) preferably contains a functional group which can interact with the inorganic oxide (B) to be described later. The interaction referred to herein may be a chemical interaction, and examples thereof include hydrogen bonding, covalent bonding, ionic bonding, and Van der Waals' forces. The hydrogen bond may, for example, be a hydrogen bond between a hydroxyl group such as a metal oxide particle and a functional group (for example, a hydroxyl group, an amine group, a guanamine group, or the like) of the polymer particle. The covalent bond may be, for example, a covalent bond produced by a condensation reaction (dehydration condensation reaction) between a hydroxyl group having a metal oxide particle or the like and a hydroxyl group of the polymer particle. Examples of the ionic bond include an ionic bond between a hydroxyl group such as a metal oxide particle and a cationic group (for example, an amine group or an imido group) in the polymer particle.

The functional group which can interact with the inorganic oxide (B) is not limited to the following, and examples thereof include a mercaptoamine group, a hydroxyl group, a carboxyl group, a carbonyl group, a stanol group, a thiol group, an amine group, an imido group, and a urea group. Base. These functional groups may be contained alone or in combination of two or more.

The aqueous coating composition of the present embodiment may further contain a compound having a functional group reactive with a functional group contained in the polymer (A), in addition to the component (A). The compound is not limited to the following, and examples thereof include a (poly)isocyanate compound, a (poly)epoxy compound, an amine compound, a (poly)carboxy compound, a (poly)hydroxy compound, and a diol compound. A stanol compound, a decyl compound, an alkoxy compound, a (meth) acrylate compound, or the like. These compounds may be used alone or in combination of two or more.

The component (A) is preferably a polymer obtained by polymerizing a vinyl monomer and a hydrolyzable hydrazine compound in the presence of water and an emulsifier.

Thereby, the effect of improving the weather resistance of a coating film can be acquired.

The number average particle diameter of the component (A) is not particularly limited, and is preferably from 10 to 300 nm, more preferably from 50 to 200 nm, still more preferably from 80 to 150 nm.

Since the component (A) having a number average particle diameter within the above range is used, the weather resistance of the obtained coating film can be further improved. Further, since the factor average particle diameter is 10 nm or more, the contamination resistance of the coating film can be further improved, and the factor average particle diameter is 300 nm or less, so that the transparency of the coating film can be further improved.

Further, the number average particle diameter referred to herein can be measured by a wet particle size analyzer.

The vinyl monomer which can be used for the production of the component (A) is not limited to the following, and examples thereof include a (meth) acrylate, an aromatic vinyl compound, an ethylene cyanide compound, and a carboxyl group-containing vinyl compound. A vinyl monomer having a functional group such as a hydroxyl group-containing vinyl compound, a epoxy group-containing vinyl compound, a vinyl compound having a quaternary and/or tertiary guanamine group, or an anionic vinyl compound.

The (meth) acrylate is not limited to the following, and examples thereof include an alkyl (meth)acrylate having an alkyl group having 1 to 50 carbon atoms, and an epoxy group having a carbon number of 1 to 100 (poly). Oxyethylene di(meth)acrylate Wait. Specific examples of such are not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethyl (meth)acrylate. Hexyl ester, methylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, and the like.

The (poly)oxyethylene di(meth)acrylate is not limited to the following, and examples thereof include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and methoxy group ( Diethylene glycol dimethacrylate, tetraethylene glycol di(meth)acrylate, and the like.

The aromatic vinyl compound is not limited to the following, and examples thereof include styrene, α-methylstyrene, p-t-butylstyrene, chlorostyrene, and vinyltoluene.

The vinyl cyanide compound is not limited to the following, and examples thereof include (meth)acrylonitrile and α-chloroacrylonitrile.

The vinyl compound containing a carboxyl group is not limited to the following, and examples thereof include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, or clothing. A half ester of a dibasic acid such as butyric acid, maleic acid or fumaric acid. The carboxyl group can be introduced into the component (A) by using a carboxyl group-containing vinyl monomer. It is presumed that the stability as an emulsion can be further improved, and the coating film is highly resistant to the dispersion and breakage action from the outside (however, the effect of the embodiment is not limited to these properties). Part or all of the introduced carboxyl group may be neutralized with an alkali such as ammonia or an amine such as triethylamine or dimethylethanolamine or NaOH or KOH. The amount of the vinyl monomer having a carboxyl group in the total amount of the above vinyl monomer, In terms of water resistance, although it is preferably 0 to 50% by mass, it is not limited to this range.

The vinyl compound having a hydroxyl group is not limited to the following, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (methyl). a hydroxyalkyl ester of (meth)acrylic acid such as acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate; (poly)oxygen having a number of from 1 to 100, 2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fumarate, allyl alcohol or epoxy ethyl Ethylene mono (meth) acrylate; (poly) oxypropylene mono (meth) acrylate having a number of epoxy propylene of 1 to 100, and "PLACCEL FM, FA monomer" (made by Daicel Chemical Co., Ltd.) The caprolactone additional monomer trade name) or other hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids.

The (poly)oxyethylene mono(meth)acrylate is not limited to the following, and examples thereof include ethylene glycol (meth)acrylate, ethylene glycol (meth)acrylate, and (methyl). Diethylene glycol acrylate, diethylene glycol (meth)acrylate, tetraethylene glycol (meth)acrylate, tetraethylene glycol (meth)acrylate, and the like.

The (poly)oxypropylene mono(meth)acrylate is not limited to the following, and examples thereof include propylene glycol (meth)acrylate, propylene glycol (meth)acrylate, and dipropylene glycol (meth)acrylate. And propylene (meth)acrylic acid dipropylene glycol ester, (meth)acrylic acid tetrapropylene glycol ester, methoxy (meth)acrylic acid tetrapropylene glycol ester, and the like.

Among the total amount of the above vinyl monomers, the hydroxyl group The ratio of the alkenyl monomer is not limited to the following, but the water resistance of the coating film is preferably from 0 to 80% by mass, more preferably from 0.1 to 50% by mass.

The vinyl compound containing a glycidyl group is not limited to the following, and examples thereof include epoxypropyl (meth) acrylate, allyl epoxidized propyl ether, and allyl dimethyl epoxypropyl group. Ether, etc.

Among the above vinyl monomers, the reactivity of the component (A) can be further improved by using a vinyl monomer containing a glycidyl group. Therefore, it is possible to obtain a coating film which is more excellent in solvent resistance and the like by crosslinking with an anthracene derivative, a carboxylic acid derivative, an isocyanate derivative or the like. In this regard, the total amount of the vinyl monomer containing a glycidyl group in the total amount of the above vinyl monomers is preferably from 0 to 50% by mass.

The vinyl compound having a quaternary amino group and/or a decylamino group is not limited to the following, and examples thereof include an N-alkyl-substituted (meth) acrylamide, and an N-alkyl-substituted (meth) propylene. Amidoxime and the like.

The N-alkyl substituted (meth) acrylamide is not limited to the following, and examples thereof include N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N,N. - dimethyl (meth) acrylamide, N, N-diethyl acrylamide, N-methyl-N-ethyl (meth) acrylamide, N-isopropyl (meth) propylene Indoleamine, N-n-propyl (meth) acrylamide, N-methyl-N-n-propyl (meth) acrylamide, N-methyl-N-isopropyl (methyl) Propylene decylamine, N-(methyl) propylene decyl pyrrolidine, N-(methyl) propylene hydrazino piperidine, N-propenyl fluorinated hexahydroquinone, N-(methyl) propylene decylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N,N'-methylenebis(meth)acrylamide, N-vinylacetamide, diacetone (meth) decylamine N-hydroxymethyl (meth) propylene oxime Amines, etc.

The vinyl monomer other than the above is not limited to the following, and examples thereof include olefins such as (meth) acrylamide, ethylene, propylene, and isobutylene; and dienes such as butadiene; vinyl chloride and vinylidene chloride. , halogenated olefins such as vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene; vinyl acetate, vinyl propionate, vinyl n-butyrate, ethyl benzoate, vinyl p-butyl butyl benzoate, Vinyl carboxylic acid esters such as trimethyl vinyl acetate, vinyl 2-ethylhexanoate, vinyl versatate, vinyl laurate, etc.; isopropenyl acetate, isopropenyl propionate, etc. Isopropyl acrylates; vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether; aromatic vinyl compounds such as styrene and vinyl toluene; allyl acetate, allyl benzoate and the like Propyl esters; allyl ethers such as allyl ether and allyl phenyl ether; 4-(methyl)propenyloxy-2,2,6,6-tetramethylpiperidine, 4-(A) Acryloxy-1,2,2,6,6-pentamethylpiperidine, perfluoromethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluoropropyl Methyl (meth) acrylate, vinyl pyrrolidone, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, and the like. These monomers 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 to be used.

The chain transfer agent is not limited to the following, and examples thereof include alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, and tri-dodecyl mercaptan; and benzyl sulfide An aromatic thiol such as an alcohol or dodecylbenzyl mercaptan; a thiocarboxylic acid such as malic acid or a salt thereof or an alkyl ester thereof; a polythiol; a diisopropyl xanthogen disulfide, a di(methylenetrimethylolpropane) xanthogen disulfide Such as disulfides; allylic compounds such as thioethylene glycol, a dimer of α-methylstyrene, and the like. These compounds may be used alone or in combination of two or more.

The amount of the chain transfer agent to be used is not particularly limited with respect to the total amount of the above vinyl monomers, and is preferably 0.001 to 30% by mass, and more preferably 0.05 to 10% by mass.

When the polymer (A) is produced by polymerization of a vinyl monomer and a hydrolyzable hydrazine compound, the hydrolyzable hydrazine compound used in the production of the polymer (A) is not limited to the following, and examples thereof include the following formula ( The compound represented by 1), the decane coupling agent, and the like are preferred.

SiW _x R _y ‧‧‧(1)

In the above formula (1), W represents an alkoxy group selected from a carbon number of 1 to 20, a hydroxyl group, an ethoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, a fluorenyl group having 1 to 20 carbon atoms, and an alkene. At least one selected from the group consisting of an oxy group, an amine group, and an amidino group.

R represents a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number 6 substituted with a halogen atom. At least one of the groups of the aryl groups of 20.

x represents an integer of 1 or more and 4 or less, and y represents an integer of 0 or more and 3 or less, and satisfies the relationship of x + y = 4.

When W is plural, and R is plural, each of W and R may be the same or different from each other.

The compound represented by the formula (1) is not limited to the following, and examples thereof include a decane oxide represented by the formula (1). In terms of hydrolysis rate, the decane oxide is preferably a 4-functional decane oxide.

The decane coupling agent may, for example, be a hydrolyzable group (for example, an alkoxy group selected from a carbon number of 1 to 20, a hydroxyl group, an ethyloxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, and a carbon number of 1 to 20). a group of at least one selected from the group consisting of a mercapto group, an alkenyloxy group, an aminooxy group, and a decylamino group, and a functional group reactive with another compound (for example, a vinyl polymerizable group, an epoxy group, or an amine) A hydrolyzable hydrazine compound (decane coupling agent) such as a group, a methacryl group, a thiol group or an isocyanate group. When such a decane coupling agent is used as the hydrolyzable hydrazine compound, the hydrolyzable hydrazine compound and the polycondensate of the vinyl monomer can be chemically bonded to each other. Thereby, the compatibility can be further improved, and the transparency of the coating film can be further improved.

Among the above, a decane coupling agent having at least a vinyl polymerizable group and/or a thiol group is preferred, and a decane coupling agent group having at least a vinyl polymerizable group is more preferable.

Since the vinyl polymerizable group or the thiol group has high reactivity with the above vinyl monomer, a chemical bond can be efficiently formed by a copolymerization reaction or a chain transfer reaction with a vinyl monomer. Therefore, when a decane coupling agent having a vinyl polymerizable group or a thiol group is used, it can be effectively compounded with other components (for example, a vinyl monomer or the like) constituting the component (A). When the component (A) which is compounded by a chemical bond such as a hydrolyzable hydrazine compound (or a polymerization product thereof) and/or a vinyl monomer (or a polymerization product thereof) is used, weather resistance and strength can be further improved. The coating film (however, the effect of the embodiment is not limited to this equivalent).

The decane coupling agent having a vinyl polymerizable group is not limited to the following, and examples thereof include 3-(meth)acryloxypropyltrimethoxydecane and 3-(meth)acryloxypropylpropyl group. Triethoxy decane, 3-(methyl) propylene methoxy propyl methyl dimethoxy decane, 3-(methyl) propylene methoxy propyl tri-n-propoxy decane, 3- (A) Acrylate methoxypropyl triisopropoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, allyl trimethoxy decane, 2-trimethoxy decyl ethyl vinyl ether Wait for the right one.

The decane coupling agent having a thiol group is not limited to the following, and examples thereof include 3-thiolpropyltrimethoxydecane and 3-thiolpropyltriethoxydecane.

The hydrolyzable hydrazine compound and the decane coupling agent represented by the formula (1) are not limited to the following, and examples thereof include tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, and tetraisopropoxy. Tetraalkoxydecanes such as decane, tetra-n-butoxydecane; methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, positive -propyltrimethoxydecane, n-propyltriethoxydecane, isopropyltrimethoxydecane, isopropyltriethoxydecane, n-butyltrimethoxydecane, n-butyltriethyl Oxydecane, n-pentyltrimethoxydecane, n-hexyltrimethoxydecane, n-heptyltrimethoxydecane, n-octyltrimethoxydecane,vinyltrimethoxydecane,vinyltriethyl Oxydecane, allyltrimethoxydecane, cyclohexyltrimethoxydecane, cyclohexyltriethoxydecane,phenyltrimethoxydecane,phenyltriethoxydecane,3-chloropropyltrimethoxy Decane, 3-chloropropyltriethoxydecane, 3,3,3-trifluoropropyltrimethoxy Decane, 3,3,3-trifluoropropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-hydroxyethyltrimethoxydecane , 2-hydroxyethyltriethoxydecane, 2-hydroxypropyltrimethoxydecane, 2-hydroxypropyltriethoxydecane, 3-hydroxypropyltrimethoxydecane, 3-hydroxypropyltriethyl Oxy decane, 3-thiol propyl trimethoxy decane, 3-thiol propyl triethoxy decane, 3-isocyanate propyl trimethoxy decane, 3-isocyanate propyl triethoxy decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2 -(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(methyl)propenyloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyl three Ethoxy decane, 3-(methyl) propylene methoxypropyl tri-n-propoxy decane, 3-(methyl) propylene methoxy propyl triisopropoxy decane, 3-ureido propyl a trialkoxy decane such as trimethoxy decane or 3-ureidopropyltriethoxy decane; dimethyl Methoxydecane, dimethyldiethoxydecane, diethyldimethoxydecane, diethyldiethoxydecane, di-n-propyldimethoxydecane, di-n-propyl Diethoxydecane, di-isopropyldimethoxydecane, di-isopropyldiethoxydecane, di-n-butyldimethoxydecane, di-n-butyldiethoxy Decane, di-n-pentyldimethoxydecane, di-n-pentyldiethoxydecane, di-n-hexyldimethoxydecane, di-n-hexyldiethoxydecane, di- n-Heptyldimethoxydecane, di-n-heptyldiethoxydecane, di-n-octyldimethoxydecane, di-n-octyldiethoxydecane, di-positive- Cyclohexyldimethoxydecane, di-n-cyclohexyldiethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, 3-(methyl)propenyloxypropyl methyl a dialkoxy decane such as dimethoxy decane; a monoalkoxy decane such as trimethyl methoxy decane or trimethyl ethoxy decane; and the like.

Among these decane coupling agents, tetraalkoxy decanes, trialkoxy decanes, dialkoxy decanes, and tetraethoxy decane, methyltrimethoxy decane, and phenyl trimethyl are preferred. Oxydecane, 3-(meth)acryloxypropyltrimethoxydecane, dimethyldimethoxydecane are more preferable, and in the case of a high hydrolysis rate, it is a tetra-functional decane oxide More preferably, oxydecane or tetraethoxydecane.

When a condensate of the compound represented by the formula (1) or a decane coupling agent is used as the hydrolyzable hydrazine compound for producing the polymer (A), the condensate of the compound represented by the formula (1) or the decane coupling agent is converted into polystyrene. The weight average molecular weight is not particularly limited and is preferably from 200 to 5,000, more preferably from 300 to 1,000. Since the condensate having a weight average molecular weight of the above range is used, the polymerization stability can be further improved.

The decane oxide or the decane coupling agent represented by the above formula (1) may be used singly or in combination of two or more. Among them, in view of the improvement of the performance of the aqueous coating composition or the obtained coating film, it is preferred to use a combination of a decane oxide and a decane coupling agent represented by the formula (1), and to be selected from tetraethoxy decane. At least one selected from the group consisting of methyltrimethoxydecane, phenyltrimethoxydecane, and dimethyldimethoxydecane, and 3-(meth)acryloxypropyltrimethoxydecane Better combined use.

The total amount of the decane coupling agent having at least a vinyl polymerizable group and/or a thiol group in 100 parts by mass of the component (A) is preferably 0.01 to 20 parts by mass in terms of polymerization stability. Between 0.1 and 10 The amount is better.

In the present embodiment, in addition to the above, the hydrolyzable hydrazine compound may be used in combination with a cyclic siloxane oligomer. By using a cyclic alumoxane oligomer in combination, a coating film which is more excellent in flexibility and the like can be obtained.

The cyclic siloxane oxide oligomer is not limited to the following, and examples thereof include a compound represented by the following formula (2).

(R' ₂ SiO) _m ‧‧‧(2)

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

Among the cyclic siloxane oxide oligomers, a cyclic dimethyl methoxy olefin oligomer such as octamethylcyclotetraoxane is preferred in terms of reactivity and the like.

When the component (A) is produced, a titanium alkoxide, a zirconium alkoxide, a condensation product or a chelate compound may be used in combination with the hydrolyzable ruthenium compound. By using these compounds in combination, a coating film which is more excellent in water resistance and the like can be obtained.

The titanium alkoxide is not limited to the following, and examples thereof include tetramethoxytitanium, tetraethoxytitanium, tetra-iso-propoxytitanium, tetra-n-propoxytitanium, and tetra-n-butadiene. Titanium oxide, titanium tetra-butoxide, titanium tetra-tert-butoxide, and the like.

When a condensate of titanium alkoxide is used, the weight average molecular weight of the converted polystyrene is not particularly limited, and is 200 to 5,000 is preferred and preferably 300 to 1,000.

The zirconium alkoxide is not limited to the following, and examples thereof include tetramethoxy zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-propoxy zirconium, and tetra-n-butyl. Oxy zirconium, tetra-second butoxy zirconium, tetra-t-butoxy zirconium, and the like.

When the zirconium alkoxide is used as a condensate, the weight average molecular weight of the condensate-converting polystyrene is not particularly limited, and is preferably from 200 to 5,000, more preferably from 300 to 1,000.

The mass ratio of the hydrolyzable hydrazine compound is preferably from 0.5/99.5 to 99.5/0.5, and more preferably from 0.5/99.5 to 15/85, relative to the vinyl monomer used in the polymerization of the polymer (A).

When the component (A) is produced, a chelating agent may be used in combination, which may coordinate to form a chelate compound on the free metal ion of the metal compound.

Examples of suitable chelating agents include alkanolamines such as diethanolamine and triethanolamine; glycols such as ethylene glycol, diethylene glycol, and propylene glycol; acetamidineacetone; ethyl acetate and the like.

The molecular weight of the chelating agent is not limited to the following, and is preferably 10,000 or less.

By using these chelating agents, the polymerization rate of the hydrolyzable hydrazine compound or the like can be controlled, and the polymerization stability in the presence of water and an emulsifier can be further improved.

The amount of the chelating agent to be formulated is not particularly limited, and it is preferably from 0.1 mol to 2 mol per mol of the free metal ion to be coordinated.

An emulsifier which can be used in the manufacture of the component (A), The following are limited to, for example, alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, polyoxyethylene alkylarylsulfuric acid, polyoxyethylene distyrylbenzene An acidic emulsifier such as ether sulfonic acid; an alkali metal (Li, Na, K, etc.) salt of the acidic emulsifier; an ammonium salt of the acidic emulsifier; an anionic surfactant such as a fatty acid soap; for example, an alkyltrimethylammonium bromide a quaternary ammonium salt such as an alkyl pyridinium bromide or an imidazolinium laurate, a pyridinium salt, an imidazolinium salt type cationic surfactant; a polyoxyethylene alkyl aryl ether and a polyoxyethylene deionized water A nonionic surfactant such as a sorbitol fatty acid ester, a polyoxyethylene oxypropylene block oligomer, or a polyoxyethylene distyryl phenyl ether; a reactive emulsifier having a radical polymerizable double bond; and the like.

Among these emulsifiers, a reactive emulsifier (reactive emulsifier) having a radical polymerizable double bond is preferred. When such a reactive emulsifier is used, the water dispersion stability of the polymer (A) can be made very good, and the water resistance of the obtained coating film can be further improved.

The anionic reactive emulsifier is not limited to the following, and examples thereof include an ethylenically unsaturated monomer having a sulfonic acid group, a sulfonate group or a sulfate group, and the like, and have a sulfonic acid. A compound of a group or an ammonium salt or an alkali metal salt (ammonium sulfonate group or an alkali metal sulfonate group) is preferred.

For example, an alkyl allyl sulfosuccinate (for example, "Eleminol (trademark) JS-20" manufactured by Sanyo Chemical Co., Ltd.; "Latemul (trademark) S-120", "made by Kao Corporation", " Latemul S-180A", "Latemul S-180", etc., for example, polyoxyethylene alkyl propylene phenyl ether sulfate (for example, "Aqualon (trademark) HS-10" manufactured by Dai-ichi Kogyo Co., Ltd.). , For example, α-[1-[(allyloxy)methyl]-2-(indolylphenoxy)ethyl]-ω-polyoxyethylene sulfate salt (for example, ADEKA, "Adekariasoap" (trademark) SE-10N", etc.), for example, ammonium-α-sulfonate-ω-1-(allyloxymethyl)alkoxypolyoxyethylene (for example, the first industrial pharmaceutical company, " Aqualon KH-1025", etc.), for example, styrene sulfonate (for example, manufactured by Tohso Organic Chemical Co., Ltd., "Spinomar (trademark) NaSS", etc.), for example, α-[2-[(allyloxy)) -1-(alkoxymethyl)ethyl]-ω-polyoxyethylene sulfate salt (for example, ADEKA CORPORATION, "Adekariasoap (trademark) SR-1025", etc.), for example, polyoxyethylene polyoxybutylene The sulfate salt of the olefin (3-methyl-3-butenyl) ether (for example, manufactured by Kao Corporation, "Latemul (trademark) PD-104, etc.)).

Among these compounds, ammonium-α-sulfonyl-ω-1-(allyloxymethyl)alkoxypolyoxyethylene, α-[2-[(allyloxy)-1-( Alkoxymethyl)ethyl]-ω-polyoxyethylene sulfate salt is preferred.

Meanwhile, as the nonionic reactive emulsifier, for example, α-[1-[(allyloxy)methyl]-2-(nonylphenoxy)ethyl]-ω-hydroxypolyoxyethylene can be cited. (For example, "Adekariasoap NE-20", "Adekariasoap NE-30", "Adekariasoap NE-40", etc.), for example, polyoxyethylene alkyl propylene phenyl ether (for example, the first "Aqualon RN-10", "Aqualon RN-20", "Aqualon RN-30", "Aqualon RN-50", etc., such as α-[2-[(allyloxy)) -1-(alkoxymethyl)ethyl]-ω-hydroxypolyoxyethylene (for example, ADEKA CORPORATION, "Adekariasoap (trademark) ER-10, etc.), for example, polyoxyethylene polyoxybutylene (3) -methyl-3-butenyl)ether (for example: flower Wang company, "Latemul (trademark) PD-420", etc.).

The amount of the emulsifier used is preferably 10 parts by mass or less, and more preferably 0.001 to 5 parts by mass, based on 100 parts by mass of the total of the hydrolyzable hydrazine compound and the vinyl monomer of the raw material of the polymer (A) component. . When the amount of the emulsifier used is in the above range, the polymerization stability and the water resistance of the coating film can be further improved.

The polymerization of the vinyl monomer and the hydrolyzable ruthenium compound is preferably carried out in the presence of a polymerization catalyst.

The polymerization catalyst of the vinyl monomer is not particularly limited, and when it is decomposed by a thermal radical or a reducing substance, it is preferably a radical polymerization catalyst which causes addition polymerization of a vinyl monomer. .

The radical polymerization catalyst is not limited to the following, and examples thereof include persulfate, peroxide, and azobis compounds. These compounds may be water soluble or oil soluble.

The radical polymerization catalyst is not limited to the following, and examples thereof include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, and tert-butylperoxybenzophenone. Acid ester, 2,2-azobisisobutyronitrile, 2,2-azobis(2-diaminopropane)hydrochloride, 2,2-azobis(2,4-dimethylvaleronitrile )Wait.

The blending amount of the radical polymerization catalyst is not particularly limited, and is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of the vinyl monomers. Further, when it is desired to accelerate the polymerization rate or to efficiently polymerize at a low temperature (for example, 70 or less), for example, sodium hydrogen sulfite, ferrous chloride, ascorbate, and a white block (that is, sodium formaldehyde sulfoxylate) may be used. reduction It is preferred to use a combination of a free radical polymerization catalyst.

The polymerization catalyst of the hydrolyzable hydrazine compound is not limited to the following, and examples thereof include hydrogen halides such as hydrochloric acid and hydrofluoric acid; carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid, and lactic acid; and sulfuric acid and p-toluenesulfonic acid. Sulfonic acid; alkyl benzene sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulphate, polyoxyethylene alkyl aryl sulphate, polyoxyethylene distyryl phenyl ether sulfonic acid, etc. Acidic emulsifiers; acidic or weakly acidic inorganic salts; acidic compounds such as phthalic acid, phosphoric acid, nitric acid; sodium hydroxide, potassium hydroxide, sodium methoxide, sodium acetate, tetramethylammonium chloride, tetramethyl Ammonium hydroxide, tributylamine, diazabicycloundecene, ethylenediamine, diethylenetriamine, ethanolamine, γ-aminopropyltrimethoxydecane, γ-(2-aminoethyl a basic compound such as aminopropyltrimethoxydecane; a tin compound such as dibutyltin octoate or dibutyltin dilaurate.

Among these polymerization catalysts, the polymerization catalyst of the hydrolyzable ruthenium compound is preferably an acidic emulsifier, not only a polymerization catalyst but also an emulsifier. The acidic emulsifier is preferably an alkylbenzenesulfonic acid having a carbon number of 5 to 30 (e.g., dodecylbenzenesulfonic acid or the like).

The polymerization of the vinyl monomer and the hydrolyzable ruthenium compound can be carried out separately, but it can be more effectively achieved by simultaneous implementation.

A suitable method for obtaining the component (A) is, for example, a so-called emulsion polymerization in which a emulsifier is formed into a micelle in the presence of a sufficient amount of water to polymerize a vinyl monomer and a hydrolyzable hydrazine compound. The specific method of the emulsion polymerization is not particularly limited, and examples thereof include a vinyl monomer and water. The decomposing hydrazine compound is dropped into the reaction vessel in a direct or emulsified state, once or in portions, or continuously, in the presence of a polymerization catalyst, preferably at a pressure of from atmospheric pressure to 10 MPa, at a temperature of about 30 to 150 ° C. Reaction temperature polymerization method, and the like.

The reaction temperature and the reaction pressure may be depending on the reaction conditions and the like instead of the above conditions.

The amount of the solid matter in the emulsion obtained by the emulsion polymerization is not particularly limited, and is preferably from 0.1 to 70% by mass, more preferably from 1 to 55% by mass, still more preferably from 5 to 30% by mass.

In the case of controlling the particle diameter in the emulsion polymerization, it is preferred to use a seed polymerization method in which the emulsion particles are previously polymerized in the aqueous phase. The pH of the polymerization system at this time is not particularly limited, and is preferably 1.0 to 10.0, 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 hydrogencarbonate or ammonia.

In the method of producing the component (A), the hydrolyzable hydrazine compound and the vinyl monomer may be polymerized in the presence of a solvent as needed in the presence of water and an emulsifier, and then water may be added until the polymerization product can be formed. The way of the lotion. However, in terms of easily controlling the particle diameter of the obtained component (A), emulsion polymerization is preferred.

The component (A) is preferably a core/shell structure having a core and a shell layer having one or two or more layers.

When the core/shell structure is provided, the mechanical properties (balance of strength and flexibility, etc.) of the obtained coating film can be further improved, which is preferable. The core/shell structure of the component (A), for example, by observing the morphology by a penetrating electron microscope or measuring the viscoelasticity Confirmation by analysis.

The method for producing the component (A) having a core/shell structure is not particularly limited, and a multistage emulsion polymerization is preferred.

The multistage emulsion polymerization referred to herein means a method of preparing two or more kinds of reaction solutions containing different compositions of a vinyl monomer or a hydrolyzable ruthenium compound, and separating the reaction solutions at respective stages.

The method of synthesizing the component (A) having a core/shell structure by two-stage emulsion polymerization is mainly described as an example of multistage emulsion polymerization.

An example of the two-stage emulsion polymerization is a step of obtaining a seed particle by polymerizing a vinyl monomer and/or a hydrolyzable hydrazine compound in the presence of water and an emulsifier (first stage), and the obtained A method (step 2) of polymerizing a hydrolyzable hydrazine compound and a vinyl monomer in the presence of seed particles.

The component (A) produced by two-stage emulsion polymerization is carried out by a polymerization step comprising the following two stages, which is the first stage of emulsion polymerization by supplying the first series (vinyl monomer and/or hydrolyzable ruthenium compound). The polymerization is carried out in the second stage polymerization in which the second series (vinyl monomer and/or hydrolyzable ruthenium compound) is supplied in the first stage and further emulsified and polymerized in an aqueous medium. In this case, the mass ratio (M1) in the first series is not particularly limited to the mass ratio ((M1)/(M2)) of the solid content (M2) in the second series, and is 9/1 to 1/9 is better and better from 8/2 to 2/8.

When such multistage emulsion polymerization is carried out, polymer particles having a more uniform particle diameter can be obtained. The method of adding the raw materials in the multistage emulsion polymerization is to prepare seed particles (core) in the polymerization in the first stage, and then chase It is preferred to add other monomers or the like. Thereby, the ratio of the volume average particle diameter to the number average particle diameter of the seed particles (core) obtained in the polymerization of the first stage can be made constant, and the particle diameter of the polymer particles obtained in the polymerization of the second stage can be made. Become bigger.

When the multistage emulsion polymerization of three or more stages is carried out, the same operation as the two-stage polymerization is carried out, and the number of polymerization stages can be increased.

The content of the component (A) in the aqueous coating composition of the present embodiment is not particularly limited, and is preferably 0.4 to 1.2% by mass, more preferably 0.4 to 0.6% by mass. When the content of the component (A) in the aqueous coating composition is within the above range, a coating film having more excellent weather resistance and stain resistance can be obtained.

The content of the component (A) in the coating film obtained from the aqueous coating composition of the present embodiment is not particularly limited, and is preferably from 30.0 to 80.0% by mass, more preferably from 40.0 to 70.0% by mass. It is more preferably 45.0 to 65.0% by mass. When the content of the component (A) in the coating film is at least the above lower limit value, the weather resistance of the coating film can be further improved, and when it is at most the above upper limit value, the stain resistance of the coating film can be further improved.

<Inorganic oxide (B)>

The aqueous coating composition of the present 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 which does not have photocatalytic activity.

As used herein, it does not have photocatalytic activity, which means that it is not exposed to light. Will cause oxidation and reduction reactions.

The component (B) is not limited to the following, and examples thereof include cerium oxide (cerium oxide), aluminum oxide (alumina), calcium citrate, magnesium oxide, cerium oxide, zirconium oxide, and composite oxides thereof. . Among these oxides, when the surface hydroxyl group is large, it is preferably cerium oxide, aluminum oxide, cerium oxide or a composite oxide thereof, and cerium oxide is more preferable.

The inorganic oxide (B) is preferably present as a colloidal particle such as a hydrate. In other words, the inorganic oxide colloidal particles can further recombine the other components of the component (A) or the component (C), and further improve the stability of the composition as an aqueous coating agent.

The cerium oxide of the inorganic oxide (B) is preferably colloidal cerium oxide. The colloidal cerium oxide may, for example, be a colloidal cerium oxide of a dispersion of water or a water-soluble solvent of cerium oxide having cerium oxide as a basic unit.

The method for producing the colloidal cerium oxide is not particularly limited, and for example, it can also be prepared by a sol-gel method. For preparation by sol-gel method, refer to Werner Stober et al.; Journal of Colloid And Interface Science, vol. 26, pp. 62-69 (1968) or Rickey D. Badley et al.; Lang muir 6, 792- 801 (1990) or "Color Materials Association", 61 [9] 488-493 (1988), etc.

The number average particle diameter of the component (B) is not particularly limited, and is preferably from 1 to 400 nm, more preferably from 1 to 100 nm, still more preferably from 5 to 30 nm.

When the number average particle diameter of the component (B) is 1 nm or more, the storage stability of the aqueous coating composition can be further improved. The number average particle diameter of the component (B) is When it is 400 nm or less, the transparency of the obtained coating film can be further improved. Further, the number average particle diameter can be measured by a wet particle size analyzer.

The colloidal cerium oxide may be acidic or basic in the state of an aqueous dispersion.

A commercially available product can also be used as the acidic colloidal cerium oxide using water as a dispersion medium. Such a commercial product is not limited to the following, and examples thereof include "Snow-Tex (trademark)-OXS", "Snow-Tex-OS", "Snow-Tex-O", and "" manufactured by Nissan Chemical Industries, Ltd." "Snow-Tex-O-40", "Snow-Tex-OL" and "Snow-Tex-OYL", "Adelite (trademark) AT-20Q" by ADEKA, and "Klebosol (trademark) 20H12 by Clariant Japan) And "Klebosol 30CAL25" and so on.

The basic colloidal cerium oxide is a colloidal cerium oxide which is stabilized by the addition of an alkali metal ion, an ammonium ion, an amine or the like. Commercially available products of such colloidal cerium oxide can also be used. These commercially available products are not limited to the following, and examples thereof include "Snow-Tex-XS", "Snow-Tex-S", "Snow-Tex-30", and "Snow-" manufactured by Nissan Chemical Industries, Ltd. Tex-50", "Snow-Tex-20L", "Snow-Tex-XL", "Snow-Tex-YL", "Snow-Tex-ZL", "Snow-Tex-NXS", "Snow-Tex-" NS", "Snow-Tex-N", "Snow-Tex-N40", "Snow-Tex-CXS", "Snow-Tex-C", "Snow-Tex-CM", "Snow-Tex-PS-" S" and "Snow-Tex-PS-M"; "Adelite AT-20", "Adelite AT-30", "Adelite AT-20N", "Adelite AT-30N", "Adelite AT-20A" manufactured by ADEKA "Adelite AT-30A", "Adelite AT-40" and "Adelite AT-50"; "Klebosol" by Clariant Japan 30R9", "Klebosol 30R50", "Klebosol 50R50", "Ludox (trademark) HS-40", "Ludox HS-30", "Ludox LS" and "Ludox SM-30" manufactured by DuPont.

A commercially available product can also be used as a colloidal cerium oxide having a water-soluble solvent as a dispersion medium. The commercially available product is not limited to the following, and examples thereof include "MA-ST-M (methanol dispersion type having a particle diameter of 20 to 25 nm)" manufactured by Nissan Chemical Industries, Ltd., and "IPAST (particle size 10 to 15 nm). "Isopropanol dispersion type", "EG-ST (ethylene glycol dispersion type of 10 to 15 nm)", "EG-ST-ZL (ethylene glycol dispersion type of 70 to 100 nm)", " NPC-ST (ethylene glycol monopropyl ether dispersion type having a particle diameter of 10 to 15 nm) and the like.

The colloidal cerium oxide may be used singly or in combination of two or more. Further, a small amount of components such as alumina or sodium aluminate may be contained. Meanwhile, the colloidal cerium oxide may also contain a stabilizer of an inorganic base (sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc.) or an organic base (tetramethylammonium or the like).

The content of the component (B) in the aqueous coating composition of the present embodiment is not particularly limited, and is preferably from 0.05 to 1.0% by mass, more preferably from 0.1 to 0.9% by mass.

When the content of the component (B) in the aqueous coating composition is within the above range, a coating film having more excellent weather resistance and stain resistance can be obtained.

The content of the component (B) in the coating film obtained from the aqueous coating composition of the present embodiment is not particularly limited, and is preferably 3.0 to 70% by mass, more preferably 3.0 to 60.0% by mass. More preferably, it is 5.0 to 50.0% by mass. The content of the component (B) in the coating film is set as described above. When the value is at least the limit, the stain resistance of the coating film can be further improved. When the value is at least the above upper limit, the weather resistance of the coating film can be further improved.

<Hydroxyethyl cellulose-based tackifier (C)>

The aqueous coating composition of the present embodiment contains a hydroxyethylcellulose-based tackifier (C). In the present specification, the hydroxyethylcellulose-based tackifier (C) may be simply referred to as the component (C).

The hydroxyethyl cellulose-based tackifier (C) includes hydroxyethyl cellulose and a modified product thereof.

As the hydroxyethyl cellulose-based tackifier (C), a commercially available product can also be used. The above-mentioned commercial products are not limited to the following, and examples thereof include "HEC Daicel SP200" manufactured by Daicel Precision Chemical Co., Ltd., "HEC Daicel SP400", "HEC Daicel SP500", "HEC Daicel SP550", and "HEC". Daicel SP600, HEC Daicel SP800, HEC Daicel SP850 and HEC Daicel SP900, Sanhec (trademark) HH, Sanhec H, Sanhec M and Sanhec G&L, "HECSZ-25F" made by Sumitomo Seiki Co., Ltd., etc.

These hydroxyethylcellulose-based tackifiers (C) may be used singly or in combination of two or more.

The weight average molecular weight of the hydroxyethyl cellulose-based tackifier (C) is not particularly limited, and is preferably from 700,000 to 2,000,000, and more preferably from 1,000,000 to 1.6 million. Since the weight average molecular weight is 700,000 or more, droplets of the aqueous coating composition can be further prevented. When the weight average molecular weight is 2,000,000 or less, the composition obtained by the aqueous coating agent can be further improved. The transparency of the film. The weight average molecular weight can be determined by gel permeation chromatography (GPC).

The content of the component (C) in the aqueous coating composition of the present embodiment is not particularly limited, and is preferably from 0.05 to 0.1% by mass, more preferably from 0.07 to 0.09% by mass. When the content of the component (C) in the aqueous coating composition is in the above range, a coating film having more excellent transparency and weather resistance can be obtained.

The content of the component (C) in the coating film obtained from the aqueous coating composition of the present embodiment is not particularly limited, and is preferably 2.0 to 10.0% by mass, more preferably 4.0 to 9.0% by mass. When the content of the component (C) in the coating film is at least the above lower limit value, the transparency of the coating film can be further improved, and when it is at most the above upper limit value, the weather resistance of the coating film can be further improved.

<(Meth)acrylic tackifier (D)>

The aqueous coating composition of the present embodiment contains a (meth)acrylic tackifier (D). In the present specification, the (meth)acrylic tackifier (D) may be simply referred to as the component (D).

The (meth)acrylic tackifier (D) contains at least (meth)acrylic acid in (meth)acrylic acid and (meth)acrylic acid, and contains such (meth)acrylic acid and/or A copolymer of (meth) acrylate as a main component.

The term "main component" means that the copolymer contains 50% by mass or more of (meth)acrylic acid and/or (meth)acrylic acid ester.

The (meth)acrylic acid is not limited to the following, but for example, Acrylic acid, methacrylic acid, etc. Meanwhile, the (meth) acrylate is not limited to the following, and examples thereof include methyl methacrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and n-propyl (meth) acrylate. Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (a) Base) 2-hydroxypropyl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like. Also, other monomers may be copolymerized, such as crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, acrylonitrile, (meth) propylene. Guanidine, N-methylol acrylamide, glycidyl methacrylate, and the like.

The (meth)acrylic tackifier (D) is usually used in the form of an aqueous solution neutralized with a basic substance. The basic substance is not limited to the following, and examples thereof include an alkanolamine such as triethanolamine or monoethanolamine, an inorganic base such as ammonia, sodium hydroxide or potassium hydroxide, or a basic amino acid such as arginine. In addition, the amount of the basic substance to be added may be any amount sufficient to neutralize the above-mentioned copolymer, and may be appropriately formulated in accordance with the kind or amount of the components.

The (meth)acrylic tackifier (D) may be any of a powder, an aqueous solution or an emulsion.

A commercially available product can also be used as the (meth)acrylic tackifier (D) of the powder. The commercial product is not limited to the following, and examples thereof include "Aron (trademark) A-20P-X", "Aronvis (trademark) MX", and "JURYMER (trademark) AC-10LHP" manufactured by Toagos Corporation. "JURYMER AC-10SHP", "Rheogic (trademark) 260H", "Rheogic 262L", "Rheogic 845H", "Junlon (trademark) PW-120", "Junlon PW-121" and "Junlon PW-160".

A commercially available product can also be used as the (meth)acrylic tackifier (D) in an aqueous solution. Such a commercial product is not limited to the following, and examples thereof include "Aron A-20L", "Aron A-7100", "Aron A-10H", "Aron A-30", and "Aron A-30" manufactured by Toagos Corporation. Aron A-7255", "Aron A-7185" and "Aron A-7195".

As the (meth)acrylic tackifier (D) of the emulsion, a commercially available product can also be used. Such a commercial product is not limited to the following, and examples thereof include "Aron A-7075", "Aron A-7055", "Aron B-300K", and "Aron B-500" manufactured by Toagos Corporation. "SN-Thickener (trademark) 630", "SN-Thickener634", "SN-Thickener 636", and "SN-Thickener 640" manufactured by San Nopco Co., Ltd.

These (meth)acrylic tackifiers (D) may be used singly or in combination of two or more.

The weight average molecular weight of the (meth)acrylic tackifier (D) is not particularly limited, and is preferably from 100,000 to 6,000,000, and more preferably from 500,000 to 5,000,000. Since the weight average molecular weight is 100,000 or more, droplets of the aqueous coating composition can be further prevented. Since the weight average molecular weight is 6,000,000 or less, the transparency of the coating film obtained from the aqueous coating composition can be further improved. The weight average molecular weight can be determined by gel permeation chromatography (GPC).

The content of the component (D) in the aqueous coating composition of the present embodiment is not particularly limited, and is 0.005 to 0.1% by mass. Preferably, it is preferably 0.01 to 0.07 mass%. When the content of the component (D) in the aqueous coating composition is in the above range, a coating film which is more excellent in transparency and weather resistance can be obtained.

The content of the component (D) in the coating film obtained from the aqueous coating composition of the present embodiment is not particularly limited, and is preferably from 0.5 to 8.0% by mass, more preferably from 1.0 to 6.0% by mass.

When the content of the component (D) in the coating film is at least the above lower limit value, the transparency of the coating film can be further improved, and when it is at most the above upper limit value, the weather resistance of the coating film can be further improved.

Further, in the range in which the effects of the present embodiment can be obtained, other thickeners may be used in combination with the aqueous coating composition of the present embodiment.

The other tackifiers are not limited to the following, and examples thereof include a polysaccharide-based tackifier and a vinyl ether-based tackifier.

<Inorganic oxide (E) having photocatalytic activity>

The aqueous coating composition of the present embodiment preferably contains an inorganic oxide (E) having photocatalytic activity. Thereby, photocatalytic activity and hydrophilicity can be exhibited by irradiating light onto the coating film.

In the present specification, the inorganic oxide (E) may be simply referred to as the component (E).

The inorganic oxide (E) is not particularly limited as long as it is an inorganic oxide having photocatalytic activity.

Component (E) is not limited by the following, but examples thereof _{include: 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 ; having a selected from the group consisting of Ti, Nb, Ta, and V A layered oxide of at least one of the elements in the group (for example, JP-A-62-074452, JP-A-2002-172535, JP-A-H07-024329, JP-A-2008-- Japanese Laid-Open Patent Publication No. Hei 08-089800, Japanese Laid-Open Patent Publication No. Hei 08-089804 .

The (E) component is preferably TiO ₂ (titanium oxide) in terms of chemical stability, toxicity, environmental surface, and the like. The titanium oxide may be any crystal structure of an anatase type, a rutile type or a brookite type.

The component (E) is an inorganic oxide having photocatalytic activity, and a metal compound whose surface is modified by a particle is preferred. By modifying the surface of the particles, the amount of active oxygen species such as H ₂ O ₂ or ‧ OH can be suppressed, and the damage of the undercoat film can be prevented.

The substance for modifying the surface of the particles is not limited to the following, and examples thereof include cerium oxide, aluminum oxide, copper oxide, and iron oxide. Among these substances, cerium oxide is preferred. Further, the surface of the particles is modified with a complex such as Fe, Cu, Al, or Pt, or a complex such as chloroplatinic acid, and the same effect can be obtained.

A method of modifying the surface of the component (E) by using titanium oxide as an example will be described.

The method of modifying the surface of the titanium oxide is not particularly limited, and examples thereof include a method in which a cerium compound is added to a slurry of titanium oxide, and a hydrated oxide of cerium is precipitated by a step of neutralization treatment or the like.

The hydrazine compound is not particularly limited, and a water-soluble ceric acid alkali metal salt such as sodium citrate can be used. Among these compounds, sodium citrate is preferred because it is colorless and does not cause the titanium oxide sol to be uncolored.

The amount of the hydrated oxide to be treated is preferably from 3 to 25% by mass, and more preferably from 5 to 20% by mass, based on the oxide of the titanium oxide.

When the amount of the treatment is at least the above lower limit value, the amount of the active oxygen species can be prevented from increasing, so that the undercoat film can be prevented from being damaged. At the same time, since the treatment amount is at most the above upper limit value, aggregation of titanium oxide can be prevented, and the viscosity of the sol can be prevented from increasing, so that dispersibility or transparency can be further improved.

The content of the component (E) in the aqueous coating composition of the present embodiment is not particularly limited, and is preferably 0.1 to 0.3% by mass, more preferably 0.15 to 0.20% by mass. When the content of the component (E) in the aqueous coating agent is in the above range, a coating film which is more excellent in stain resistance and transparency can be obtained.

The content of the component (E) in the coating film obtained from the aqueous coating composition of the present embodiment is not particularly limited, and is preferably from 10.0 to 25.0% by mass, more preferably from 15.0 to 20.0% by mass. When the content of the component (E) in the coating film is at least the above lower limit value, the stain resistance of the coating film can be further improved, and when it is at most the above upper limit value, the transparency of the coating film can be further improved.

<Fluorocarbon surfactant (F)>

The aqueous coating composition of the present embodiment preferably further contains a fluorocarbon surfactant (F). In this specification, fluorocarbon surfactant (F) is sometimes used. Referred to as (F) component.

When the aqueous coating composition of the present embodiment contains the component (F) and is coated with the aqueous coating composition of the present embodiment or the aqueous coating material containing the same, the organic substrate can be further improved. The wettability prevents the appearance of problems such as drainage. In addition, the uniformity of the coating film can be further improved. Although it is not clear about these reasons, it is estimated that the surface tension of the aqueous coating composition can be lowered by containing the component (F) (however, the action of the embodiment is not limited thereto).

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, a nonionic amphoteric surfactant is preferred, and an amphoteric surfactant having a perfluoroalkyl group having 3 to 20 carbon atoms is more preferred.

The amphoteric surfactant having a perfluoroalkyl group having 3 to 20 carbon atoms is not limited to the following, and examples thereof include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, and perfluoroalkyl epoxy. Ethane adducts, etc. Among these, in terms of a decrease in the surface tension of the coating, a perfluoroalkyl ethylene oxide adduct is preferred. As the perfluoroalkyl ethylene oxide adduct, for example, a commercially available product can also be used. The commercially available product is not limited to the following, and examples thereof include "Megafac (trademark) F-444" manufactured by DIC Corporation, "Surflon (trademark) S-242" manufactured by AGC Semi Chemical Co., Ltd., and the like. These may be used alone or in combination of two or more.

The content of the component (F) in the aqueous coating composition of the present embodiment is not particularly limited, and is 0.01 to 0.1% by mass. Preferably, it is preferably 0.02 to 0.05% by mass. When the content of the component (F) is at least the above lower limit value, the uniformity of the obtained coating film can be further improved. When the content of the component (F) is at most the above upper limit value, the weather resistance of the obtained coating film can be further improved.

<Fading Pigment (G)>

The aqueous coating composition of the present embodiment preferably contains a fading dye (G). In the present specification, the fading dye (G) may be simply referred to as the (G) component. Since the aqueous coating composition of the present embodiment contains the discolored pigment (G), problems such as forgetting to apply, repeating coating, and uneven coating can be prevented.

The component (G) is preferably designed to be discolored by irradiation with sunlight and does not impair the design of the substrate. The time until the fading varies depending on the season or the direction of the irradiation, but it is usually visually confirmed until the fading period is preferably 20 days or less, more preferably 10 days or less, and still more preferably 3 days or less.

The component (G) is not particularly limited as long as it has a property of fading by sunlight, and examples thereof include, for example, methylene blue, crystal violet, malachite green, brilliant blue-FCF, and red algae. One of the group of red, neocarmine, phloxin, bengal rose red, acid red, and fast green FCF. Among these ingredients, methylene blue is preferred in terms of good color rendering and fast fading speed. These components may be used alone or in combination of two or more.

The content of the component (G) in the aqueous coating composition of the present embodiment is not particularly limited, and is 0.0005 to 0.01% by mass. Preferably, it is preferably 0.001 to 0.003 mass%. When the content of the component (G) in the aqueous coating composition is within the above range, the color developability or fading property of the coating film can be further improved. The color rendering property referred to herein means the coloring property which can be visually distinguished from the color of the painted surface and the uncoated surface; the fading property refers to the degree of fading to the extent that the design of the substrate is not damaged. The nature.

The content of the component (G) in the coating film obtained from the aqueous coating composition of the present embodiment is not particularly limited, and is preferably 0.01 to 0.5% by mass, more preferably 0.05 to 0.2% by mass. It is more preferably 0.1 to 0.2% by mass. When the content of the component (G) is at least the above lower limit value, the color developability of the coating film can be further improved, and when it is at most the above upper limit value, the fading property of the coating film can be further improved.

<Other ingredients>

The aqueous coating composition of the present embodiment may contain other components than the above, as needed, within the range in which the effect can be obtained. Such other components are not limited to the following, and examples thereof include an antifoaming agent, a freeze stabilizer, a light-reducing agent, a crosslinking reaction catalyst, a pigment, a curing catalyst, a crosslinking agent, a filler, and an anti-knot. Skin agent, dispersant, wetting agent, light stabilizer, antioxidant, ultraviolet absorber, film forming aid, rust inhibitor, plasticizer, lubricant, reducing agent, preservative, antifungal agent, anti-algae agent, Deodorant, anti-yellowing agent, antistatic agent or conductive modifier. These components may be used alone or in combination of two or more.

[Water-based paint]

The above aqueous coating composition can be suitably used as an aqueous coating.

That is, the aqueous coating material of the present embodiment contains the above aqueous coating composition.

The aqueous coating material can be obtained by mixing other components as needed in the aqueous coating composition of the present embodiment.

The other components are not limited to the following, and examples thereof include an antifoaming agent, a freeze stabilizer, a light-reducing agent, a crosslinking reaction catalyst, a pigment, a curing catalyst, a crosslinking agent, a filler, and an anti-skinning agent. , dispersant, wetting agent, light stabilizer, antioxidant, UV absorber, filming aid, rust inhibitor, plasticizer, lubricant, reducing agent, preservative, mold inhibitor, algaecide, deodorant Agent, anti-yellowing agent, antistatic agent or conductive modifier.

The aqueous coating material of the present embodiment can be applied by an appropriate method in accordance with the use thereof, the material to be coated, and the like. The coating method is not limited to the following, and examples thereof include a spray blowing method, a flow coating method, a roll coating method, a brush coating method, a dip coating method, a spin coating method, a screen printing method, a casting method, and a gravure printing method. , flexographic printing method.

[coating film]

The coating film of the present embodiment can be obtained by applying the aqueous coating material to a predetermined application target, drying it, and removing volatile matter. At this time, it is also possible to carry out heat treatment at a temperature of about 40 to 120 ° C or ultraviolet irradiation treatment as necessary.

[painted products]

The coated article of the present embodiment contains a substrate and the coating film formed on at least a part of the surface of the substrate.

The coated article of the present embodiment can be obtained, for example, by applying the above aqueous coating material to the surface of various substrates and drying it.

The base material used in the coated product of the present embodiment is not particularly limited as long as it can form a coating film on the surface thereof, and may be an organic base material or an inorganic base material, but the weather resistance and the stain resistance are improved. In other words, organic substrates are preferred.

The material of the substrate is not limited to the following, and examples thereof include organic substrates such as synthetic resins and natural resins; and inorganic substrates such as metals, ceramics, glass, stone, cement, and concrete. These materials may be used alone or in combination of two or more.

The synthetic resin is not limited to the following, and examples thereof include a thermoplastic resin and a curable resin (thermosetting resin, photocurable resin, moisture curable resin, and the like).

Specific examples of the synthetic resin are not limited to the following, and examples thereof include a polyoxyxylene resin, an acrylic resin, a methacrylic resin, a fluororesin, an alkyd resin, an amino alkyd resin, a vinyl resin, and a polyester resin. , styrene-butadiene resin, polyolefin resin, polystyrene resin, polyketone resin, polyamide resin, polycarbonate resin, polyacetal resin, polyether ether ketone resin, polyphenylene ether resin, polyfluorene Resin, polyphenylene resin, polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, urea resin, phenol resin, melamine resin, epoxy resin, polyurethane resin, polyoxyl-acrylic resin, and the like.

The natural resin is not limited to the following, but examples thereof are mentioned Examples include a cellulose resin, a isopentenyl resin such as natural rubber, and a protein resin such as casein.

When the base material is a base material made of a resin such as the above synthetic resin or natural resin, surface treatment such as corona discharge treatment, flame treatment, or plasma treatment may be applied as needed.

The coated product of the present embodiment includes a substrate and the above-mentioned coating film formed on the substrate, and the coating film can also be applied as a paint or the like.

Since the coating film obtained from the aqueous coating composition of the present embodiment can maintain a high level of appearance and antifouling properties for a long period of time, it can be applied to an environment that has been difficult to use for a long time.

In this regard, the coated product of the present embodiment is not limited to the following, and examples thereof include building materials, building exteriors, building interiors, window frames, window glass, various lenses, structural members, and houses. Lamps and window glazing for construction equipment, vehicle lighting, exterior decoration of mechanical devices or articles, dust cover and painting, display, cover, traffic signs, various displays, advertising towers, etc., roads and railways Electrical and electrical equipment exterior parts used in exteriors such as soundproof walls, bridges, exteriors and coatings for guard rails, tunnel interiors and coatings, insulators, solar cell covers, and solar thermal water heaters. Especially for exterior parts of transparent components, plastic greenhouses, greenhouses, etc.

In the method for producing a coated product of the present embodiment, for example, the aqueous coating material (or aqueous coating composition) is applied to at least a part of the surface of the substrate, and if necessary, dried to form a coating film. Method, but not limited to this method. For example, after the coating film of the present embodiment is applied onto a substrate, the coating film may be peeled off from the substrate, and the coating film may be peeled off from the substrate. Substrate followed by. Alternatively, after the coating film of the present embodiment is applied onto a substrate, it is adhered to the other substrate in a state of being adhered to the substrate.

The aqueous coating composition of the present embodiment can also be blended in various aqueous coating materials. Such a water-based paint can form a coating film excellent in appearance and stain resistance, and excellent in transparency and weather resistance. Therefore, the coating film of the present embodiment can be used for a wide range of applications including exterior coatings and the like for appearance and stain resistance, and also excellent in transparency and weather resistance.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples below.

The methods for measuring the physical properties in the examples and comparative examples described later are as follows.

(Method for measuring physical properties) <1. Solid amount>

2 g of the sample was placed on an aluminum dish and heated at 150 ° C for 1 hour. The mass of the sample before and after heating was measured, and the amount of solid matter (% by mass) was calculated from the difference.

<2. Number average particle diameter>

The mixture was diluted with ion-exchanged water until the load index was 1.5 to 3.0, and it was measured by a wet particle size analyzer ("MicroTrack UPA-9230", manufactured by Nikkiso Co., Ltd.). The measurement conditions are presented below.

‧Load index: 1.5 to 3.0

‧ Measurement time: 60 seconds

‧Number of measurements: 3 times

<3. Viscosity>

It was measured by a BM type viscometer (manufactured by Toki Sangyo Co., Ltd.). The measurement conditions are presented below.

‧ Temperature: 23 ° C

‧Rotator: No 1

‧Number of rotation: 60rpm

<4. Glass transition temperature>

The "DCS6220" manufactured by Seiko Instruments Co., Ltd. was measured at a temperature rising rate of 10 ° C /min, and the glass transition temperature was determined by the inflection point of the obtained DSC curve. Further, the measurement conditions are shown below.

‧Measurement storage tank: aluminum container

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

<5. Appearance of film (droplet)>

On the single side of the 7 cm × 15 cm substrate on which the enamel paint described later was pre-coated (the surface of the enamel paint was pre-coated), the aqueous coating composition was applied by spraying to make the coating amount 25 g/m ² . proportion. The coated substrate was kept vertical, and the degree of liquid droplets after standing for 10 minutes was visually evaluated under the conditions of a temperature of 23 ° C and a relative humidity of 50%. The appearance of the coating (droplet) was evaluated by the following criteria.

○: It was confirmed that there were almost no droplets.

△: A number of droplets were confirmed.

×: A lot of droplets were confirmed.

<6. Gloss>

The 60° gloss of the measurement sample was measured by a "micro-TRI-gloss μ" manufactured by BYK-Gardner Co., Ltd.

<7. Gloss retention rate after coating of aqueous coating composition>

On the single side of the 7 cm × 15 cm substrate (pre-coated enamel coating surface) of the enamel coating which has been pre-coated, the first coating is applied by spraying to make the coating amount of the aqueous coating composition become A ratio of 25 g/m ² . The coated substrate was kept vertical, and after standing at a temperature of 23 ° C and a relative humidity of 50% for 2 hours, the second coating was performed in the same manner as the first coating. The coated substrate was held vertically, and allowed to stand at a temperature of 23 ° C and a relative humidity of 50% for 24 hours, and then measured by a gloss meter ("micro-TRI-gloss μ" manufactured by BYK-Gardner Co., Ltd.). 60° gloss. At the same time, the 60° gloss of the surface of the substrate before the application of the aqueous coating composition was also determined in advance using a gloss meter.

Then, the gloss retention ratio was calculated according to the following formula.

The higher the value of the gloss retention, the more excellent the transparency and the better the substrate design.

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

<8. Gloss retention rate after 3,000 hours of weather resistance test>

On the one side of the 7 cm × 15 cm substrate of the enamel coating (the surface of the precoated enamel coating), the first coating was applied by spraying to make the coating amount of the aqueous coating composition become A ratio of 25 g/m ² . The coated substrate was kept vertical, and after standing at a temperature of 23 ° C and a relative humidity of 50% for 2 hours, the second coating was performed in the same manner as the first coating. The coated substrate was kept vertical, and allowed to stand at a temperature of 23 ° C and a relative humidity of 50% for 24 hours to prepare a test plate.

The exposure test of this test plate was carried out using a "Sunshine Weathermeter" manufactured by Suga Test Machine Co., Ltd. (black panel temperature: 63 ° C, rainfall: 18 minutes / 2 hours). The 60° gloss before and after the exposure test was measured using a gloss meter ("Microtrigloss μ" manufactured by BYK Gardner Co., Ltd.).

Then, the gloss retention ratio was calculated according to the following formula. The higher the value of the gloss retention, the better the weather resistance.

Further, the 60° gloss retention of the substrate on which only the enamel paint was precoated was 95%.

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

<9. Pollution resistance>

On the one side of the 7 cm × 15 cm substrate (pre-coated enamel coating surface) of the enamel coating which has been pre-coated, the first coating is applied by spraying to make the coating amount of the aqueous coating composition as It became a ratio of 25 g/m ² . The coated substrate was kept vertical, and after standing at a temperature of 23 ° C and a relative humidity of 50% for 2 hours, the second coating was performed in the same manner as the first coating.

The coated substrate was kept vertical, and allowed to stand at a temperature of 23 ° C and a relative humidity of 50% for 24 hours to prepare a test plate.

Adhere the test panel to a fence facing the general road (about 500 to 1,000 vehicles per day) and let it stand for 6 months or 1 year.

According to the above criteria, the degree of contamination of the test plate after standing was visually evaluated.

Moreover, the results of only the substrates on which the enamels were pre-coated were evaluated, and were evaluated as "x" at 6 months and 1 year.

○: Confirm that there is almost no pollution.

△: It is confirmed how much pollution is present.

×: A large amount of contamination was confirmed.

<10. Wet decomposition performance>

On the single side of the 7 cm × 15 cm substrate (pre-coated enamel coating surface) of the enamel coating which has been pre-coated, the first coating is applied by spraying to make the coating amount of the aqueous coating composition become A ratio of 25 g/m ² .

The coated substrate was kept vertical, and after standing at a temperature of 23 ° C and a relative humidity of 50% for 2 hours, the second coating was performed in the same manner as the first coating.

The coated substrate was kept vertical, and allowed to stand at a temperature of 23 ° C and a relative humidity of 50% for 24 hours to prepare a test plate.

According to JIS R1703-2 (Fine Ceramics - Photocatalyst) Self-cleaning performance test method - part 2: wet decomposition performance), the test plate was tested to obtain a decomposition activity index.

The higher the decomposition activity index, the better the self-cleaning property.

The method for producing the substrate for the measurement sample used in the method for measuring the physical properties is as follows.

<Preparation of 7cm × 15cm substrate with pre-coated enamel paint> ‧Production of pigment dispersion

5.35 g of a dispersing agent ("Pig‧Disperser MD20" manufactured by BASF Japan Co., Ltd.), 0.50 g of ammonia water, 23.50 g of propylene glycol, 147.50 g of water, and titanium oxide (chlorinated rutile type titanium dioxide; manufactured by Ishihara Sangyo Co., Ltd., "Tipaque CR-97" ” 333.50g, defoamer (modified polyoxane system; San Nopco company, "SN Defoamer-1310") 2.85g formula, with table sand mill (Kanpepapio company, batch table sand The mill was allowed to disperse for 20 minutes to obtain pigment dispersion.

‧Enamel paint production

To 109.0 g of the polymer emulsion of Production Example 1, 2,2,4-trimethyl-1,3-butanediol isobutyrate ("CS-12", manufactured by Chisso Co., Ltd.) was added in an amount of 10.0 g, and ethylene 10.0 g of a mixture of 50 parts by mass of alcohol 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 tackifier ("ADEKANOL UH-438" manufactured by ADEKA CORPORATION) were mixed. 1 hour, that is, enamel paint.

‧Preparation of 7cm×15cm substrate with pre-coated enamel paint

The enamel paint obtained above was applied to a 7 cm × 15 cm sulfuric acid anodized aluminum plate by a wire bar coater-No 50, and dried at a temperature of 23 ° C and a relative humidity of 50% for 48 hours to obtain a pre-coated enamel. A 7 cm x 15 cm substrate of the coating. The gloss of the resulting substrate was 75.

The following are the aqueous dispersions of the polymers (Production Examples 1 to 5) used in Examples and Comparative Examples described later, and the production methods of the inorganic oxides having photocatalytic activity (Production Examples 6 to 7).

[Manufacturing Example 1] <Synthesis of Polymer Emulsion>

In a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device, 290 g of ion-exchanged water and a reactive emulsifier ("Adekariasoap SR-1025" manufactured by Adeka; 25% by mass aqueous solution of solid content) 8.0 g were charged. The temperature in the reactor was warmed to 80 ° C while stirring. Into this reactor, 10 g of a 2% by mass aqueous solution of ammonium persulfate was charged. 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, and a reactive emulsifier (manufactured by Adeka Co., Ltd., "Adekariasoap SR-1025"; a solid content of 25% by mass aqueous solution) 4.0 g, an emulsion mixture of 15 g of a 2% by mass aqueous solution of ammonium persulfate and 48 g of ion-exchanged water was dropped from the dropping tank over 40 minutes. The temperature of the reaction vessel was maintained at 80 ° C during the dropwise addition. The temperature in the reactor was also maintained at 80 ° C after the end of the dropwise addition, and stirring was continued for 30 minutes.

Next, the temperature in the reactor was maintained at 80 ° C, and a mixture containing 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 were contained. (Adekariasoap SR-1025, manufactured by Adeka Co., Ltd.; 25% by mass aqueous solution), 16.0 g, 60 g of a 2% by mass aqueous solution of ammonium persulfate, and 192 g of ion-exchanged water, and 3-methyl propylene oxide A mixture of 1 g of propyltrimethoxydecane, 20 g of dimethyldimethoxydecane and 20 g of methyltrimethoxydecane was added dropwise over 160 minutes by means of separate dropping tanks. Further, the temperature in the reactor after the completion of the dropwise addition 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 liquid, and the reaction liquid was filtered through a metal mesh of 100 mesh while adjusting the pH to 8, to obtain a polymer emulsion. The amount of the solid matter of the obtained polymer emulsion was 44.5 mass%.

For the polymer contained in this polymer emulsion, the glass transition temperature determined from the inflection point of the DSC curve was 40 ° C according to the above method.

[Manufacturing 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 stirring device, 500 g of ion-exchanged water and a reactive emulsifier ("Adekariasoap SR-1025" manufactured by Adeka; 25% by mass aqueous solution of solid content) were charged. After 15 g of a 2% by mass aqueous solution of ammonium sulfate, the temperature in the reactor was heated to 80 ° C with stirring. The temperature in the reactor was maintained at 80 ° C, and 400 g of methyl methacrylate, 250 g of cyclohexyl methacrylate, 300 g of n-butyl acrylate, and 2-hydroxyethyl methacrylate were added dropwise over about 4 hours. 20 g, 30 g of methacrylic acid, and a reactive emulsifier ("Adekariasoap SR-1025" manufactured by ADEKA Co., Ltd.; solid content: 25% by mass water-soluble 40 g of an aqueous solution of 40 g of a 2% by mass aqueous solution of ammonium persulfate and 700 g of ion-exchanged water.

After the end of the dropwise addition, the temperature in the reactor was also maintained at 80 ° C, and stirring was continued for 2 hours.

After cooling to room temperature, the hydrogen ion concentration of the reaction liquid in the reactor was measured, and the pH was 2.1.

After adding a 25% aqueous ammonia solution to the reaction liquid and adjusting the pH to 8, the reaction liquid was filtered through a metal mesh of 100 mesh.

Further, the amount of the solid matter was adjusted to 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion (AD-1) of the polymer (A-1) having a number average particle diameter of 130 nm.

[Manufacturing 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 stirring device, 609 g of ion-exchanged water and a reactive emulsifier (manufactured by Kao Corporation, "Latemul S-180A") were added in an amount of 10 g of a 25 mass% aqueous solution, methacrylic acid. 26 g of cyclohexyl ester, 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 the reactor was stirred under stirring. The temperature in the temperature was raised to 80 °C. In this reactor, 5 g of a 2% by mass aqueous solution of ammonium persulfate, 1 g of 3-methylpropenyloxypropyltrimethoxydecane, 68 g of methyltrimethoxydecane, and 27 g of dimethyldimethoxydecane were charged. Then, after confirming that heat was generated by the initiation of the polymerization, the temperature in the reactor was warmed to 85 ° C and held for 30 minutes.

Then, in a state where the temperature in the reactor was lowered and maintained at 80 ° C, a 25% aqueous solution containing 45 g of ion-exchanged water and a reactive emulsifier (manufactured by Kao Corporation, "Latemul S-180A"), and a methyl group were added. 26 g of cyclohexyl acrylate, 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 2 masses of ammonium persulfate. 5 g of an aqueous solution of an emulsified mixture, and a mixture containing 46 g of methyltrimethoxydecane and 18 g of dimethyldimethoxydecane, which were injected into the reactor from respective dropping tanks for 30 minutes, and at 80 ° C. Maintain for 2 hours.

Then, in a state where the temperature in the reactor was lowered and maintained at 80 ° C, a 25% aqueous solution containing 130 g of ion-exchanged water and a reactive emulsifier (manufactured by Kao Corporation, "Latemul S-180A"), and a methyl group were added. An emulsion mixture of 123 g of cyclohexyl acrylate, 37 g of n-butyl methacrylate, 4 g of methyl methacrylate, 79 g of n-butyl acrylate, 4 g of methacrylic acid, and 4 g of a 2% by mass aqueous solution of ammonium persulfate, and 3- a mixture of 2 g of methacryloxypropyltrimethoxydecane, 170 g of methyltrimethoxydecane, and 68 g of dimethyldimethoxydecane was injected into the reactor through separate dropping tanks for 2 hours, and It was maintained at 80 ° C for 1.5 hours.

After cooling to room temperature, the hydrogen ion concentration of the reaction liquid in the reactor was measured, and the pH was 2.8.

Next, a 25% aqueous ammonia solution was added to the reaction liquid, and the pH was adjusted to 8, and then the reaction liquid was filtered through a metal mesh of 100 mesh.

Further, the amount of the solid matter was adjusted to 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion of the polymer (A-2) having a number average particle diameter of 127 nm. (AD-2).

[Manufacturing Example 3] <Synthesis of aqueous dispersion (AD-3) of polymer (A-3)>

In a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device, after adding 880 g of ion-exchanged water and 10.0 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid, the temperature in the reactor was added under stirring. Warm to 80 ° C. While maintaining the temperature in the reactor at 80 ° C, a mixture of 83.4 g of dimethyldimethoxydecane, 73.0 g of phenyltrimethoxydecane, and 42.6 g of methyltrimethoxydecane was used for about 2 hours. At the same time, it was dropped into the reactor.

Then, the temperature in the reactor was maintained at 80 ° C and stirring was continued for 30 minutes. Next, after 5.6 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid was charged, the temperature in the reactor was maintained at 80 ° C and stirring was continued for 2 hours. Next, 22.5 g of methyl methacrylate, 11.2 g of n-butyl acrylate, 12.3 g of phenyltrimethoxydecane, 28.6 g of tetraethoxydecane, and 3-methylpropenyloxypropyltrimethoxydecane were contained. 1.1 g of the mixed liquid, and 0.9 g of acrylic acid, a reactive emulsifier ("Adekariasoap SR-1025" manufactured by Adeka Co., Ltd.; 25% by mass of solid content), and a reactive emulsifier (manufactured by Daiichi Kogyo Co., Ltd.) , "Aqualon KH-1025"; a solid content of 25% by mass aqueous solution), a mixed liquid of 0.8 g of a 0.5% by mass aqueous solution of ammonium persulfate, and a flux of 256.4 g of ion-exchanged water, maintained at a temperature of 80 ° C in the reactor. Next, drip in at the same time for about 2 hours.

And, maintaining the temperature in the reactor at 80 ° C and stirring for about 1 hour, after cooling to room temperature, measuring the hydrogen ion concentration of the liquid in the reactor In degrees, the pH is 2.0.

Next, a 25% aqueous ammonia solution was added to the reaction liquid, and the pH was adjusted to 8, and then filtered through a metal mesh of 100 mesh. Further, the amount of the solid matter was adjusted to 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion (AD-3) of the polymer (A-3) having a number average particle diameter of 80 nm.

[Manufacturing Example 5] <Synthesis of aqueous dispersion of polymer (A-4) (AD-4)>

In a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device, after introducing 560 g of ion-exchanged water and 15.0 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid, the temperature in the reactor was added under stirring. Warm to 80 ° C. A mixed solution comprising 125.9 g of dimethyldimethoxydecane and 39.4 g of methyltrimethoxydecane was added to the reactor while maintaining the temperature in the reactor at 80 ° C for about 2 hours. in. Then, 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 aqueous solution of dodecylbenzenesulfonic acid was charged, and then the temperature in the reactor was maintained at 80 ° C and stirring was continued for 2 hours.

A mixture comprising 36.8 g of phenyltrimethoxydecane, 28.6 g of tetraethoxydecane, and 1.1 g of 3-methylpropenyloxypropyltrimethoxydecane, and 0.9 g of acrylic acid, a reactive emulsifier ( ADEKA Co., Ltd., "Adekariasoap SR-1025"; solid content: 25% by mass aqueous solution) 1.5 g, reactive emulsifier ("Aqualon KH-1025" manufactured by Dai-ichi Kogyo Co., Ltd.; solid content: 25% by mass aqueous solution) 3.0 g, a mixture of 146.4 g of a 0.5% by mass aqueous solution of ammonium persulfate and 256.4 g of ion-exchanged water in the reactor The temperature was maintained at 80 ° C and dropped simultaneously over about 2 hours.

After the end of the dropwise addition, the temperature in the reactor was also maintained at 80 ° C, and stirring was continued for about 1 hour.

After cooling to room temperature, the pH of the reaction liquid in the reactor was measured and the pH was 1.9. After adding a 25% aqueous ammonia solution to the reaction liquid and adjusting the pH to 8, the reaction liquid was filtered through a metal mesh of 100 mesh.

Further, the amount of the solid matter was adjusted to 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion (AD-4) of the polymer (A-4) having a number average particle diameter of 100 nm.

[Manufacturing Example 6] <Synthesis of inorganic oxide (E-1) having photocatalytic activity> Cerium oxide modified rutile titanium oxide

While maintaining 700 mL of a titanium tetrachloride aqueous solution having a concentration of 200 g/L of TiO _{2 and} a sodium hydroxide aqueous solution having a concentration of 100 g/L of Na ₂ O, the pH of the reaction liquid was maintained at 5 to 9. Then, after adjusting the pH of the reaction liquid to 7, the mixture was filtered and washed until the conductivity of the filtrate became 100 μS/cm, and the titanium oxide wet cake 1 having a solid content of 28.3% by mass was obtained. This titanium oxide wet cake 1 contains fine particles having a rutile structure, and the number average particle diameter of the primary particles is 8 nm.

The obtained titanium oxide wet cake 1 was diluted with pure water to prepare a slurry of 1 mol/L. 1 L of this slurry was placed in a 3 L flask, and 1 N of nitric acid was added to make the molar ratio of titanium oxide/nitric acid 1/1, and the temperature was raised to 95 ° C, and the temperature was maintained for 2 hours to carry out acid heat treatment. After heating the acid The slurry was cooled to room temperature, neutralized to pH 6.7 using 28% aqueous ammonia, and filtered. Then, the conductivity of the filtrate was washed to 100 μS/cm, and a titanium oxide wet cake 2 having a solid content of 25% by mass was obtained.

In the obtained titanium oxide wet cake 2, a 10% strength aqueous sodium hydroxide solution was added thereto, followed by slurrying, and then dispersed in an ultrasonic cleaner for 3 hours to obtain an alkaline titanium oxide sol having a pH of 10.5 and a solid content of 10% by mass. . The alkaline titanium oxide sol 2L was placed in a 3 L flask, the temperature was raised to 70° C., and 69.4 mL of a sodium silicate aqueous solution having a concentration of 432 g/L as SiO ₂ was added thereto, and the temperature was raised to 90° C. for 1 hour, and then added. The pH of the 10% sulfuric acid was adjusted to 6, and the surface treated titanium oxide sol of the surface of the titanium oxide was obtained.

The obtained titanium oxide sol was cooled to room temperature, and 5.4 L of pure water was added thereto, and the impurities were removed and concentrated by a desalting and concentrating device to obtain a neutrality of pH 7.3, a solid content of 29% by mass, and a conductivity of 1.18 mS/cm. Rutile titanium oxide sol. This neutral rutile-type titanium oxide sol contains 15% by mass of a hydrated oxide of cerium with respect to the standard of SiO ₂ with respect to TiO ₂ . The number average particle diameter of the primary particles of titanium oxide in this sol was 9 nm.

[Manufacturing Example 7] <Synthesis of Inorganic Oxide (E-2) Having Photocatalytic Activity> Cerium oxide modified anatase titanium oxide

The titanium sulfate solution obtained by reacting titanium ore with sulfuric acid is heated and hydrolyzed to form agglomerated metatitanic acid, and an aqueous slurry of 30% by mass of TiO ₂ is converted.

Adding ammonia to the aqueous slurry to neutralize to pH 7, and then by filtration, The sulfate ion is removed by washing to obtain a dehydrated cake.

Nitric acid was added to the obtained dehydrated cake to carry out a degumming treatment to obtain an acidic titanium oxide sol having a pH of 1.5, which was formed of titanium oxide fine particles having an anatase-type crystal structure (number average particle diameter of primary particles of 7 nm).

The obtained acidic titanium oxide sol was diluted with pure water to prepare 600 mL of an acidic titanium oxide sol having a TiO ₂ concentration of 200 g/L, and then the temperature was raised to 70° C., and an aqueous solution of sodium citrate having a SiO ₂ concentration of 432 g/L was added in an amount of 20.8 mL. With 20% sulfuric acid.

Then, ripe for 30 minutes. Next, a 10% aqueous sodium hydroxide solution was added, the pH was adjusted to 8, and the pH was adjusted to 6 with a 2% sulfuric acid aqueous solution, followed by filtration and washing to obtain a wet cake. After the wet cake was repulped in pure water, ultrasonic dispersion was carried out to obtain a neutral-domain and stable anatase-type titanium oxide sol (solid content: 20% by mass, pH 7.5).

In this sample, agglomerated cerium oxide was deposited on the surface of the titanium oxide fine particles in a porous state, and the content thereof was converted into SiO _{2 in an} amount of 7 parts by mass based on 100 parts by mass of TiO ₂ .

In the following [Examples 1 to 24] and [Comparative Examples 1 to 5], an aqueous coating composition and a coating film were prepared.

[Example 1]

In an aqueous dispersion (AD-1) of the polymer (A-1) (51.6 g (solid content: 10.0% by mass), water-dispersed colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm was mixed (Nissan Chemical Industry Co., Ltd.) "Snow-Tex OS"; solid content: 20.0% by mass) 17.2 g and hydroxyethyl cellulose-based tackifier (C-1) adjusted to 1.0% by mass of solid content by ion-exchanged water (Daicel Finechem Co., Ltd., "HEC Daicel SP900") 80.0g, (meth)acrylic tackifier (D) which adjusted the pH of the liquid to 8 by adding 25% ammonia water, and adjusted the amount of the solid matter to 1.0% by mass by ion-exchanged water (D) -1) ("SN Thickner-636" manufactured by San Nopco Co., Ltd.) 60.0 g, 150 g of ethanol, and 641.2 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-1) having a solid content of 1.0% by mass. The viscosity of this aqueous coating composition (H-1) was 30 mPa‧s.

Next, on the one side of the 7 cm × 15 cm substrate on which the enamel paint has been pre-coated (the surface on which the enamel paint has been pre-coated), the aqueous coating composition (H-1) is applied by the above method to obtain A test plate (I-1) on which a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-1) are shown in Table 1.

[Embodiment 2]

A (meth)acrylic tackifier (D-2) ("SN Thickner-640", manufactured by San Nopco Co., Ltd.) having a solid content of 1.0% by mass adjusted with ion-exchanged water was used, and it was replaced with ion-exchanged water. 60.0 g of (meth)acrylic tackifier (D-1) having a solid content of 1.0% by mass. Other conditions were the same as in Example 1, and an aqueous coating composition (H-2) having a solid content of 1.0% by mass was obtained. The viscosity of this aqueous coating composition (H-2) was 25 mPa‧s.

Next, after coating the aqueous coating composition (H-2) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been precoated (the surface on which the enamel coating has been pre-coated), A test plate (I-2) in which a coating film was formed on a substrate.

The various evaluation results of this test plate (I-2) are shown in Table 1.

[Example 3]

In an aqueous dispersion (AD-3) of the polymer (A-3), 51.6 g (solid content: 10.0% by mass), a water-dispersed colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm was mixed (Nissan Chemical Industry Co., Ltd.) "Snow-Tex OS"; solid content: 20.0% by mass) 17.2 g and hydroxyethyl cellulose-based tackifier (C-1) adjusted to 1.0% by mass in terms of ion-exchanged water (manufactured by Daicel Finechem Co., Ltd.) (HEC Daicel SP900)) 80.0 g, after adding a 25% aqueous ammonia solution to adjust the pH of the liquid to 8, and adjusting the amount of the solid matter to 1.0% by mass of the (meth)acrylic acid-based viscosity by adjusting the ion-exchanged water 60.0 g of the agent (D-2) ("SN Thickner-640" manufactured by San Nopco Co., Ltd.), 150 g of ethanol, and 641.2 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition having a solid content of 1.0% by mass (H- 3). The viscosity of this aqueous coating composition (H-3) was 25 mPa‧s.

Next, after coating the aqueous coating composition (H-3) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been precoated (the surface on which the enamel coating has been pre-coated), A test plate (I-3) in which a coating film was formed on a substrate.

The results of various evaluations of this test plate (I-3) are shown in Table 1.

[Example 4]

In place of ion-exchanged water, a (meth)acrylic tackifier (D-3) ("Aron A-7055", manufactured by Toagosei Co., Ltd.) was used to adjust the solid content by 1.0% by mass. An aqueous coating agent having a solid content of 1.0% by mass was obtained in the same manner as in Example 3 except that 60.0 g of a (meth)acrylic tackifier (D-2) having a solid content of 1.0% by mass was adjusted. Composition (H-4). The viscosity of this aqueous coating composition (H-4) was 30 mPa‧s.

Next, after coating the aqueous coating composition (H-4) on the one side of the 7 cm × 15 cm substrate on which the enamel paint has been precoated (the surface on which the enamel coating has been pre-coated), A test plate (I-4) in which a coating film was formed on a substrate.

The results of various evaluations of this test plate (I-4) are shown in Table 1.

[Example 5]

In the aqueous dispersion (AD-3) of the polymer (A-3), 54.0 g (solid content: 10.0% by mass), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by the company, "Snow-Tex OS"; solid content: 20.0% by mass) 18.0 g of hydroxyethyl cellulose-based tackifier (C-1) adjusted to 1.0% by mass of solid content by ion-exchanged water (Daicel Finechem) (MEC Daicel SP900), 80.0 g, (meth)acrylic tackifier (D-4) adjusted to a mass ratio of 1.0% by mass by ion exchange water (Aron A-20P, manufactured by Toagosei Co., Ltd.) -X") 20.0 g, 150 g of ethanol, and 678.0 g of ion-exchanged water were mixed and stirred, and the aqueous coating composition (H-5) of the solid content of 1.0 mass % was obtained. The viscosity of this aqueous coating composition (H-5) was 35 mPa‧s.

Next, after coating the aqueous coating composition (H-5) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been precoated (the surface on which the enamel coating has been pre-coated), A test plate (I-5) in which a coating film was formed on a substrate.

The results of various evaluations of this test plate (I-5) are shown in Table 1.

[Embodiment 6]

54.6 g (solid content: 10.0% by mass) of the aqueous dispersion (AD-3) of the polymer (A-3), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) "Snow-Tex OS", "Snow-Tex OS"; solid content: 20.0 g%), hydroxyethylcellulose-based tackifier (C-1) adjusted to 1.0% by mass of solid content by ion-exchanged water (Daicel Finechem) (MEC Daicel SP900), 80.0 g, (meth)acrylic tackifier (D-4) adjusted to a mass ratio of 1.0% by mass by ion exchange water (Aron A-20P, manufactured by Toagosei Co., Ltd.) -X") 10.0 g, 150 g of ethanol, and 687.2 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-6) having a solid content of 1.0% by mass. The viscosity of this aqueous coating composition (H-6) was 25 mPa‧s.

Next, after coating the aqueous coating composition (H-6) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been pre-coated (the surface on which the enamel coating has been pre-coated), A test plate (I-6) of a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-6) are shown in Table 1.

[Embodiment 7]

In the aqueous dispersion (AD-2) of the polymer (A-2), 54.0 g (solid content: 10.0% by mass), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) "Snow-Tex OS", "Snow-Tex OS"; solid content: 20.0% by mass), hydroxyethylcellulose-based tackifier (C-1) adjusted to 1.0% by mass of solid content by ion-exchanged water (Daicel Finechem) Company system, "HEC Daicel SP900") 80.0g, adjusted by ion exchange water 20.0 g of a (meth)acrylic tackifier (D-4) ("Aron A-20P-X" manufactured by Toagosei Co., Ltd.), 150 g of ethanol, and 678.0 g of ion-exchanged water were mixed and stirred. An aqueous coating composition (H-7) having a solid content of 1.0% by mass was obtained. The viscosity of this aqueous coating composition (H-7) was 33 mPa‧s.

Next, after coating the aqueous coating composition (H-7) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been pre-coated (the surface on which the enamel coating has been pre-coated), A test plate (I-7) in which a coating film was formed on a substrate.

The results of various evaluations of this test plate (I-7) are shown in Table 1.

[Embodiment 8]

54.0 g (solid content: 10.0% by mass) of the aqueous dispersion (AD-4) of the polymer (A-4) was used, and 54.0 g of the aqueous dispersion (AD-2) of the polymer (A-2) was replaced (solid content: 10.0) quality%). Other conditions were the same as in Example 7, and an aqueous coating composition (H-8) having a solid content of 1.0% by mass was obtained. The viscosity of this aqueous coating composition (H-8) was 32 mPa‧s.

Next, after coating the aqueous coating composition (H-8) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been precoated (the surface on which the enamel coating has been pre-coated), A test plate (I-8) of a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-8) are shown in Table 1.

[Embodiment 9]

In the aqueous dispersion (AD-3) of the polymer (A-3), 54.0 g (solid content: 10.0% by mass), by dispersing colloidal cerium oxide having a number average particle diameter of 8 nm (B-2) (Snow-Tex OS, manufactured by Nissan Chemical Industries, Ltd.; solid content: 30.0% by mass) 12.0 g, hydroxyethyl cellulose-based tackifier adjusted to 1.0% by mass of solid content by ion-exchanged water (C-1) ("HEC Daicel SP900" manufactured by Daicel Finechem Co., Ltd.) 80.0 g, (meth)acrylic tackifier (D-4) adjusted to a mass of 1.0% by mass by ion-exchanged water (East Asia Synthesis) 20.0 g of "Aron A-20P-X"), 150 g of ethanol, and 684.0 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-9) having a solid content of 1.0% by mass. The viscosity of this aqueous coating composition (H-9) was 36 mPa‧s.

Next, after coating the aqueous coating composition (H-9) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been pre-coated (the surface on which the enamel coating has been pre-coated), A test plate (I-9) of a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-9) are shown in Table 1.

[Embodiment 10]

In the aqueous dispersion (AD-3) of the polymer (A-3), 54.0 g (solid content: 10.0% by mass), by dispersing colloidal cerium oxide (B-3) having a number average particle diameter of 22 nm (Nissan Chemical Co., Ltd.) Manufactured by Industrial Co., Ltd., "Snow-Tex OL"; solid content: 20.0% by mass) 18.0 g, hydroxyethylcellulose-based tackifier (C-1) adjusted to 1.0% by mass of solid content by ion-exchanged water (Daicel Finechem) (MEC Daicel SP900), 80.0 g, (meth)acrylic tackifier (D-4) adjusted to a mass ratio of 1.0% by mass by ion exchange water (Aron A-20P, manufactured by Toagosei Co., Ltd.) -X") 20.0 g, 150 g of ethanol and 678.0 g of ion-exchanged water were mixed and stirred to obtain an aqueous substance having a solid content of 1.0% by mass. Coating composition (H-10). The viscosity of this aqueous coating composition (H-10) was 30 mPa‧s.

Next, after coating the aqueous coating composition (H-10) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been precoated (the surface on which the enamel coating has been pre-coated), A test plate (I-10) of a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-10) are shown in Table 1.

[Example 11]

In the aqueous dispersion (AD-1) of the polymer (A-1) (52.2 g (solid content: 10.0% by mass), water-dispersed colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm was mixed (Nissan Chemical Industry Co., Ltd.) "Snow-Tex OS"; solid content: 20.0% by mass) 17.4g, hydroxyethyl cellulose-based tackifier (C-2) which is adjusted to 1.0% by mass of solid content by ion-exchanged water (Sumitomo Seiko Co., Ltd.) 70.0g of "HECSZ-25F"), after adjusting the pH of the liquid to 8 by adding a 25% aqueous ammonia solution, and adjusting the amount of solid matter to 1.0% by mass of (meth)acrylic acid by ion-exchanged water 60.0 g of an adhesive (D-1) ("SN Thickner-636" by San Nopco Co., Ltd.), 150 g of ethanol, and 650.4 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition having a solid content of 1.0% by mass (H) -11). The viscosity of this aqueous coating composition (H-11) was 29 mPa‧s.

Next, after coating the aqueous coating composition (H-11) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been precoated (the surface on which the enamel coating has been pre-coated), A test plate (I-11) on which a coating film was formed on a substrate.

The results of various evaluations of this test plate (I-11) are shown in Table 1.

[Embodiment 12]

In an aqueous dispersion (AD-1) of the polymer (A-1) (51.6 g (solid content: 10.0% by mass), water-dispersed colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm was mixed (Nissan Chemical Industry Co., Ltd.) "Snow-Tex OS"; solid content: 20.0% by mass) 17.2 g and hydroxyethyl cellulose-based tackifier (C-3) adjusted to 1.0% by mass of solid content by ion-exchanged water (manufactured by Sanchang Co., Ltd.) , "Sanhec HH") 90.0 g, after adjusting the pH of the liquid to 8 by adding a 25% aqueous ammonia solution, and adjusting the amount of the solid matter to 1.0% by mass of the (meth)acrylic tackifier by ion-exchanged water (D-1) ("SN Thickner-636" manufactured by San Nopco Co., Ltd.) 50.0 g, 150 g of ethanol and 641.2 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-12) having a solid content of 1.0% by mass. ). The viscosity of this aqueous coating composition (H-12) was 31 mPa‧s.

Next, after coating the aqueous coating composition (H-12) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been precoated (the surface on which the enamel coating has been pre-coated), A test plate (I-12) of a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-12) are shown in Table 1.

[Example 13]

In 45.0 g (solid content: 10.0% by mass) of the aqueous dispersion (AD-4) of the polymer (A-4), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by the company, "Snow-Tex OS"; 20.0 g of solid content (20.0 mass%), hydroxyethylcellulose-based tackifier (C-1) adjusted to 1.0% by mass of solid content by ion-exchanged water (Daicel Finechem) Company system, "HEC Daicel SP900") 80.0g, adjusted by ion exchange water 20.0 g of a (meth)acrylic tackifier (D-4) ("Aron A-20P-X" manufactured by Toagosei Co., Ltd.), 150 g of ethanol, and 682.5 g of ion-exchanged water were mixed and stirred. An aqueous coating composition (H-13) having a solid content of 1.0% by mass was obtained. The viscosity of this aqueous coating composition (H-13) was 35 mPa‧s.

Next, after coating the aqueous coating composition (H-13) on the one side of the 7 cm × 15 cm substrate which has been precoated with the enamel paint (the surface on which the enamel coating has been pre-coated), A test plate (I-13) of a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-13) are shown in Table 2.

[Embodiment 14]

In 63.0 g (solid content: 10.0% by mass) of the aqueous dispersion (AD-4) of the polymer (A-4), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) "Snow-Tex OS", "Snow-Tex OS"; solid content: 20.0 g%), hydroxyethylcellulose-based tackifier (C-1) adjusted to 1.0% by mass of solid content by ion-exchanged water (Daicel Finechem) (MEC Daicel SP900), 80.0 g, (meth)acrylic tackifier (D-4) adjusted to a mass ratio of 1.0% by mass by ion exchange water (Aron A-20P, manufactured by Toagosei Co., Ltd.) -X") 20.0 g, 150 g of ethanol and 673.5 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-14) having a solid content of 1.0% by mass. The viscosity of this aqueous coating composition (H-14) was 29 mPa‧s.

Next, on one side of the 7 cm × 15 cm substrate of the pre-coated enamel paint (the surface of the pre-coated enamel paint), the aqueous coating was applied by the above method. After the agent composition (H-14), a test plate (I-14) in which a coating film was formed on a substrate was obtained.

The results of various evaluations of this test plate (I-14) are shown in Table 2.

[Example 15]

In the aqueous dispersion (AD-4) of the polymer (A-4), 57.0 g (solid content: 10.0% by mass), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by the company, "Snow-Tex OS"; solid content: 20.0% by mass), hydroxyethylcellulose-based tackifier (C-1) having a solid content of 1.0% by mass adjusted by ion-exchanged water (Daicel Finechem) ("HEC Daicel SP900") 40.0g (meth)acrylic tackifier (D-4) adjusted to a 1.0% by mass solid content by ion exchange water (Aron A-20P-made by Toagosei Co., Ltd. X") 10.0 g, 75 g of ethanol and 299.0 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-15) having a solid content of 2.0% by mass. The viscosity of this aqueous coating composition (H-15) was 30 mPa‧s.

Next, after coating the aqueous coating composition (H-15) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been pre-coated (the surface on which the enamel coating has been pre-coated), A test plate (I-15) of a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-15) are shown in Table 2.

[Example 16]

In the aqueous dispersion (AD-4) of the polymer (A-4), 62.0 g (solid content: 10.0% by mass), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) Industrial company, "Snow-Tex OS"; solid content 20.0 5% by mass of hydroxyethylcellulose-based tackifier (C-1) ("HEC Daicel SP900" manufactured by Daicel Finechem Co., Ltd.) having a solid content of 5.0 g and an ion exchange amount of 1.0% by mass. Water-adjusted (meth)acrylic tackifier (D-4) ("Aron A-20P-X", manufactured by Toagosei Co., Ltd.) having a solid content of 1.0% by mass, and an inorganic oxide having photocatalytic activity ( E-1) 6.2 g, 150 g of ethanol and 676.8 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-16) having a solid content of 1.0% by mass. The viscosity of this aqueous coating composition (H-16) was 33 mPa‧s.

Next, after coating the aqueous coating composition (H-16) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been pre-coated (the surface on which the enamel coating has been pre-coated), A test plate (I-16) in which a coating film was formed on a substrate.

The results of various evaluations of this test plate (I-16) are shown in Table 2.

[Example 17]

In the aqueous dispersion (AD-4) of the polymer (A-4), 59.2 g (solid content: 10.0% by mass), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) "Snow-Tex OS", "Snow-Tex OS"; solid content: 20.0 mass%) 4.8 g, and hydroxyethyl cellulose-based tackifier (C-1) having a solid content of 1.0% by mass adjusted by ion-exchanged water (Daicel Finechem Co., Ltd.) ("HEC Daicel SP900") 80.0 g (meth)acrylic tackifier (D-4) adjusted to a mass ratio of 1.0% by mass by ion exchange water (manufactured by Toagosei Co., Ltd., "Aron A-20P- X") 20.0 g, 5.9 g of inorganic oxide (E-1) having photocatalytic activity, fluorocarbon surfactant (F-1) ("Megafac F-444", manufactured by DIC Corporation) 0.4 g, 150 g of ethanol and ions Exchange water 679.7g The mixture was stirred and stirred to obtain an aqueous coating composition (H-17) having a solid content of 1.0% by mass. The viscosity of this aqueous coating composition (H-17) was 31 mPa‧s.

Next, after coating the aqueous coating composition (H-17) on the one side of the 7 cm × 15 cm substrate which has been precoated with the enamel paint (the surface on which the enamel coating has been pre-coated), A test plate (I-17) in which a coating film was formed on a substrate.

The results of various evaluations of this test plate (I-17) are shown in Table 2.

[Embodiment 18]

In the aqueous dispersion (AD-4) of the polymer (A-4), 58.0 g (solid content: 10.0% by mass), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) "Snow-Tex OS", "Snow-Tex OS"; solid content: 20.0 mass%) 5.0 g, and hydroxyethyl cellulose-based tackifier (C-1) having a solid content of 1.0% by mass adjusted by ion-exchanged water (Daicel Finechem Co., Ltd.) ("HEC Daicel SP900") 80.0 g (meth)acrylic tackifier (D-4) adjusted to a mass ratio of 1.0% by mass by ion exchange water (manufactured by Toagosei Co., Ltd., "Aron A-20P- X") 10.0 g, 6.6 g of inorganic oxide (E-1) having photocatalytic activity, and fluorocarbon surfactant (F-1) ("Megafac F-444", manufactured by DIC Corporation) 0.4 g, ethanol 150 g and 690.0 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-18) having a solid content of 1.0% by mass. The viscosity of this aqueous coating composition (H-18) was 23 mPa‧s.

Next, after coating the aqueous coating composition (H-18) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been precoated (the surface on which the enamel coating has been pre-coated), A test plate (I-18) of a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-18) are shown in Table 2.

[Embodiment 19]

Addition of water-dispersed colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm to 56.0 g (solid content: 10.0% by mass) of the aqueous dispersion (AD-4) of the polymer (A-4) (Nissan Chemical Industries, Ltd.) "Snow-Tex OS"; a solid content of 20.0% by mass) of 5.0 g, and a hydroxyethylcellulose-based tackifier (C-1) having a solid content of 1.0% by mass adjusted by ion-exchanged water (manufactured by Daicel Finechem Co., Ltd., "HEC Daicel SP900") 80.0 g and 25% aqueous ammonia solution, after adjusting the pH of the liquid to 8, and adjusting the amount of the solid matter to 1.0% by mass of the (meth)acrylic tackifier by adjusting the ion exchange water ( D-1) ("SN Thickner-636" manufactured by San Nopco Co., Ltd.) 60.0 g, inorganic oxide (E-1) having photocatalytic activity (5.5 g), and fluorocarbon surfactant (F-1) (manufactured by DIC Corporation) 0.4 g of "Megafac F-444"), 150 g of ethanol and 643.1 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-19) having a solid content of 1.0% by mass. The viscosity of this aqueous coating composition (H-19) was 29 mPa‧s.

Next, after coating the aqueous coating composition (H-19) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been pre-coated (the surface on which the enamel coating has been pre-coated), A test plate (I-19) in which a coating film was formed on a substrate.

The results of various evaluations of this test plate (I-19) are shown in Table 2.

[Example 20]

In the aqueous dispersion (AD-4) of the polymer (A-4), 56.0 g (solid content: 10.0% by mass), water-dispersed colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm was mixed (Nissan Chemical Industry Co., Ltd.) System, "Snow-Tex OS"; solid content 20.0 5% by mass of hydroxyethylcellulose-based tackifier (C-1) ("HEC Daicel SP900" manufactured by Daicel Finechem Co., Ltd.) having a solid content of 1.0% by mass and 25% by weight. After the pH of the liquid was adjusted to 8 by the aqueous ammonia solution, the (meth)acrylic tackifier (D-1) having a solid content of 1.0% by mass adjusted by ion-exchanged water (manufactured by San Nopco Co., Ltd., "SN Thickner-636") 60.0 g, 8.0 g of inorganic oxide (E-2) having photocatalytic activity, fluorocarbon surfactant (F-1) ("Megafac F-444", manufactured by DIC Corporation) 0.4 g, ethanol 150 g The mixture was mixed with 640.6 g of ion-exchanged water and stirred to obtain an aqueous coating composition (H-20) having a solid content of 1.0% by mass. The viscosity of this aqueous coating composition (H-20) was 28 mPa‧s.

Next, after coating the aqueous coating composition (H-20) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been pre-coated (the surface on which the enamel coating has been pre-coated), A test plate (I-20) of a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-20) are shown in Table 2.

[Example 21]

In the aqueous dispersion (AD-4) of the polymer (A-4), 56.0 g (solid content: 10.0% by mass), water-dispersed colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm was mixed (Nissan Chemical Industry Co., Ltd.) "Snow-Tex OS"; solid content: 20.0% by mass) 3.0 g of hydroxyethyl cellulose-based tackifier (C-1) having a solid content of 1.0% by mass adjusted by ion-exchanged water (Daicel Finechem Co., Ltd., "HEC Daicel SP900") 80.0g, a (meth)acrylic tackifier which adjusted the pH of the liquid to 8 by adding a 25% aqueous ammonia solution, and adjusted the amount of the solid matter to 1.0% by mass by ion-exchanged water ( D-1) (San 60.0 g of "SN Thickner-636" manufactured by Nopco Co., Ltd., 10.0 g of inorganic oxide (E-2) having photocatalytic activity, and fluorocarbon surfactant (F-1) (Megafac F-444, manufactured by DIC Corporation) 0.4 g, 150 g of ethanol, and 640.6 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-21) having a solid content of 1.0% by mass. The viscosity of this aqueous coating composition (H-21) was 27 mPa‧s.

Next, after coating the aqueous coating composition (H-21) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been precoated (the surface on which the enamel coating has been pre-coated), A test plate (I-21) on which a coating film was formed on a substrate.

The results of various evaluations of this test plate (I-21) are shown in Table 2.

[Example 22]

In the aqueous dispersion (AD-4) of the polymer (A-4), 58.0 g (solid content: 10.0% by mass), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) "Snow-Tex OS", "Snow-Tex OS"; solid content: 20.0 mass%) 5.0 g, and hydroxyethyl cellulose-based tackifier (C-1) having a solid content of 1.0% by mass adjusted by ion-exchanged water (Daicel Finechem Co., Ltd.) ("HEC Daicel SP900") 80.0 g (meth)acrylic tackifier (D-4) adjusted to a mass ratio of 1.0% by mass by ion exchange water (manufactured by Toagosei Co., Ltd., "Aron A-20P- X") 10.0 g, 6.6 g of inorganic oxide (E-1) having photocatalytic activity, fluorocarbon surfactant (F-1) ("Megafac F-444", manufactured by DIC Corporation) 0.4 g, ion-exchanged water 1.0 g of a fading coloring matter (G-1) ("Acid Red: Acid Red", manufactured by Hodogaya Chemical Co., Ltd.), 1.0 g of ethanol, and 68 9.0 g of ion-exchanged water were mixed and stirred to obtain a solid content. 1.0% by mass of aqueous coating composition (H-22). The viscosity of this aqueous coating composition (H-22) was 23 mPa‧s.

Next, after coating the aqueous coating composition (H-22) on the one side of the 7 cm × 15 cm substrate on which the enamel paint has been precoated (the surface on which the enamel coating has been pre-coated), A test plate (I-22) of a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-22) are shown in Table 2.

[Example 23]

The discoloring pigment (G-2) ("methylene blue" manufactured by Kishida Chemical Co., Ltd.) of 1.0 g of the solid content was adjusted to 1.0% by mass by ion-exchanged water, and the amount of solid matter was adjusted to 1.0% by mass instead of ion-exchanged water. The fading pigment (G-1) was 1.0 g. Other conditions were the same as in Example 22, and an aqueous coating composition (H-23) having a solid content of 1.0% by mass was obtained. The viscosity of this aqueous coating composition (H-23) was 24 mPa‧s.

Next, after coating the aqueous coating composition (H-23) on the one side of the 7 cm × 15 cm substrate which has been precoated with the enamel paint (the surface on which the enamel coating has been pre-coated), A test plate (I-23) of a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-23) are shown in Table 2.

[Example 24]

In the aqueous dispersion (AD-4) of the polymer (A-4), 58.0 g (solid content: 10.0% by mass), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) Manufactured by the company, "Snow-Tex OS"; solid content: 20.0 mass%) 5.0 g, and hydroxyethyl cellulose-based tackifier (C-1) having a solid content of 1.0% by mass adjusted by ion-exchanged water (Daicel Finechem Co., Ltd.) system, "HEC Daicel SP900") 80.0g (meth)acrylic tackifier (D-4) adjusted to a 1.0% by mass solid content by ion exchange water (Aron A-20P-X, manufactured by Toagosei Co., Ltd.) 10.0 g, 6.6 g of inorganic oxide (E-1) having photocatalytic activity, and fluorocarbon surfactant (F-1) ("Megafac F-444", manufactured by DIC Corporation) 0.4 g, and solid-adjusted by ion-exchanged water 2.0 g of a fading dye (G-2) ("methylene blue" manufactured by Kishida Chemical Co., Ltd.), and 150 g of ethanol and 688.0 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating having a solid content of 1.0% by mass. Covering composition (H-24). The viscosity of this aqueous coating composition (H-24) was 25 mPa‧s.

Next, after coating the aqueous coating composition (H-24) on the one side of the 7 cm × 15 cm substrate which has been precoated with the enamel paint (the surface on which the enamel coating has been pre-coated), A test plate (I-24) of a coating film was formed on the substrate. The results of various evaluations of this test plate (I-24) are shown in Table 2.

[Comparative Example 1]

In the aqueous dispersion (AD-3) of the polymer (A-3) (60.0 g (solid content: 10.0% by mass), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) Industrial Co., Ltd., "Snow-Tex OS"; 20.0 g of solid content (20.0 mass%), 150 g of ethanol and 770.0 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-25) having a solid content of 1.0% by mass. . The viscosity of this aqueous coating composition (H-25) was 2 mPa‧s.

Next, after coating the aqueous coating composition (H-25) on the one side of the 7 cm × 15 cm substrate which has been precoated with the enamel paint (the surface on which the enamel coating has been pre-coated), a test plate (I-25) for forming a coating film on a substrate, The appearance of the coating film (droplet) was evaluated. The result of the assessment is ×. The gloss retention after the coating of the aqueous coating composition, the gloss retention after 3,000 hours of the weather resistance test, and the evaluation of the stain resistance were not performed.

[Comparative Example 2]

In 51.6 g (solid content: 10.0% by mass) of the aqueous dispersion (AD-3) of the polymer (A-3), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) "Snow-Tex OS", "Snow-Tex OS"; solid content: 20.0% by mass), hydroxyethylcellulose-based tackifier (C-1) having a solid content of 1.0% by mass adjusted by ion-exchanged water (Daicel Finechem) 140.0 g of "HEC Daicel SP900", 150 g of ethanol, and 641.2 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-26) having a solid content of 1.0% by mass. The viscosity of this aqueous coating composition (H-26) was 10 mPa‧s.

Next, after coating the aqueous coating composition (H-26) on the one side of the 7 cm × 15 cm substrate on which the enamel coating has been precoated (the surface on which the enamel coating has been pre-coated), A test plate (I-26) of a coating film was formed on the substrate, and the appearance (droplet) of the coating film was evaluated. The result of the assessment is ×. The gloss retention after the coating of the aqueous coating composition, the gloss retention after 3,000 hours of the weather resistance test, and the evaluation of the stain resistance were not performed.

[Comparative Example 3]

In the aqueous dispersion (AD-3) of the polymer (A-3), 48.0 g (solid content: 10.0% by mass), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) Industrial company, "Snow-Tex OS"; solid content 20.0 1% by mass of hydroxyethylcellulose-based tackifier (C-1) ("HEC Daicel SP900" manufactured by Daicel Finechem Co., Ltd.) having a solid content of 16.0 g and ion-exchanged water adjusted to 1.0% by mass, and 150 g of ethanol and 586.0 g of ion-exchanged water was mixed and stirred to obtain an aqueous coating composition (H-27) having a solid content of 1.0% by mass. The viscosity of this aqueous coating composition (H-27) was 30 mPa‧s.

Next, on the one side of the 7 cm × 15 cm substrate on which the enamel paint has been pre-coated (the surface on which the enamel paint has been pre-coated), the aqueous coating composition (H-27) is applied by the above method to obtain A test plate (I-27) on which a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-27) are shown in Table 3.

[Comparative Example 4]

57.6 g (solid content: 10.0% by mass) of the aqueous dispersion (AD-3) of the polymer (A-3), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) "Snow-Tex OS", a solid content of 20.0% by mass, and a (meth)acrylic tackifier (D-4), which is adjusted to a solid content of 1.0% by mass, manufactured by Toagosei Co., Ltd. 40.0 g of "Aron A-20P-X"), 150 g of ethanol, and 733.2 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-28) having a solid content of 1.0% by mass. The viscosity of this aqueous coating composition (H-28) was 32 mPa‧s.

Next, on the one side of the 7 cm × 15 cm substrate on which the enamel paint has been pre-coated (the surface on which the enamel paint has been pre-coated), the aqueous coating composition (H-28) is applied by the above method to obtain A test plate (I-28) on which a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-28) are shown in Table 3.

[Comparative Example 5]

56.4 g (solid content: 10.0% by mass) of the aqueous dispersion (AD-3) of the polymer (A-3), by dispersing colloidal cerium oxide (B-1) having a number average particle diameter of 8 nm (Nissan Chemical Co., Ltd.) "Snow-Tex OS", "Snow-Tex OS"; solid content: 20.0 g%), x-ray adhesive-based tackifier (S-1) adjusted to 1.0% by mass by ion-exchanged water (CP Kelco A Huber) 60.0 g of "KELZAN ST" manufactured by the company, 150 g of ethanol, and 714.8 g of ion-exchanged water were mixed and stirred to obtain an aqueous coating composition (H-29) having a solid content of 1.0% by mass. The viscosity of this aqueous coating composition (H-29) was 35 mPa‧s.

Next, on the one side of the 7 cm × 15 cm substrate on which the enamel paint has been pre-coated (the surface on which the enamel paint has been pre-coated), the aqueous coating composition (H-29) is applied by the above method to obtain A test plate (I-29) on which a coating film was formed on the substrate.

The results of various evaluations of this test plate (I-29) are shown in Table 3.

As described above, it was confirmed by the aqueous coating composition of the present embodiment that a coating film capable of maintaining a high level of appearance and stain resistance for a long period of time can be formed.

[Possibility of application in industry]

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

Claims (10)

An aqueous coating composition having an amount of solid content of 0.5 to 2% by mass of an aqueous coating composition containing an aqueous dispersion (AD) of an polymer (A), an inorganic oxide (B), and a hydroxyethyl group Cellulose tackifier (C) and (meth)acrylic tackifier (D). The aqueous coating composition according to claim 1, wherein the component (A) contains a polymerization obtained by polymerizing a vinyl monomer and a hydrolyzable hydrazine compound in the presence of water and an emulsifier. Things. The aqueous coating composition according to claim 1 or 2, wherein the component (B) is cerium oxide. The aqueous coating composition according to any one of claims 1 to 3, which further contains an inorganic oxide (E) having photocatalytic activity. The aqueous coating composition according to any one of claims 1 to 4, which further contains a fluorocarbon surfactant (F). The aqueous coating composition according to any one of claims 1 to 5, which further contains a fading pigment (G). An aqueous coating composition comprising the aqueous coating composition of any one of claims 1 to 6. A coating film obtained by the aqueous coating described in claim 7 of the patent application. A coated article comprising a substrate and a coating film according to claim 8 formed on at least a part of a surface of the substrate. The coated article of claim 9, wherein the substrate is an organic substrate.