JP7209525B2 - Water-based compositions, water-based paints, coatings, composite coatings, and coated products - Google Patents

Description

The present invention relates to waterborne compositions, waterborne coatings, coatings, composite coatings, and coated products.

The surfaces of outdoor structures such as building exteriors, bridges, tanks, etc. are coated with paint, etc., but the coating film surface is exposed to dust, soot, sand, etc. in the air, contaminants eluted from sealing materials, It is polluted by contaminants discharged from the outlet, or organisms such as algae and mold. Such paint film contamination is usually dingy or green in color and significantly detracts from the aesthetic appearance of buildings and outdoor structures.

The aqueous topcoat composition for suppressing contamination of the coating film as described above comprises an undercoat layer and a topcoat layer provided on the undercoat layer, wherein the undercoat layer comprises a silicone-modified resin and an organic antifungal agent. and the topcoat layer is a layer containing photocatalyst particles, inorganic oxide particles and hydrolyzable silicone, a multi-coating body has been proposed (see, for example, Patent Document 1). Also proposed is a water-based coating agent composition containing an anti-alg and anti-mold agent in an aqueous dispersion of a copolymer having a specific composition (see, for example, Patent Document 2).

Japanese Patent No. 4092434 JP 2017-149869 A

The techniques described in Patent Documents 1 and 2 are techniques that are excellent in biofouling resistance because the undercoat layer contains an antifungal agent.

However, the techniques described in Patent Documents 1 and 2 improve the sprayability assuming painting at construction sites, the spreadability of the coating liquid on the substrate, the cracks in the coating film and / or the water retention of the coating film. There is room for

Therefore, in the present invention, in view of the above-described circumstances, the appearance is not impaired even on a dark-colored substrate, the cracks of the coating film and the water retention of the coating film are good, and the appearance, stain resistance, and sealing stain resistance are improved over a long period of time. And it aims at providing the aqueous composition which can form the coating film which can maintain biofouling resistance at a high level.

The present inventors have made intensive studies to solve the above-described problems of the prior art, and found that the inorganic oxide B having no photocatalytic activity and the inorganic oxide C having photocatalytic activity are contained, and the photocatalytic activity is present. The inventors have found that the above-described problems of the prior art can be solved by using an aqueous composition in which the number average particle size of the inorganic oxide B is within a predetermined range, and have completed the present invention.

That is, the present invention is as follows.
[1]
Containing an inorganic oxide B having no photocatalytic activity, an inorganic oxide C having photocatalytic activity, and a fluorocarbon surfactant D ,
The inorganic oxide B having no photocatalytic activity has a number average particle size of more than 30 nm and 160 nm or less ,
In terms of solid content, it contains 50 to 94 parts by mass of an inorganic compound B that does not have photocatalytic activity and 6 to 21 parts by mass of an inorganic oxide C that has photocatalytic activity (however, the polymer A and an inorganic compound that does not have photocatalytic activity The total amount of oxide B and inorganic oxide C having photocatalytic activity shall be 100 parts by mass), water-based composition.
[2]
Contains 0 to 27 parts by mass of polymer A in terms of solid content (however, the total amount of polymer A, inorganic oxide B having no photocatalytic activity, and inorganic oxide C having photocatalytic activity is 100 parts by mass and the water-based composition according to [1] above.
[ 3 ]
The water-based composition according to the above [1] or [2] , further comprising a fading dye E.
[ 4 ]
A water-based paint containing the water-based composition according to any one of [1] to [ 3 ].
[ 5 ]
A coating film obtained from the water-based coating composition described in [ 4 ] above.
[ 6 ]
A composite coating film comprising at least two layers of the coating film according to [ 5 ] and a coating film comprising an undercoat layer,
A composite coating film, wherein the coating film comprising the undercoat layer contains a polymer and an anti-algae and/or anti-mold agent.
[ 7 ]
A coated product comprising a substrate and the coating film according to [ 5 ] or the composite coating film according to [ 6 ].
[ 8 ]
The coated product according to claim 7 , wherein the substrate is an organic substrate.

According to the present invention, the appearance is not impaired even on a dark-colored substrate, cracks in the coating film and water retention of the coating film are good, and the appearance, stain resistance, sealing stain resistance, and biological stain resistance are maintained over a long period of time. It is possible to provide a water-based composition capable of forming a coating film that can be maintained at a high level.

EMBODIMENT OF THE INVENTION Hereinafter, the form (it describes as "this embodiment" hereafter.) for implementing this invention is demonstrated in detail.
It should be noted that the present embodiment below is an example for explaining the present invention, and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist thereof.

[Aqueous composition]
The aqueous composition of the present embodiment contains an inorganic oxide B having no photocatalytic activity and an inorganic oxide C having photocatalytic activity, and the number average particle diameter of the inorganic oxide B having no photocatalytic activity is greater than 30 nm. 160 nm or less.

The coating film obtained from the water-based composition of the present embodiment does not impair the appearance even on a dark-colored substrate, has good cracks in the coating film and water retention of the coating film, and has excellent appearance, stain resistance, and sealing properties over a long period of time. A high level of fouling and biofouling resistance can be maintained.

<Polymer A>
The aqueous composition of the present embodiment may contain an aqueous dispersion AD (hereinafter, sometimes simply referred to as the AD component) of the polymer A (hereinafter, sometimes simply referred to as the A component). good.

In the water-based composition of the present embodiment, the total amount of the polymer A, the inorganic oxide B having no photocatalytic activity described later, and the inorganic oxide C having photocatalytic activity described later was set to 100 parts by mass in terms of solid content. Sometimes the polymer A may be contained in an amount of preferably 0 to 40.0 parts by weight, more preferably 0 to 30.0 parts by weight, even more preferably 0 to 27.0 parts by weight. By setting the content of the A component in the water-based composition to the above range, the water-based composition is further excellent in appearance, weather resistance, stain resistance, sealing stain resistance, biological stain resistance, and water retention on dark-colored substrates. A composition can be obtained.

Although the polymer A is not particularly limited, for example, a polymer obtained by a method such as emulsion polymerization can be used. Specific examples of the polymer (A) include, but are not particularly limited to, polymers obtained by performing any one of radical polymerization, anionic polymerization, and cationic polymerization in an aqueous medium. .

The number average particle size of polymer A is preferably 10 nm to 200 nm, more preferably 10 nm to 150 nm, even more preferably 10 nm to 100 nm, and even more preferably 10 nm to 40 nm.

By using the polymer A whose number average particle size is within the above range, the water-based composition of the present embodiment does not have cloudiness even when applied to a dark-colored substrate, and the resulting coating film tends not to impair the appearance. be. Further, when the number average particle size of the polymer A is 10 nm or more, the stain resistance of the coating film is further improved, and when the number average particle size of the polymer A is 40 nm or less, the weather resistance of the coating film is further improved.

The method for controlling the number average particle size of the polymer A within the above-described range is not particularly limited. By increasing the amount, the number average particle size can be reduced.

Moreover, the number average particle diameter of the polymer A can be measured using a wet particle size analyzer, and specifically, it can be measured by the method described in the examples below.

Specific examples of component A include, but are not limited to, poly(meth)acrylate-based polymers, polyvinyl acetate-based polymers, vinyl acetate-(meth)acrylic-based polymers, and ethylene vinyl acetate-based polymers. Polymers, silicone-based polymers, fluorine-based polymers, polybutadiene-based polymers, styrene-butadiene-based polymers, NBR-based polymers, polyvinyl chloride-based polymers, chlorinated polypropylene-based polymers, polyethylene-based polymers, polystyrene-based Polymers, homopolymers or copolymers represented by vinylidene chloride polymers, polystyrene-(meth)acrylate polymers, styrene-maleic anhydride polymers, silicone-modified (meth)acrylic polymers, Modified copolymers typified by fluorine-(meth)acrylic polymers, (meth)acryl-silicone polymers, epoxy-(meth)acrylic polymers and the like can be mentioned.
These may be used individually by 1 type, and may use 2 or more types together.

In addition, "(meth)acrylate" means "acrylate" and corresponding "methacrylate", and "(meth)acryl" means "acryl" and corresponding "methacryl".

The homopolymers, copolymers, modified copolymers, and the like of polymer A described above (hereinafter, these may be collectively referred to as "polymers") are preferably obtained in the form of aqueous dispersions. Preferred embodiments of these polymers include emulsions, and specific examples thereof include, but are not particularly limited to, acrylic emulsions, acrylic silicone emulsions, silicone emulsions, and the like. These are not particularly limited, but can be obtained, for example, by emulsion polymerization of monomers such as (meth)acrylic acid esters, hydrolyzable silicon compounds described later, and the like.

The aqueous composition of the present embodiment may further contain a compound having a functional group that reacts with the functional group contained in the polymer A, in addition to the A component. Examples of such compounds include, but are not limited to, (poly)isocyanate compounds, (poly)epoxy compounds, amino compounds, (poly)carboxy compounds, (poly)hydroxy compounds, glycol compounds, silanol compounds, silyl compounds, alkoxy compounds, (meth)acrylate compounds, and the like. These may be used individually by 1 type, and may use 2 or more types together.

A vinyl monomer can be used as a polymer component of the polymer A.
Examples of vinyl monomers that can be used in the production of component A include, but are not limited to, (meth)acrylic acid esters, aromatic vinyl compounds, vinyl cyanide compounds, and carboxyl group-containing vinyl compounds. , hydroxyl group-containing vinyl compounds, glycidyl group-containing vinyl compounds, vinyl compounds having secondary and/or tertiary amide groups, and vinyl monomers containing functional groups such as anionic vinyl compounds.

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

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

Examples of aromatic vinyl compounds include, but are not limited to, styrene, α-methylstyrene, p-tert-butylstyrene, chlorostyrene, vinyltoluene, and the like.

Examples of vinyl cyanide compounds include, but are not limited to, (meth)acrylonitrile, α-chloroacrylonitrile, and the like.

Examples of the carboxyl group-containing vinyl compound include, but are not limited to, (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, or itaconic acid, maleic acid, and fumaric acid. Examples include half esters of dibasic acids such as acids. A carboxyl group can be introduced into component (A) by using a vinyl monomer containing a carboxyl group. As a result, it is presumed that the stability of the emulsion can be further improved and the coating film can be provided with high resistance to the external dispersion destruction action. Note that the effects of the present embodiment are not limited to these.

The carboxyl groups to be introduced can be partially or wholly neutralized with ammonia, amines such as triethylamine and dimethylethanolamine, and bases such as NaOH and KOH. From the viewpoint of water resistance, the amount of the carboxyl group-containing vinyl monomer used in the total amount of vinyl monomers described above is preferably 0 to 50% by mass, but is not limited thereto.

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

Examples of (poly)oxyethylene mono(meth)acrylates include, but are not limited to, ethylene glycol (meth)acrylate, ethylene glycol methoxy(meth)acrylate, diethylene glycol (meth)acrylate, methoxy Diethylene glycol (meth)acrylate, tetraethylene glycol (meth)acrylate, tetraethylene glycol methoxy(meth)acrylate, and the like can be mentioned.

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

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

Examples of glycidyl group-containing vinyl compounds include, but are not limited to, glycidyl (meth)acrylate, allyl glycidyl ether, allyl dimethyl glycidyl ether, and the like.

Among the vinyl monomers mentioned above, the use of a glycidyl group-containing vinyl monomer further improves the reactivity of component A. Therefore, by cross-linking with a hydrazine derivative, a carboxylic acid derivative, an isocyanate derivative, or the like, a coating film having even better solvent resistance and the like can be obtained. From this point of view, the total amount of the glycidyl group-containing vinyl monomer used in the total amount of the vinyl monomers described above is preferably 0 to 50% by mass, more preferably 0 to 45% by mass, and further It is preferably 0 to 40% by mass.

Examples of vinyl compounds having secondary and/or tertiary amide groups include, but are not limited to, N-alkyl-substituted (meth)acrylamides, N-alkylene-substituted (meth)acrylamides, and the like.

Examples of N-alkyl-substituted (meth)acrylamides include, but are not limited to, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N , N-diethylacrylamide, N-methyl-N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, Nn-propyl (meth)acrylamide, N-methyl-Nn-propyl (meth)acrylamide, N-methyl-N-isopropyl(meth)acrylamide, N-(meth)acryloylpyrrolidine, N-(meth)acryloylpiperidine, N-acryloylhexahydroazepine, N-(meth)acryloylmorpholine, N-vinylpyrrolidone, N- vinylcaprolactam, N,N'-methylenebis(meth)acrylamide, N-vinylacetamide, diacetone(meth)acrylamide, N-methylol(meth)acrylamide and the like.

Examples of vinyl monomers other than the vinyl monomers described above include, but are not limited to, (meth)acrylamide, olefins such as ethylene, propylene, and isobutylene; dienes such as butadiene; vinyl chloride; , vinylidene chloride vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene, and other haloolefins; vinyl acetate, vinyl propionate, n-vinyl butyrate, vinyl benzoate, p-tert-butyl vinyl benzoate, vinyl pivalate, Carboxylic acid vinyl esters such as vinyl 2-ethylhexanoate, vinyl versatate and vinyl laurate; carboxylic acid isopropenyl esters such as isopropenyl acetate and isopropenyl propionate; vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether Aromatic vinyl compounds such as styrene and vinyl toluene; Allyl esters such as allyl acetate and allyl benzoate; Allyl ethers such as allyl ethyl ether and allyl phenyl ether; 4-(meth)acryloyloxy-2,2, 6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, perfluoromethyl (meth)acrylate, perfluoropropyl (meth)acrylate, perfluoropropylmethyl (meth)acrylate, vinylpyrrolidone, trimethylolpropane tri(meth)acrylate, allyl (meth)acrylate, and the like.
These may be used individually by 1 type, and may use 2 or more types together.

When the A component is produced by a polymerization reaction, a chain transfer agent may be used for the purpose of controlling the molecular weight of the polymerized product of the vinyl monomers used.

Examples of chain transfer agents include, but are not limited to, alkylmercaptans such as n-octylmercaptan, n-dodecylmercaptan and tert-dodecylmercaptan; aromatic mercaptans such as benzylmercaptan and dodecylbenzylmercaptan. ; thiocarboxylic acids such as thiomalic acid, salts thereof, or alkyl esters thereof; polythiols; disulfides such as diisopropyl xanthogen disulfide, di(methylenetrimethylolpropane) xanthogen disulfide; Allyl compounds and the like can be mentioned.
These may be used individually by 1 type, and may use 2 or more types together.

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

Polymer A is preferably produced by a polymerization reaction between the vinyl monomer and the hydrolyzable silicon compound described above.

The hydrolyzable silicon compound used for producing the polymer A is not limited to the following, but for example, a compound represented by the following formula (1), a silane coupling agent, and condensates thereof are preferred.

_{SiWxRy (} 1)
In the above formula (1), W is an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, and an aminoxy group. and at least one selected from the group consisting of amide groups.
R is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a halogen-substituted 6 to 20 carbon atoms. represents at least one group selected from the group consisting of aryl groups.
x is an integer of 1 or more and 4 or less, y is an integer of 0 or more and 3 or less, and satisfies the relationship x+y=4.
When W is plural, when R is plural, each W and R may be the same or different.

Examples of the compound represented by formula (1) include, but are not limited to, silicon alkoxide represented by formula (1). As the silicon alkoxide, a tetrafunctional silicon alkoxide is preferable from the viewpoint of hydrolysis rate.

Examples of the silane coupling agent include, but are not limited to, hydrolyzable groups (e.g., alkoxy groups having 1 to 20 carbon atoms, hydroxyl groups, acetoxy groups having 1 to 20 carbon atoms, halogen atoms, hydrogen at least one selected from the group consisting of atoms, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group and an amide group, etc.) and a functional group having reactivity with other compounds (for example, a vinyl polymerizable group , epoxy group, amino group, methacrylic group, thiol group, isocyanate group, etc.) (silane coupling agent).

By using such a silane coupling agent as the hydrolyzable silicon compound, the polycondensate of the hydrolyzable silicon compound and the vinyl monomer can be chemically bonded to each other. Thereby, the compatibility is further improved, and the transparency of the coating film is further improved.

As the silane coupling agent, among the above, a silane coupling agent having at least a vinyl polymerizable group and/or a thiol group is preferable, and a silane coupling agent having at least a vinyl polymerizable group is more preferable.

Since the vinyl polymerizable group and the thiol group have high reactivity with the above-mentioned vinyl monomer, they can efficiently form a chemical bond through a copolymerization reaction or a chain transfer reaction with the vinyl monomer. Therefore, by using a silane coupling agent having a vinyl polymerizable group or a thiol group, it can be efficiently combined with other components (for example, vinyl monomers) constituting component A. Weather resistance and strength are improved by using component A in which a hydrolyzable silicon compound (or its polymerization product) and/or a vinyl monomer (or its polymerization product) are chemically bonded. etc. can be obtained.
Note that the effect of the present embodiment is not limited to such characteristics.

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

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

Examples of the hydrolyzable silicon compound and silane coupling agent represented by formula (1) include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra tetraalkoxysilanes such as isopropoxysilane and tetra-n-buxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane silane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane ethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltri Methoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-( 3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane , 3-(meth)acryloyloxypropyl tri-n-propoxysilane, 3-(meth)acryloyloxypropyl Trialkoxysilanes such as lyisopropoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyl Dimethoxysilane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n- Pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n - dialkoxysilanes such as octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane; monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane; and the like.

Among these, tetraalkoxysilanes, trialkoxysilanes, and dialkoxysilanes are preferable, and tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, and dimethyldimethoxysilane. is more preferable, and tetramethoxysilane and tetraethoxysilane, which are tetrafunctional silicon alkoxides, are more preferable from the viewpoint of high hydrolysis rate.

As the hydrolyzed silicon compound used for producing the polymer A, it is preferable to use a condensate of the compound represented by the formula (1) or a silane coupling agent.

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

The silicon alkoxide and silane coupling agent represented by the formula (1) may be used alone or in combination of two or more. Among them, from the viewpoint of improving the performance of the water-based composition and the resulting coating film, it is preferable to use the silicon alkoxide represented by the formula (1) in combination with a silane coupling agent, such as tetraethoxysilane and methyltrimethoxysilane. , phenyltrimethoxysilane and dimethyldimethoxysilane, and 3-(meth)acryloxypropyltrimethoxysilane are more preferably used in combination.

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

In this embodiment, as the hydrolyzable silicon compound used for producing the polymer A, in addition to the above-described compounds, a cyclic siloxane oligomer can be used in combination. By using a cyclic siloxane oligomer together, it is possible to obtain a coating film with even better flexibility and the like.

Examples of the cyclic siloxane oligomer include, but are not limited to, compounds represented by the following formula (2).

(R' ₂ SiO) _m (2)
In the formula (2), each R' is independently a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. and an aryl group having 6 to 20 carbon atoms substituted with a halogen atom. m is an integer of 2 or more and 20 or less.

Among the cyclic siloxane oligomers, cyclic dimethylsiloxane oligomers such as octamethylcyclotetrasiloxane are preferred from the viewpoint of reactivity and the like.

Titanium alkoxide, zirconium alkoxide, condensation products or chelates thereof can be used in combination with the hydrolyzable silicon compound in the production of component A. By using these compounds in combination, it is possible to obtain a coating film having even better water resistance and the like.

Examples of titanium alkoxides include, but are not limited to, tetramethoxytitanium, tetraethoxytitanium, tetra-i-propoxytitanium, tetra-n-propoxytitanium, tetra-n-butoxytitanium, tetra-sec- butoxytitanium, tetra-tert-butoxytitanium, and the like.

A condensate thereof may be used as the titanium alkoxide, and in that case, the polystyrene-equivalent weight average molecular weight of the condensate is not particularly limited, but is preferably 200 to 5000, more preferably 300 to 1000. .

Examples of zirconium alkoxides include, but are not limited to, tetramethoxyzirconium, tetraethoxyzirconium, tetra-i-propoxyzirconium, tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, tetra-sec- butoxyzirconium and tetra-tert-butoxyzirconium.

As the zirconium alkoxide, its condensate may be used, and in that case, the polystyrene-equivalent weight average molecular weight of the condensate is not particularly limited, but is preferably 200 to 5000, more preferably 300 to 1000. .

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

Component A preferably contains 20 to 70% by mass of structural units derived from dimethyldimethoxysilane (a) in terms of hydrolysis condensate.

The lower limit of the content of structural units derived from dimethyldimethoxysilane in component A is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 35% by mass in terms of hydrolysis condensate. That's it.

The upper limit of the content of structural units derived from dimethyldimethoxysilane in component A is preferably 70% by mass or less, more preferably 68% by mass or less, and still more preferably 65% by mass in terms of hydrolysis condensate. It is below.

When the content of the structural unit derived from dimethyldimethoxysilane in component A is within the above range, the effect of improving the weather resistance of the coating film can be obtained.

The hydrolytic condensate referred to here is a condensate in which reactive groups (eg, alkoxy groups) of dimethyldimethoxysilane are converted to silanol bonds by hydrolysis or condensation reaction.

The content (% by mass) of dimethyldimethoxysilane in terms of hydrolysis condensate is calculated from the content (total solid content) of polymer A obtained as the heating residue of the AD component and the amount of dimethyldimethoxysilane charged. be able to.

Content of dimethyldimethoxysilane in terms of hydrolyzed condensate (% by mass) = charged amount of dimethyldimethoxysilane (g) x 0.617/total solid content (g) x 100

A chelating agent that forms a chelate by coordinating with the free metal ion of the metal compound can also be used in combination when the A component is produced.

Preferable chelating agents include, but are not limited to, alkanolamines such as diethanolamine and triethanolamine; glycols such as ethylene glycol, diethylene glycol and propylene glycol; acetylacetone; ethyl acetoacetate; be done.

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

By using these chelating agents, it is possible to control the polymerization rate of the hydrolyzable silicon compound and the like, and further improve the polymerization stability in the presence of water and an emulsifier.

The amount of the chelating agent to be blended is not particularly limited, but is preferably 0.1 mol to 2 mol per 1 mol of free metal ions to be coordinated.

Examples of emulsifiers that can be used in the production of component A include, but are not limited to, alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfate, polyoxyethylene alkylarylsulfate, Acidic emulsifiers such as polyoxyethylene distyrylphenyl ether sulfonic acid; alkali metal (Li, Na, K, etc.) salts of said acidic emulsifiers, ammonium salts of said acidic emulsifiers; anionic surfactants such as fatty acid soaps; Alkyltrimethylammonium bromide, alkylpyridinium bromide, quaternary ammonium salts such as imidazolinium laurate, pyridinium salts, imidazolinium salt type cationic surfactants; polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan fatty acid esters, nonionic surfactants such as polyoxyethyleneoxypropylene block copolymers and polyoxyethylene distyrylphenyl ether; reactive emulsifiers having radically polymerizable double bonds;

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

Examples of anionic reactive emulsifiers include, but are not limited to, ethylenically unsaturated monomers having a sulfonic acid group, a sulfonate group, a sulfate ester group, and salts thereof. Compounds having an acid group or a group that is an ammonium salt or an alkali metal salt thereof (ammonium sulfonate group or alkali metal sulfonate group) are preferred.

For example, alkylaryl sulfosuccinate (e.g., Sanyo Kasei Co., Ltd., "Eleminol (trademark) JS-20", e.g., Kao Corporation, "Latemul (trademark) S-120", "Latemul S-180A", "Latemul S-180” and the like.), for example, polyoxyethylene alkylpropenylphenyl ether sulfate (for example, Dai-ichi Kogyo Seiyaku Co., Ltd., “Aqualon (trademark) HS-10” and the like.), for example , α-[1-[(allyloxy)methyl]-2-(nonylphenoxy)ethyl]-ω-polyoxyethylene sulfate (for example, manufactured by ADEKA, "Adekari Soap (trademark) SE-10N", etc. ), for example, ammonium-α-sulfonato-ω-1-(allyloxymethyl)alkyloxypolyoxyethylene (for example, "Aqualon KH-1025" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), For example, styrene sulfonate (e.g., Tosoh Organic Chemical Co., Ltd., "Spinomer (trademark) NaSS", etc.), e.g., α-[2-[(allyloxy)-1-(alkyloxymethyl)ethyl]- ω-polyoxyethylene sulfate (e.g., manufactured by ADEKA, "Adekari Soap (trademark) SR-1025", etc.), e.g., polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) Ether sulfate ester salts (eg, "Latemul (trademark) PD-104" manufactured by Kao Corporation) and the like can be mentioned.

Among these, ammonium-α-sulfonato-ω-1-(allyloxymethyl)alkyloxypolyoxyethylene, α-[2-[(allyloxy)-1-(alkyloxymethyl)ethyl]-ω-polyoxyethylene Sulfate salts are preferred.

Examples of nonionic reactive emulsifiers include, but are not limited to, α-[1-[(allyloxy)methyl]-2-(nonylphenoxy)ethyl]-ω-hydroxypolyoxyethylene (For example, (Manufactured by ADEKA Co., Ltd., "Adekari Soap NE-20", "Adekari Soap NE-30", "Adekari Soap NE-40", etc.), for example, polyoxyethylene alkyl propenyl phenyl ether (For example, Daiichi Kogyo Seiyaku Co., Ltd., "Aqualon RN-10", "Aqualon RN-20", "Aqualon RN-30", "Aqualon RN-50", etc.), for example, α-[2 -[(allyloxy)-1-(alkyloxymethyl)ethyl]-ω-hydroxypolyoxyethylene (e.g., manufactured by ADEKA, "Adekari Soap (trademark) ER-10", etc.), e.g., poly Oxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (eg, "Latemul (trademark) PD-420" manufactured by Kao Corporation) and the like.

The amount of the emulsifier to be used is preferably 10 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the total amount of raw materials for component A, which is a polymer (e.g., hydrolyzable silicon compound and vinyl monomer). It is 0.001 to 5 parts by mass. By setting the amount of the emulsifier to be used within the above range, the polymerization stability is further improved, and the water resistance of the coating film is further improved.

Polymerization of the vinyl monomer and the hydrolyzable silicon compound in producing the polymer A is preferably carried out in the presence of a polymerization catalyst.

The polymerization catalyst for the vinyl monomer is not particularly limited, but is preferably a radical polymerization catalyst that causes addition polymerization of the vinyl monomer by being radically decomposed by heat or a reducing substance.

Examples of such radical polymerization catalysts include, but are not limited to, persulfates, peroxides, azobis compounds, and the like. These may be water-soluble or oil-soluble.

Examples of radical polymerization catalysts include, but are not limited to, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, 2,2 -azobisisobutyronitrile, 2,2-azobis(2-diaminopropane) hydrochloride, 2,2-azobis(2,4-dimethylvaleronitrile) and the like.

Although the amount of the radical polymerization catalyst to be blended is not particularly limited, it is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of vinyl monomers. In addition, if acceleration of the polymerization rate or efficient polymerization at low temperature (for example, 70 ° C. or less) is desired, for example, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, Rongalite, etc. is used as a radical polymerization catalyst. It is preferable to use in combination with

Polymerization catalysts for hydrolyzable silicon compounds include, but are not limited to, hydrogen halides such as hydrochloric acid and hydrofluoric acid; carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid and lactic acid; , p-toluenesulfonic acid; acidic emulsifiers such as alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, polyoxyethylene alkylarylsulfuric acid, polyoxyethylene distyrylphenyl ether sulfonic acid acidic or weakly acidic inorganic salts; acidic compounds such as phthalic acid, phosphoric acid, nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine , diazabicycloundecene, ethylenediamine, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)-aminopropyltrimethoxysilane, and other basic compounds; dibutyltin octylate, dibutyltin Examples include tin compounds such as dilaurate.

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

Although the vinyl monomer and the hydrolyzable silicon compound can be polymerized separately, it is preferable to carry out the polymerization at the same time because the formation of a composite can be efficiently achieved.

Suitable methods for obtaining component A include, for example, so-called emulsion polymerization, in which a vinyl monomer and a hydrolyzable silicon compound are polymerized in the presence of a sufficient amount of water for the emulsifier to form micelles. . A specific method for emulsion polymerization is not particularly limited. For example, the vinyl monomer and the hydrolyzable silicon compound are dropped into the reaction vessel as they are or in an emulsified state, all at once, in portions, or continuously. and a method of polymerizing at a reaction temperature of about 30 to 150° C. in the presence of a polymerization catalyst, preferably under atmospheric pressure to 10 MPa.
The reaction temperature and reaction pressure may not be the conditions described above depending on the reaction conditions and the like.

The solid content in the emulsion obtained by emulsion polymerization is not particularly limited, but is preferably 0.1 to 70% by mass, more preferably 1 to 55% by mass, and still more preferably 5 to 30% by mass. be.

If it is desired to further control the particle size during emulsion polymerization, it is preferable to employ a seed polymerization method in which emulsion particles are preliminarily present in an aqueous phase for polymerization. Although the pH of the polymerization system in this case is not particularly limited, it 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 (such as borax), sodium bicarbonate, and ammonia.

The method for producing component A is not particularly limited, but for example, a hydrolyzable silicon compound and a vinyl monomer are polymerized in the presence of water and an emulsifier, optionally in the presence of a solvent, and the polymerization product is an emulsion. A method of further adding water can also be adopted until it becomes However, emulsion polymerization is preferable from the viewpoint of facilitating control of the particle size of the obtained component A.

Component A preferably has a core/shell structure having a core and one or more shell layers.

Having a core/shell structure is preferable because the mechanical properties (balance between strength and flexibility, etc.) of the resulting coating film are further improved.

The confirmation of the core/shell structure of the A component can be performed, for example, by morphological observation using a transmission electron microscope or the like, analysis by viscoelasticity measurement, or the like.

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

The multistage emulsion polymerization as used herein is a method of preparing two or more reaction solutions having different compositions containing a vinyl monomer and a hydrolyzable silicon compound and polymerizing them in separate stages.

As an example of multistage emulsion polymerization, a method of synthesizing component A having a core/shell structure by two-stage emulsion polymerization will be mainly described.

An example of two-step emulsion polymerization is not particularly limited, but for example, a step of polymerizing a vinyl monomer and/or a hydrolyzable silicon compound in the presence of water and an emulsifier to obtain seed particles (first step). and a step of polymerizing a hydrolyzable silicon compound and a vinyl monomer in the presence of the obtained seed particles (second step).

The production of component A by two-stage emulsion polymerization consists of the first stage polymerization in which the first series (vinyl monomer and/or hydrolyzable silicon compound) is supplied and emulsion polymerization is performed, followed by the first stage followed by the second A two-stage polymerization process comprising supplying a series (vinyl monomer and/or hydrolyzable silicon compound) and a second stage of emulsion polymerization in an aqueous medium. At this time, the mass ratio ((M1)/(M2)) of the solid content (M1) in the first series to the solid content (M2) in the second series is not particularly limited, but is preferably 9/1 to 1 /9.

By performing such multistage emulsion polymerization, polymer particles having a more uniform particle size can be obtained. As a method of adding raw materials in multistage emulsion polymerization, a method of preparing seed particles (cores) in the first stage polymerization and then adding other monomers and the like is preferable. As a result, the particle diameter of the polymer particles obtained in the second stage polymerization is increased without changing the ratio of the volume average particle diameter/number average particle diameter of the seed particles (cores) obtained in the first stage polymerization. It is also possible to

When carrying out multi-stage emulsion polymerization of three or more stages, the number of polymerization stages may be increased in the same manner as in two-stage polymerization.

The content of component A in the aqueous composition of the present embodiment is not particularly limited, but is preferably 0 to 5.0% by mass, more preferably 0 to 4.0% by mass, and still more preferably 0 ~3.0% by mass.

By setting the content of the A component in the water-based composition to the above range, the coating has even better appearance, weather resistance, stain resistance, sealing stain resistance, biological stain resistance, and water retention on dark-colored substrates. membranes can be obtained.

The content of component A in the coating film obtained from the aqueous composition of the present embodiment is preferably 0 to 38.0% by mass, more preferably 0 to 28.0% by mass, and still more preferably 0 to 25% by mass. .0% by mass. By setting the content of the A component in the coating film to the above range, the coating film has even better appearance, weather resistance, stain resistance, sealing stain resistance, biological stain resistance, and water retention on dark-colored substrates. can be obtained.

<Inorganic oxide B having no photocatalytic activity>
The water-based composition of the present embodiment contains an inorganic oxide B that does not have photocatalytic activity. The term "having no photocatalytic activity" as used herein means that neither an oxidation reaction nor a reduction reaction occurs upon irradiation with light. In this specification, the inorganic oxide B having no photocatalytic activity may be simply referred to as the B component.

Component B is not particularly limited, and examples thereof include silicon dioxide (silica), aluminum oxide (alumina), calcium silicate, magnesium oxide, antimony oxide, zirconium oxide, and composite oxides thereof. Among these, silicon dioxide, aluminum oxide, antimony oxide, and composite oxides thereof are preferable, and silicon dioxide is more preferable, from the viewpoint of having many surface hydroxyl groups.

The inorganic oxide particles used as component B are preferably present as colloidal particles such as hydrates. That is, the inorganic oxide colloidal particles enable further formation of a composite with other components such as the C component, further improving the stability of the aqueous composition.

Silicon dioxide is preferably colloidal silica. Colloidal silica is not particularly limited, and examples thereof include colloidal silica, which is a dispersion of silica having silicon dioxide as a basic unit in water or a water-soluble solvent.

The method for producing colloidal silica is not particularly limited, and for example, it can be prepared by a sol-gel method. When prepared by the sol-gel method, Werner Stober et al. ; Journal of Colloid And Interface Science, vol. 26, pp. 62-69 (1968) and Rickey D. Badley et al. ; Lang muir 6, 792-801 (1990), "Shikizai Kyokai Zasshi", 61 [9] 488-493 (1988), etc. can be referred to.

The lower limit of the number average particle size of component B is usually more than 30 nm, preferably 35 nm or more, more preferably 40 nm or more. The upper limit of the number average particle size of component B is usually 160 nm or less, preferably 150 nm or less, more preferably 130 nm or less, and still more preferably 100 nm or less.

By setting the number average particle size of component B to more than 30 nm, cracks in the coating film and water retention of the coating film are further improved. Although the mechanism by which cracks are improved has not been clarified, by setting the number average particle size to more than 30 nm, the viscosity increase in the process of drying the aqueous composition to form a coating film is suppressed, so cracks in the coating film is assumed to be less likely to occur. Moreover, it is presumed that the specific surface area of the dried product of component (B) is reduced by setting the number average particle size to more than 30 nm, and the water retention is further improved. By setting the number average particle size of the B component to 160 nm or less, the appearance is further improved when a dark-colored base material is used. Incidentally, the number average particle diameter can be measured by a method using a transmission electron microscope described in Examples described later.

Colloidal silica may be either acidic or basic in the form of an aqueous dispersion.

A commercially available product can also be used as the acidic colloidal silica that uses water as a dispersion medium. Examples of such commercially available products include, but are not limited to, "Snowtex (trademark)-OL" and "Snowtex-OYL" manufactured by Nissan Chemical Industries, Ltd.

Examples of basic colloidal silica include, but are not limited to, colloidal silica stabilized by the addition of alkali metal ions, ammonium ions, amines, and the like. These can also use a commercial item. Examples of such commercially available products include, but are not limited to, Nissan Chemical Industries, Ltd. "Snowtex-30L", "Snowtex-XL", "Snowtex-YL", "Snowtex -ZL”, “Snowtex-MP-1040”, “Cataroid SI-45P”, “Cataroid SI-80P”, “Cataroid SS-120”, “Cataroid SS-140” manufactured by JGC Catalysts and Chemicals Co., Ltd., etc. be done.

A commercial product can also be used as colloidal silica using a water-soluble solvent as a dispersion medium. Examples of such commercially available products include, but are not limited to the following, for example, "IPA-ST-L (isopropyl alcohol dispersion type)" and "IPA-ST-ZL (isopropyl alcohol dispersion type)" manufactured by Nissan Chemical Industries, Ltd. type)” and the like.

The colloidal silica mentioned above may be used individually by 1 type, and may use 2 or more types together. Furthermore, alumina, sodium aluminate, and the like may be included as minor components. Colloidal silica may also contain inorganic bases (sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc.) and organic bases (tetramethylammonium, etc.) as stabilizers.

The content of component B in the aqueous composition of the present embodiment is not particularly limited, but is preferably 0.3 to 8.0% by mass, more preferably 0.7 to 7.5% by mass, More preferably, it is 1.0 to 7.0% by mass.
By setting the content of the B component in the water-based composition within the above range, the coating film has even better appearance, weather resistance, stain resistance, sealing stain resistance, biological stain resistance, and cracks on dark-colored substrates. can be obtained.

In the water-based composition of the present embodiment, when the total amount of the polymer A, the inorganic oxide B having no photocatalytic activity, and the inorganic oxide C having photocatalytic activity described later is 100 parts by mass in terms of solid content, The inorganic oxide B having no photocatalytic activity may be contained in an amount of preferably 20 to 99 parts by mass, more preferably 40 to 98 parts by mass, and even more preferably 50 to 98.0 parts by mass. By setting the content of the B component in the water-based composition within the above range, the coating film has even better appearance, weather resistance, stain resistance, sealing stain resistance, biological stain resistance, and cracks on dark-colored substrates. can be obtained.

The content of component B in the coating film obtained from the aqueous composition of the present embodiment is preferably 18.25 to 99.85% by mass, more preferably 46.00 to 99.85% by mass, More preferably, it is 56.00 to 99.85% by mass.

By setting the content of the B component in the coating film to the above range, a coating film having even better appearance, weather resistance, stain resistance, sealing stain resistance, biological stain resistance, and cracking on dark-colored substrates can be obtained. Obtainable.

<Inorganic oxide C having photocatalytic activity>
The aqueous composition of the present embodiment contains an inorganic oxide C having photocatalytic activity.
As a result, photocatalytic activity and hydrophilicity can be expressed by irradiating the coating film with light.
In this specification, the inorganic oxide C having photocatalytic activity may be simply referred to as the C component.

The inorganic oxide C having photocatalytic activity is not particularly limited as long as it is an inorganic oxide having photocatalytic activity.

Examples of the _C component include, but _are not limited to, _TiO2 , ZnO, _SrTiO3 , _BaTiO3 , _BaTiO4 , _BaTi4O9 , _{K2NbO3 , Nb2O5 , Fe2O3} . , Ta2O5 _{, K3Ta3Si2O3 , WO3 , SnO2 , Bi2O3} , _{BiVO4 , NiO} , _Cu2O , _RuO2 , _CeO2 ; from Ti, Nb, Ta, and V A layered oxide having at least one element selected from the group consisting of , JP-A-08-089800, JP-A-08-089804, JP-A-09-248465, JP-A-10-099694, JP-A-10-244165, etc.).

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

Component C is an inorganic oxide having photocatalytic activity, and is preferably an inorganic oxide having photocatalytic activity whose particle surfaces have been modified.

By modifying the particle surface, the generation of reactive oxygen species such as H ₂ O ₂ or .OH can be suppressed, and damage to the coating film can be further suppressed.

Substances that modify the particle surface include, but are not limited to, silica, aluminum, copper oxides, iron oxides, and the like. Among these, silica is preferred. A similar effect can be obtained by modifying the particle surface with a metal such as Fe, Cu, Al or Pt or a complex such as chloroplatinic acid.

A method for modifying the surface of the C component will be described using titanium oxide as an example.
The method of modifying the surface of titanium oxide is not particularly limited, and examples thereof include a method of adding a silicon compound to a slurry of titanium oxide and precipitating a hydrous oxide of silicon through a process such as neutralization. be done.

The silicon compound is not particularly limited, and for example, a water-soluble alkali metal silicate such as sodium silicate can be used. Among these, sodium silicate is preferable from the viewpoint of being colorless and not coloring the titanium oxide sol.

The amount of silicon oxide to be modified with a hydrous oxide is preferably 3 to 25% by mass, more preferably 4 to 23% by mass, and even more preferably 5 to 20% by mass based on the oxide based on titanium oxide.
When the amount of modification treatment is equal to or higher than the lower limit, an increase in the amount of active oxygen species can be suppressed, and damage to the coating film can be prevented. In addition, when the modification treatment amount is equal to or less than the upper limit, aggregation of titanium oxide can be suppressed, and an increase in the viscosity of the sol can be suppressed, so that dispersibility and transparency are further improved.

As the C component, an inorganic oxide in which the surface of particles having photocatalytic activity is modified, and a metal element such as gold, silver, copper, platinum, and zinc is supported on the inorganic oxide. can also be used.

The method for supporting a metal on the C component is not particularly limited. Examples include a method of reacting with trisodium dihydrate, tannic acid, or the like, and a silane compound having a thiol group or an amino group or the like may be used for the purpose of further firmly supporting. The silane compound having a thiol group is not particularly limited. - mercaptopropylethyldiethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyltributoxysilane, 1,4-dimercapto-2-(trimethoxysilyl)butane, 1,4-dimercapto-2-(triethoxy silyl)butane, 1,4-dimercapto-2-(tripropoxysilyl)butane, 1,4-dimercapto-2-(tributoxysilyl)butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercapto methyl-3-mercaptopropyltriethoxysilane, 2-mercaptomethyl-3-mercaptopropyltripropoxysilane, 2-mercaptomethyl-3-mercaptopropyltributoxysilane, 1,2-dimercaptoethyltrimethoxysilane, 1,2 -dimercaptoethyltriethoxysilane, 1,2-dimercaptoethyltripropoxysilane, 1,2-dimercaptoethyltributoxysilane, (trimercaptomethyl)methoxysilane, (trimercaptoethyl)methoxysilane, (trimercaptopropyl ) methoxysilane and the like. Among them, 3-mercaptopropyltrimethoxysilane is preferred because of its high hydrolytic reactivity and easy availability. N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane and the like. Among them, 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane are preferred because of their high hydrolysis reactivity and easy availability.

The amount of metal supported is preferably 0.1 to 5% by mass, more preferably 0.1 to 4.8% by mass, more preferably 0.1 to 4.6% by mass, relative to titanium oxide. % is more preferred.
When the supported amount is within the above range, sedimentation of the metal-supported titanium oxide can be suppressed, and a coating film excellent in biofouling resistance can be obtained.

The content of component C in the water-based composition of the present embodiment is preferably 0.05 to 2.5% by mass, more preferably 0.10 to 2.0% by mass, and still more preferably 0.1% by mass. 15 to 1.4% by mass.
By setting the content of the C component within the above range, a coating film having even better appearance, weather resistance, stain resistance, sealing stain resistance, biological stain resistance, cracking, and water retention on dark-colored substrates can be obtained. be able to.

In the water-based composition of the present embodiment, when the total amount of the polymer A, the inorganic oxide B having no photocatalytic activity, and the inorganic oxide C having photocatalytic activity is 100 parts by mass in terms of solid content, it is particularly limited However, the inorganic oxide C having photocatalytic activity may be contained in an amount of preferably 1 to 40 parts by mass, more preferably 3 to 38 parts by mass, and even more preferably 3 to 35 parts by mass. By setting the content of the inorganic oxide C having photocatalytic activity in the water-based composition within the above range, the appearance, weather resistance, stain resistance, sealing stain resistance, biological stain resistance, crack, And a coating film with even better water retention can be obtained.

The content of component C in the coating film obtained from the aqueous composition of the present embodiment is not particularly limited, but is preferably 1% by mass to 35.0% by mass, more preferably 4.0 to 35.0% by mass. %, more preferably 4.0% by mass to 33.0% by mass, still more preferably 6.0% by mass to 33.0% by mass, still more preferably 6.0% by mass to 29.0% by mass is.
By setting the content of the component C within the above range, it is possible to obtain a coating film with even better appearance, weather resistance, stain resistance, sealing stain resistance, biological stain resistance, and water retention on dark-colored substrates. can.

<Fluorocarbon Surfactant D>
The aqueous composition of the present embodiment preferably further contains a fluorocarbon surfactant D.
In this specification, the fluorocarbon surfactant D may be simply referred to as the D component.

By containing component D, when the water-based composition of the present embodiment and the water-based paint containing the same are used for coating, the wettability to organic substrates and the like is further improved, and appearance problems such as repelling are also prevented. can be further suppressed. Furthermore, the uniformity of the coating film is further improved. Although the reasons for this are not clear, it is presumed that the surface tension of the water-based composition can be lowered by containing the D component. Note that the effects of the present embodiment are not limited to these.

Component D is not particularly limited, but amphoteric surfactants are preferred, for example.
Examples of amphoteric surfactants include, but are not limited to, nonionic amphoteric surfactants, anionic amphoteric surfactants, and cationic amphoteric surfactants. Preferred specific examples include amphoteric surfactants having perfluoroalkyl groups of 3 to 20 carbon atoms.
Examples of amphoteric surfactants having a perfluoroalkyl group having 3 to 20 carbon atoms include, but are not limited to, perfluoroalkylsulfonates, perfluoroalkylcarboxylates, perfluoroalkylamine oxides, perfluoroalkyl Examples include ethylene oxide adducts, perfluoroalkyl compounds having an anionic group and a cationic group, and the like. Among these, perfluoroalkyl ethylene oxide adducts and perfluoroalkyl compounds having an anionic group and a cationic group are preferred from the viewpoint of lowering the surface tension of the paint.

Examples of perfluoroalkylsulfonates include, but are not limited to, ammonium salts and potassium salts of perfluorooctane sulfonic acid.

For example, a commercially available product can be used as the perfluoroalkylcarboxylate. Examples of such commercially available products include, but are not limited to, "Surflon S-211" manufactured by AGC Seimi Chemical Co., Ltd., and the like.

As the perfluoroalkylamine oxide, for example, a commercially available product can also be used. Examples of such commercially available products include, but are not limited to, "Surflon S-241" manufactured by AGC Seimi Chemical Co., Ltd., and the like.

As the perfluoroalkylethylene oxide adduct, for example, a commercially available product can also be used. Examples of such commercially available products include, but are not limited to, DIC's "Megafac F-444" and AGC Seimi Chemical's "Surflon S-242".

As the perfluoroalkyl compound having an anionic group and a cationic group, for example, a commercially available product can be used. Examples of such commercially available products include, but are not limited to, "Surflon S-231", "Surflon S-232", "Surflon S-233" manufactured by AGC Seimi Chemical Co., Ltd., and the like.
These may be used individually by 1 type, and may use 2 or more types together.

The content of component D in the aqueous composition is not particularly limited, but is preferably 0.0001 to 0.50% by mass, more preferably 0.001 to 0.45% by mass, and still more preferably 0 0.01 to 0.40% by mass.
By setting the content of component D within the above range, it is possible to obtain a coating film with even better appearance, weather resistance, stain resistance, sealing stain resistance, and biological stain resistance on dark-colored substrates.

The content of component D in the coating film obtained from the aqueous composition of the present embodiment is not particularly limited, but is preferably 0.002% by mass to 17.5% by mass, more preferably 0.1% by mass. ~10.0% by mass, more preferably 0.15% to 10.0% by mass. By setting the content of the component D in the above range, it is possible to obtain an aqueous composition having excellent wettability and sprayability, and the appearance on dark-colored substrates, weather resistance, stain resistance, sealing stain resistance, And it is possible to obtain a coating film having even better resistance to biological contamination.

<Fading dye E>
The water-based composition of the present embodiment preferably further contains a fadeable dye E.
In this specification, the fadeable dye E may be simply referred to as the E component.

By containing the discolorable dye E in the water-based composition of the present embodiment, it is possible to prevent troubles such as failure to apply, double application, and uneven application.

The E component is preferably one that does not lose its color when exposed to sunlight and does not impair the design of the base. The time until discoloration varies depending on the season, irradiation direction, etc., but usually, the period until discoloration is visually confirmed is preferably 20 days or less, more preferably 10 days or less, and still more preferably 3 days. days or less.

The E component is not particularly limited as long as it has the property of decolorizing when exposed to sunlight. Examples include methylene blue, crystal violet, malachite green, brilliant blue FCF, erythrosine, new coccine, phloxine, One selected from the group consisting of Rose Bengal, Acid Red, and Fast Green FCF. Among these, methylene blue is preferable from the viewpoint of good color developability and high color loss speed.
These may be used individually by 1 type, and may use 2 or more types together.

The content of component E in the aqueous composition of the present embodiment is not particularly limited, but is preferably 0.0005 to 0.04% by mass, more preferably 0.001 to 0.035% by mass, More preferably, it is 0.005 to 0.03% by mass. By setting the content of component E in the water-based composition within the above range, the color developability and color fading properties of the coating film are further improved. Here, the term "color development" refers to the ability to develop color to the extent that the painted surface and the unpainted surface can be distinguished visually from the difference in color, and the term "fading" refers to the degree of color that does not impair the design of the base material. It refers to the property of fading.

The content of component E in the coating film obtained from the aqueous composition of the present embodiment is not particularly limited, but is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.9. % by mass, more preferably 0.1 to 0.8% by mass. By setting the content of component E within the above range, it is possible to obtain a coating film with even better appearance, weather resistance, stain resistance, sealing stain resistance, and biological stain resistance on dark-colored substrates.

<Antifoaming agent F>
The water-based composition of the present embodiment may contain an antifoaming agent F. By containing the antifoaming agent F, the wettability to the organic substrate and the like is further improved when the water-based composition of the present embodiment and the water-based paint containing the same are applied, and repelling and entrainment of bubbles Appearance problems such as craters (sprayability) can be further suppressed. The antifoaming agent F is not particularly limited, but for example, a mineral oil-based antifoaming agent can be used. A mineral oil-based antifoaming agent is an antifoaming agent containing mineral oil as an antifoaming component called a carrier.

Antifoaming agents are usually composed of a "carrier" and a "nucleating agent". Although the nucleating agent is not particularly limited, for example, inorganic hydrophobic silica, organic metallic soap, amide wax, or the like can be used.

The mineral oil-based antifoaming agent is not particularly limited, but commercially available products can also be used.
Hydrophobic silica type mineral oil antifoaming agents include, but are not limited to, Nopco 8034, Nopco 8034-L, SN Deformer AP, SN Deformer H-2, SN Deformer TP-33, SN Deformer VL, SN Deformer 113, SN Deformer 154, SN Deformer 154S, SN Deformer 313, SN Deformer 314, SN Deformer 316, SN Deformer 317, SN Deformer 318, SN Deformer 319, SN Deformer 321, SN Deformer 323, SN Deformer 364, SN Deformer 414, SN Deformer 456, SN Deformer 474, SN Deformer 476-L, SN Deformer 480, SN Deformer 777, SN Deformer 1341, SN Deformer 1361 (manufactured by San Nopco) BYK-1740 (manufactured by BYK) Examples of metal soap type mineral oil antifoaming agents include, but are not limited to, Nopco DF-122, Nopco DF-122-NS, Nopco NDW, Nopco NXZ, and SN Deformer 122-SV. , SN Deformer 269, and SN Deformer 1010 (manufactured by San Nopco), and amide wax type mineral oil-based defoaming agents are not limited to the following, for example, Nopco 267-A, Nopco DF- 124-L, SN Deformer TP-39, SN Deformer 477T, SN Deformer 477-NS, SN Deformer 479, SN Deformer 1044, SN Deformer 1320, SN Deformer 1340, SN Deformer 1360, SN Deformer 5100 (manufactured by San Nopco). be done.
These may be used individually by 1 type, and may use 2 or more types together.

The content of the antifoaming agent F in the aqueous composition of the present embodiment is not particularly limited, but is preferably 0.001% by mass to 5.000% by mass, more preferably 0.0020% by mass to 4.5000% by mass. % by mass, more preferably 0.0025 to 4.000% by mass. By setting the content of the antifoaming agent F within the above range, it is possible to obtain a water-based paint and a coating film which are further superior in appearance, weather resistance, stain resistance, sprayability, and wettability on dark-colored substrates. .

The content of the antifoaming agent F in the coating film is not particularly limited, but is preferably 0.024% by mass to 1.250% by mass, more preferably 0.040% by mass to 1.200% by mass, and still more preferably It is 0.0625 to 1.1000% by mass. By setting the content of the antifoaming agent F in the above range, the sprayability and wettability of the water-based composition for obtaining the coating film are improved, and the appearance, weather resistance, and stain resistance on dark-colored substrates are further improved. A good coating film can be obtained.

The solid content (solid content) in the aqueous composition of the present embodiment is not particularly limited, but from the viewpoint of uniformity of the coating film, it is preferably 0.5 to 10.0% by mass, and more preferably. is 1.0 to 8.0% by mass, more preferably 1.5 to 6.0% by mass.
By setting the solid content in the water-based composition to the above lower limit or more, the stain resistance is further improved. By setting the content of the solid content in the water-based composition to the above upper limit or less, the transparency and cracking of the coating film are further improved.

The solid content as referred to herein can be determined by the method described in the examples below. Furthermore, depending on the application of the coating film, it may be required that the thickness of the coating film is thin. Even in such a case, physical properties such as weather resistance, stain resistance, sealing stain resistance, and biological stain resistance can be obtained even though the film thickness is thin because the solid content in the water-based composition is equal to or less than the upper limit. It can be a coating film excellent in When the solid content in the water-based composition is at least the above lower limit, it becomes possible to shorten the drying time required for coating film formation, and to further improve the working efficiency.

[Water-based paint]
The water-based paint of this embodiment contains the water-based composition described above.
The water-based paint of the present embodiment can be obtained, for example, by mixing the water-based composition described above with other components as necessary.

Examples of other components include, but are not limited to, antifoaming agents, freeze stabilizers, matting agents, cross-linking reaction catalysts, pigments, curing catalysts, cross-linking agents, fillers, and anti-skinning agents. , dispersants, wetting agents, light stabilizers, antioxidants, UV absorbers, film-forming aids, rust inhibitors, plasticizers, thickeners, lubricants, reducing agents, preservatives, antifungal agents, anti-algae agents, deodorants, anti-yellowing agents, anti-static agents, charge control agents and the like.
These may be used individually by 1 type, and may use 2 or more types together.

Examples of the pigment include inorganic oxides having no photocatalytic activity. Examples thereof include, but are not limited to, copper (II) oxide (manufactured by CIK Nanotech, "CUAP15WT%-G180"), zinc oxide, and aluminum oxide.

The content of the pigment in the coating film obtained from the water-based paint of the present embodiment is not particularly limited, but is preferably 0.01 to 5.0% by mass, more preferably 0.02 to 4.5% by mass. is. By setting the content of the pigment within the above range, it is possible to obtain a coating film with excellent appearance on a dark-colored substrate and resistance to biological contamination.

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

[Coating film]
The coating film of this embodiment is obtained from the water-based paint described above.
Specifically, for example, it can be obtained by applying the water-based paint to a predetermined application target and then drying it to remove volatile matter. Although the drying temperature is not particularly limited, for example, air drying may be performed at a temperature of 3 to 40 ° C., heat drying treatment at a temperature of about 40 to 120 ° C., ultraviolet irradiation treatment, etc. good. Air drying at a temperature of 3 to 40°C is preferred. The humidity during drying is not particularly limited, but when drying at a temperature of 3 to 40° C., the humidity is preferably 10 to 100 RH%. The above drying conditions can further improve the appearance of the coating film and cracks in the coating film.

Although the thickness of the coating film of the present embodiment is not particularly limited, it is preferably 0.15 μm or more and 5.0 μm or less. It is more preferably 0.15 μm or more and 4.0 μm or less, still more preferably 0.15 μm or more and 3.5 μm or less, and even more preferably 0.15 μm or more and 3.0 μm. When the thickness of the coating film is within the above range, the appearance of the coating film and cracking of the coating film can be further improved, and the appearance, weather resistance, stain resistance, sealing stain resistance, and biological resistance of dark-colored substrates can be improved. A coating film with even better stain resistance can be obtained.

[Composite coating]
The composite coating film of the present embodiment has at least two layers, the coating film described above and a coating film consisting of an undercoat layer, and the coating film consisting of the undercoat layer contains a polymer and an anti-algae and / or anti-mold layer. agent.

The composite coating film of the present embodiment is obtained, for example, by applying the water-based paint containing the water-based composition described above to the surface of the coating film composed of the undercoat layer and drying it to form a coating film.
The coating film comprising the undercoat layer preferably contains a polymer and one or more anti-algae and/or anti-mold agents.

(Polymer Contained in Coating Film Consisting of Undercoat Layer)
The coating film composed of the undercoat layer that constitutes the composite coating film of the present embodiment contains a polymer. Thereby, a composite coating film having excellent weather resistance can be formed. Note that the effects of the present embodiment are not limited to these.

Although the polymer is not particularly limited, for example, a polymer obtained by a method such as emulsion polymerization can be used. Examples of the polymer include, but are not limited to, polymers obtained by performing any one of radical polymerization, anionic polymerization, and cationic polymerization in an aqueous medium.

Specific examples of the polymer include, but are not limited to, poly(meth)acrylate-based polymer, polyvinyl acetate-based polymer, vinyl acetate-(meth)acrylic-based polymer, and ethylene vinyl acetate-based polymer. , silicone-based polymer, fluorine-based polymer, polybutadiene-based polymer, styrene-butadiene-based polymer, NBR-based polymer, polyvinyl chloride-based polymer, chlorinated polypropylene-based polymer, polyethylene-based polymer, polystyrene-based polymer , vinylidene chloride-based polymers, polystyrene-(meth)acrylate-based polymers, styrene-maleic anhydride-based polymers, homopolymers or copolymers represented by maleic anhydride-based polymers, silicone-modified (meth)acrylic polymers, fluorine- Modified copolymers typified by (meth)acrylic polymers, (meth)acryl-silicone polymers, epoxy-(meth)acrylic polymers and the like can be mentioned.
These may be used individually by 1 type, and may use 2 or more types together.

In addition, "(meth)acrylate" means "acrylate" and corresponding "methacrylate", and "(meth)acryl" means "acryl" and corresponding "methacryl".
The homopolymers, copolymers, modified copolymers, and the like of the polymers described above (hereinafter, they may be collectively referred to as "polymers") are preferably obtained in the form of aqueous dispersions. Preferred embodiments of these polymers include emulsions, and specific examples thereof include, but are not limited to, acrylic emulsions, acrylic silicone emulsions, silicone emulsions, and the like. These are not limited to the following, but can be obtained, for example, by emulsion polymerization of monomers such as (meth)acrylic acid esters or hydrolyzable silicon compounds described later.

The coating film composed of the undercoat layer used in the composite coating film of the present embodiment may further contain, in addition to the polymer, a compound having a functional group that reacts with the functional group contained in the polymer.

Examples of such compounds include, but are not limited to, (poly)isocyanate compounds, (poly)epoxy compounds, amino compounds, (poly)carboxy compounds, (poly)hydroxy compounds, glycol compounds, silanol compounds, silyl compounds, alkoxy compounds, (meth)acrylate compounds, and the like.
These may be used individually by 1 type, and may use 2 or more types together.

The polymer may use a vinyl monomer as a polymerization monomer.
Vinyl monomers that can be used for polymer production include, but are not limited to, (meth)acrylic acid esters, aromatic vinyl compounds, vinyl cyanide compounds, and carboxyl group-containing vinyl compounds. , hydroxyl group-containing vinyl compounds, glycidyl group-containing vinyl compounds, vinyl compounds having secondary and/or tertiary amide groups, and vinyl monomers containing functional groups such as anionic vinyl compounds.

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

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

Examples of aromatic vinyl compounds include, but are not limited to, styrene, α-methylstyrene, p-tert-butylstyrene, chlorostyrene, vinyltoluene, and the like.

Examples of vinyl cyanide compounds include, but are not limited to, (meth)acrylonitrile, α-chloroacrylonitrile, and the like.

Examples of the carboxyl group-containing vinyl compound include, but are not limited to, (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, or itaconic acid, maleic acid, and fumaric acid. Examples include half esters of dibasic acids such as acids. A carboxyl group can be introduced into the polymer by using a vinyl monomer containing a carboxyl group. As a result, it is presumed that the stability of the emulsion can be further improved and the coating film can be provided with high resistance to the external dispersion destruction action. Note that the effects of the present embodiment are not limited to these. The carboxyl groups to be introduced can be partially or wholly neutralized with ammonia, amines such as triethylamine and dimethylethanolamine, and bases such as NaOH and KOH. From the viewpoint of water resistance, the amount of the carboxyl group-containing vinyl monomer used in the total amount of vinyl monomers used in the production of the polymer is preferably 0 to 50% by mass.

Examples of hydroxyl group-containing vinyl compounds include, but are not limited to, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl Hydroxyalkyl esters of (meth)acrylic acid such as (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl mono butyl fumarate, allyl alcohol and (poly)oxyethylene mono(meth)acrylate having 1 to 100 ethylene oxide groups; (poly)oxypropylene mono(meth)acrylate having 1 to 100 propylene oxide groups; Furthermore, "PLAXEL FM, FA Monomer" (trade names of caprolactone addition monomers manufactured by Daicel Chemical Industries, Ltd.) or other hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids can be used.

Examples of (poly)oxyethylene mono(meth)acrylates include, but are not limited to, ethylene glycol (meth)acrylate, ethylene glycol methoxy(meth)acrylate, diethylene glycol (meth)acrylate, methoxy Diethylene glycol (meth)acrylate, tetraethylene glycol (meth)acrylate, tetraethylene glycol methoxy(meth)acrylate, and the like can be mentioned.

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

The ratio of the hydroxyl group-containing vinyl monomer in the total amount of vinyl monomers used in the production of the polymer is not limited to the following, but from the viewpoint of the water resistance of the coating film, it is preferably 0 to 95% by mass. be.

Examples of glycidyl group-containing vinyl compounds include, but are not limited to, glycidyl (meth)acrylate, allyl glycidyl ether, allyl dimethyl glycidyl ether, and the like.

Examples of vinyl compounds having secondary and/or tertiary amide groups include, but are not limited to, N-alkyl-substituted (meth)acrylamides, N-alkylene-substituted (meth)acrylamides, and the like.

Examples of N-alkyl-substituted (meth)acrylamides include, but are not limited to, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N , N-diethylacrylamide, N-methyl-N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, Nn-propyl (meth)acrylamide, N-methyl-Nn-propyl (meth)acrylamide, N-methyl-N-isopropyl(meth)acrylamide, N-(meth)acryloylpyrrolidine, N-(meth)acryloylpiperidine, N-acryloylhexahydroazepine, N-(meth)acryloylmorpholine, N-vinylpyrrolidone, N- vinylcaprolactam, N,N'-methylenebis(meth)acrylamide, N-vinylacetamide, diacetone(meth)acrylamide, N-methylol(meth)acrylamide and the like.

The polymer can use vinyl monomers other than the vinyl monomers described above as polymerization monomers.

Examples of vinyl monomers other than the vinyl monomers described above include, but are not limited to, (meth)acrylamide, olefins such as ethylene, propylene, and isobutylene; dienes such as butadiene; vinyl chloride; , vinylidene chloride vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene, and other haloolefins; vinyl acetate, vinyl propionate, n-vinyl butyrate, vinyl benzoate, p-tert-butyl vinyl benzoate, vinyl pivalate, Carboxylic acid vinyl esters such as vinyl 2-ethylhexanoate, vinyl versatate and vinyl laurate; carboxylic acid isopropenyl esters such as isopropenyl acetate and isopropenyl propionate; vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether Aromatic vinyl compounds such as styrene and vinyl toluene; Allyl esters such as allyl acetate and allyl benzoate; Allyl ethers such as allyl ethyl ether and allyl phenyl ether; 4-(meth)acryloyloxy-2,2, 6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, perfluoromethyl (meth)acrylate, perfluoropropyl (meth)acrylate, perfluoropropylmethyl (meth)acrylate, vinylpyrrolidone, trimethylolpropane tri(meth)acrylate, allyl (meth)acrylate, and the like.
These may be used individually by 1 type, and may use 2 or more types together.

When the polymer is produced by a polymerization reaction, a chain transfer agent may be used for the purpose of controlling the molecular weight of the polymerized product of the vinyl monomers used.

Examples of chain transfer agents include, but are not limited to, alkylmercaptans such as n-octylmercaptan, n-dodecylmercaptan and tert-dodecylmercaptan; aromatic mercaptans such as benzylmercaptan and dodecylbenzylmercaptan. ; thiocarboxylic acids such as thiomalic acid, salts thereof, or alkyl esters thereof; polythiols; disulfides such as diisopropyl xanthogen disulfide, di(methylenetrimethylolpropane) xanthogen disulfide; Allyl compounds and the like can be mentioned.
These may be used individually by 1 type, and may use 2 or more types together.

The polymer is preferably produced by a polymerization reaction between the vinyl monomer and the hydrolyzable silicon compound described above.

In such a case, the hydrolyzable silicon compound used for producing the polymer is not limited to the following, but for example, a compound represented by the following formula (1), a silane coupling agent, and these are preferred.

SiWxRy (1)
In the above formula (1), W is an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, and an aminoxy group. and at least one selected from the group consisting of amide groups.
R is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a halogen-substituted 6 to 20 carbon atoms. represents at least one group selected from the group consisting of aryl groups.
x is an integer of 1 or more and 4 or less, y is an integer of 0 or more and 3 or less, and satisfies the relationship x+y=4.
When W is plural, when R is plural, each W and R may be the same or different.

Examples of the compound represented by formula (1) include, but are not limited to, silicon alkoxide represented by formula (1).

Examples of the silane coupling agent include, but are not limited to, hydrolyzable groups (e.g., alkoxy groups having 1 to 20 carbon atoms, hydroxyl groups, acetoxy groups having 1 to 20 carbon atoms, halogen atoms, hydrogen at least one selected from the group consisting of atoms, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group and an amide group, etc.) and a functional group having reactivity with other compounds (for example, a vinyl polymerizable group , epoxy group, amino group, methacrylic group, thiol group, isocyanate group, etc.) (silane coupling agent).

By using such a silane coupling agent as the hydrolyzable silicon compound, the polycondensate of the hydrolyzable silicon compound and the vinyl monomer can be chemically bonded to each other. Thereby, the compatibility is further improved, and the transparency of the coating film is further improved.

Among the silane coupling agents described above, silane coupling agents having at least a vinyl polymerizable group and/or a thiol group are preferred, and silane coupling agents having at least a vinyl polymerizable group are more preferred.

Since the vinyl polymerizable group and the thiol group have high reactivity with the above-mentioned vinyl monomer, they can efficiently form a chemical bond through a copolymerization reaction or a chain transfer reaction with the vinyl monomer. Therefore, by using a silane coupling agent having a vinyl polymerizable group or a thiol group, it can be efficiently combined with other components (for example, vinyl monomers, etc.) constituting the polymer. By using such a polymer in which a hydrolyzable silicon compound (or its polymerization product) and/or a vinyl monomer (or its polymerization product) is chemically bonded, weather resistance and strength can be improved. etc. can be obtained. Note that the effects of the present embodiment are not limited to these.

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

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

Examples of the hydrolyzable silicon compound and silane coupling agent represented by formula (1) include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra tetraalkoxysilanes such as isopropoxysilane and tetra-n-buxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane silane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane ethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltri Methoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-( 3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane , 3-(meth)acryloyloxypropyl tri-n-propoxysilane, 3-(meth)acryloyloxypropyl Trialkoxysilanes such as lyisopropoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyl Dimethoxysilane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n- Pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n - dialkoxysilanes such as octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane; monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane; and the like.

Among these, tetraalkoxysilanes, trialkoxysilanes, and dialkoxysilanes are preferable, and tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, and dimethyldimethoxysilane. is more preferred.

These silicon alkoxides and silane coupling agents represented by formula (1) may be used alone or in combination of two or more. Among these, from the viewpoint of improving the performance of the water-based composition and the resulting coating film, it is preferable to use the silicon alkoxide represented by the formula (1) in combination with a silane coupling agent, such as tetraethoxysilane, methyltrimethoxysilane, More preferably, at least one selected from the group consisting of silane, phenyltrimethoxysilane and dimethyldimethoxysilane and 3-(meth)acryloxypropyltrimethoxysilane are used in combination.

Titanium alkoxide, zirconium alkoxide, condensation products or chelates thereof can be used together with the hydrolyzable silicon compound when producing the polymer.

By using these compounds in combination, it is possible to obtain a coating film having even better water resistance and the like.

Examples of titanium alkoxides include, but are not limited to, tetramethoxytitanium, tetraethoxytitanium, tetra-i-propoxytitanium, tetra-n-propoxytitanium, tetra-n-butoxytitanium, tetra-sec- butoxytitanium, tetra-tert-butoxytitanium, and the like.

Examples of zirconium alkoxides include, but are not limited to, tetramethoxyzirconium, tetraethoxyzirconium, tetra-i-propoxyzirconium, tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, tetra-sec- butoxyzirconium and tetra-tert-butoxyzirconium.

When producing the polymer, a chelating agent that coordinates with free metal ions of the metal compound to form a chelate can also be used in combination.

Preferable chelating agents include, but are not limited to, alkanolamines such as diethanolamine and triethanolamine; glycols such as ethylene glycol, diethylene glycol and propylene glycol; acetylacetone; ethyl acetoacetate; be done.

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

By using these chelating agents, it is possible to control the polymerization rate of the hydrolyzable silicon compound and the like, and further improve the polymerization stability in the presence of water and an emulsifier.

The amount of the chelating agent to be blended is not particularly limited, but is preferably 0.1 mol to 2 mol per 1 mol of free metal ions to be coordinated.

Examples of emulsifiers that can be used in polymer production include, but are not limited to, alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfate, polyoxyethylene alkylarylsulfate, Acidic emulsifiers such as polyoxyethylene distyrylphenyl ether sulfonic acid; alkali metal (Li, Na, K, etc.) salts of said acidic emulsifiers, ammonium salts of said acidic emulsifiers; anionic surfactants such as fatty acid soaps; Alkyltrimethylammonium bromide, alkylpyridinium bromide, quaternary ammonium salts such as imidazolinium laurate, pyridinium salts, imidazolinium salt type cationic surfactants; polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan fatty acid esters, nonionic surfactants such as polyoxyethyleneoxypropylene block copolymers and polyoxyethylene distyrylphenyl ether; reactive emulsifiers having radically polymerizable double bonds;

Among these emulsifiers, reactive emulsifiers having a radically polymerizable double bond (hereinafter sometimes simply referred to as reactive emulsifiers) are preferred. By using such a reactive emulsifier, the water dispersion stability of the polymer is greatly improved, and the water resistance of the resulting coating film is further improved.

Examples of anionic reactive emulsifiers include, but are not limited to, ethylenically unsaturated monomers having a sulfonic acid group, a sulfonate group, a sulfate ester group, and salts thereof. Compounds having an acid group or a group that is an ammonium salt or an alkali metal salt thereof (ammonium sulfonate group or alkali metal sulfonate group) are preferred.

Examples of anionic reactive emulsifiers include alkylaryl sulfosuccinates (e.g., Sanyo Chemical Co., Ltd., "Eleminol (trademark) JS-20", Kao Corporation, "Latemul (trademark) S-120", "Latemul S-180A”, “Latemul S-180”, etc.), polyoxyethylene alkylpropenyl phenyl ether sulfate (for example, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., “Aqualon (trademark) HS-10”, etc.). ), α-[1-[(allyloxy)methyl]-2-(nonylphenoxy)ethyl]-ω-polyoxyethylene sulfate (for example, manufactured by ADEKA, “Adekari Soap (trademark) SE-10N ”, ammonium-α-sulfonato-ω-1-(allyloxymethyl)alkyloxypolyoxyethylene (for example, “Aqualon KH-1025” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). , styrene sulfonate (for example, Tosoh Organic Chemical Co., Ltd., "Spinomer (trademark) NaSS" etc.), α-[2-[(allyloxy)-1-(alkyloxymethyl)ethyl]-ω-poly Oxyethylene sulfate (e.g., ADEKA, "Adekari Soap (trademark) SR-1025", etc.), sulfate of polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (For example, "Latemul (trademark) PD-104" manufactured by Kao Corporation and the like can be mentioned.) and the like.

Among these, ammonium-α-sulfonato-ω-1-(allyloxymethyl)alkyloxypolyoxyethylene, α-[2-[(allyloxy)-1-(alkyloxymethyl)ethyl]-ω-polyoxyethylene Sulfate salts are preferred.

Examples of nonionic reactive emulsifiers include, but are not limited to, α-[1-[(allyloxy)methyl]-2-(nonylphenoxy)ethyl]-ω-hydroxypolyoxyethylene (For example, (Manufactured by ADEKA, "Adekari Soap NE-20", "Adekari Soap NE-30", "Adekari Soap NE-40", etc.), polyoxyethylene alkyl propenyl phenyl ether (eg , Daiichi Kogyo Seiyaku Co., Ltd., "Aqualon RN-10", "Aqualon RN-20", "Aqualon RN-30", "Aqualon RN-50", etc.), α-[2-[(allyloxy )-1-(alkyloxymethyl)ethyl]-ω-hydroxypolyoxyethylene (for example, manufactured by ADEKA, "Adekari Soap (trademark) ER-10", etc.), polyoxyethylene polyoxybutylene ( 3-methyl-3-butenyl)ether (for example, "Latemul (trademark) PD-420" manufactured by Kao Corporation) and the like.

The amount of the above-mentioned emulsifier used is preferably 10 parts by mass or less with respect to 100 parts by mass of the total amount of raw materials for the polymer (for example, the hydrolyzable silicon compound and the vinyl monomer). By setting the amount of the emulsifier to be used within the above range, the polymerization stability is further improved, and the water resistance of the coating film is further improved.

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

The polymerization catalyst for the vinyl monomer is not particularly limited, but is preferably a radical polymerization catalyst that causes addition polymerization of the vinyl monomer by being radically decomposed by heat or a reducing substance.

Examples of such radical polymerization catalysts include, but are not limited to, persulfates, peroxides, azobis compounds, and the like. These may be water-soluble or oil-soluble.

Examples of radical polymerization catalysts include, but are not limited to, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, 2,2 -azobisisobutyronitrile, 2,2-azobis(2-diaminopropane) hydrochloride, 2,2-azobis(2,4-dimethylvaleronitrile) and the like.

Although the amount of the radical polymerization catalyst to be blended is not particularly limited, it is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of vinyl monomers. In addition, if acceleration of the polymerization rate or efficient polymerization at low temperature (for example, 70 ° C. or less) is desired, for example, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, Rongalite, etc. is used as a radical polymerization catalyst. It is preferable to use in combination with

Polymerization catalysts for hydrolyzable silicon compounds include, but are not limited to, hydrogen halides such as hydrochloric acid and hydrofluoric acid; carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid and lactic acid; , p-toluenesulfonic acid; acidic emulsifiers such as alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, polyoxyethylene alkylarylsulfuric acid, polyoxyethylene distyrylphenyl ether sulfonic acid acidic or weakly acidic inorganic salts; acidic compounds such as phthalic acid, phosphoric acid, nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine , diazabicycloundecene, ethylenediamine, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)-aminopropyltrimethoxysilane, and other basic compounds; dibutyltin octylate, dibutyltin Examples include tin compounds such as dilaurate.

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

Although polymerization of the vinyl monomer and the hydrolyzable silicon compound can be carried out separately, it is preferable to carry out the polymerization at the same time because the formation of a composite can be efficiently achieved.

A suitable method for obtaining the polymer includes, for example, so-called emulsion polymerization, in which a vinyl monomer and a hydrolyzable silicon compound are polymerized in the presence of a sufficient amount of water for the emulsifier to form micelles. .

A specific method for emulsion polymerization is not particularly limited. For example, the vinyl monomer and the hydrolyzable silicon compound are dropped into the reaction vessel as they are or in an emulsified state, all at once, in portions, or continuously. and a method of polymerizing at a reaction temperature of about 30 to 150° C. in the presence of a polymerization catalyst, preferably under atmospheric pressure to 10 MPa.
The reaction temperature and reaction pressure are not limited to the above conditions depending on the reaction conditions and the like.

The solid content in the emulsion obtained by emulsion polymerization is not particularly limited, but is preferably 0.1 to 70% by mass, more preferably 1 to 55% by mass.

If it is desired to further control the particle size during emulsion polymerization, it is preferable to employ a seed polymerization method in which emulsion particles are preliminarily present in an aqueous phase for polymerization. Although the pH of the polymerization system in this case is not particularly limited, it 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 (such as borax), sodium bicarbonate, and ammonia.

The method for producing the polymer is not particularly limited, but for example, a hydrolyzable silicon compound and a vinyl monomer are polymerized in the presence of water and an emulsifier, optionally in the presence of a solvent, and then a polymerization product is obtained. A technique of adding more water until an emulsion is formed can also be employed. In addition, it is preferable to obtain the polymer by emulsion polymerization from the viewpoint that the particle size of the obtained polymer can be easily controlled.

The content of the polymer in the coating film composed of the undercoat layer used in the composite coating film of the present embodiment is not particularly limited, but is preferably 0.1 to 80% by mass, more preferably 1.0 to 75% by mass. %, more preferably 5.0 to 70% by mass.
By setting the content of the polymer in the coating film comprising the undercoat layer used in the composite coating film of the present embodiment within the above range, the appearance, weather resistance, stain resistance, and biological stain resistance on a dark-colored substrate can obtain a more excellent composite coating film.

(Anti-algae and/or anti-mold agent contained in the coating film consisting of the undercoat layer)
The coating film comprising the undercoat layer used in the composite coating film of the present embodiment further contains an anti-algae and/or anti-mold agent.
This makes it possible to form a composite coating film with excellent biofouling resistance even in places where light such as sunlight is difficult to irradiate. Note that the effects of the present embodiment are not limited to these.

The anti-algae and/or anti-mold agent is not limited to the following, but examples include organic iodine-based compounds, alcohol-based compounds, nitrile compounds, disulfide-based compounds, thiocarbamate-based compounds, nitrogen-containing ring compounds, and the like. mentioned. Among these, nitrogen-containing ring compounds are preferred. Examples of nitrogen-containing ring compounds include thiazoline-based compounds, isothiazoline-based compounds, triazine-based compounds, imidazole-based compounds, and the like. Among these, at least one compound selected from the group consisting of isothiazoline compounds, triazine compounds and imidazole compounds is preferred, and at least one compound selected from the group consisting of isothiazoline compounds and triazine compounds is more preferred.

Examples of compounds having particularly excellent anti-algae properties include triazine-based compounds.

Examples of particularly excellent antifungal properties include thiazoline-based compounds, isothiazoline-based compounds, imidazole-based compounds, and the like.

In the coating film composed of the undercoat layer used in the composite coating film of the present embodiment, one having both anti-algae and anti-mold properties may be used, and such a coating is not particularly limited, but for example, Examples include isothiazoline-based compounds containing chlorine atoms in the molecule.
These may be used individually by 1 type, and may use 2 or more types together.

A commercial item can also be used as a thiazoline type compound. Examples of such commercially available products include, but are not limited to, “Milcut-180” and “Biocut-LC3” manufactured by Nippon Soda Co., Ltd., “Amolden ALK” manufactured by Daiwa Chemical Industry Co., Ltd., and the like.

A commercial item can also be used as an isothiazoline type compound. Examples of such commercially available products include, but are not limited to, "Biocut-TR120" manufactured by Nippon Soda Co., Ltd., "PROXEL GXL" and "PROXEL BDN" manufactured by Arch Chemicals, and "KLARIX 4000" manufactured by Dow Chemicals. , “ROZONE 2000”, “ROCIMA 252”, “ROCIMA 200”, “ROCIMA 345”, “ROCIMA 350”, “ROCIMA 553”, “BIOBAN 551S”, “Scene M-8” and the like.

A commercial item can also be used as a triazine type compound. Examples of such commercially available products include, but are not limited to, "Biocut-N35", "DP-2159" and "DP-2615" manufactured by Nippon Soda Co., Ltd. "DP-2619", "DP-2623", "Amolden NBP-8" and "Amolden NBPconc" manufactured by Daiwa Chemical Industry Co., Ltd., "Sanalga 1907" manufactured by Sankyo Kasei Co., Ltd., and the like.

A commercial item can also be used as an imidazole type compound. Such commercial products are not particularly limited. is mentioned.

The content of the anti-algae and/or anti-mold agent in the coating film comprising the undercoat layer is not particularly limited, but is preferably 0.01% by mass to 30.0% by mass, more preferably 0.01% by mass. 15.0 mass %, more preferably 0.1 mass % to 15.0 mass %. By setting the content of the anti-algae and/or anti-mold agent in the coating film comprising the undercoat layer to the above lower limit or more, the biofouling resistance of the composite coating film is further improved.

In the composite coating film of the present embodiment, other antibacterial agents may also be used in combination within the range in which the effects of the present embodiment can be obtained.

Examples of other antibacterial agents include, but are not limited to, silver-based compounds, copper-based compounds, zinc-based compounds, and the like.

The coating film composed of the undercoat layer used in the composite coating film of the present embodiment may, for example, be mixed with other components in addition to the above-described polymer and anti-algae and/or anti-mold agent, if necessary. .

Examples of other components include, but are not limited to, freeze stabilizers, matting agents, cross-linking reaction catalysts, pigments, curing catalysts, cross-linking agents, fillers, anti-skinning agents, dispersants, Wetting agents, light stabilizers, antioxidants, UV absorbers, deposition aids, rust inhibitors, plasticizers, thickeners, lubricants, reducing agents, preservatives, deodorants, anti-yellowing agents, static Examples include antistatic agents and charge control agents.
These may be used individually by 1 type, and may use 2 or more types together.

The composite coating film of the present embodiment has at least two layers: the coating film described above, that is, the coating film obtained by the water-based coating containing the water-based composition described above, and the coating film composed of the undercoat layer described above.

The composite coating film of the present embodiment may have the above-described coating film formed directly on the coating film composed of the undercoat layer, a multilayer structure via another predetermined layer, or another predetermined layer It may be a multilayer structure formed under a coating film composed of an undercoat layer. It is preferable that the coating film obtained by the water-based paint containing the water-based composition described above is the uppermost layer.

The coating film composed of the undercoat layer used in the composite coating film of the present embodiment can be obtained by applying an appropriately suitable method depending on the application, the material to be coated, and the like.

Examples of coating methods include, but are not limited to, spraying, flow coating, roll coating, brush coating, dip coating, spin coating, screen printing, casting, and gravure printing. method, flexographic printing method, wire bar coating method, and the like.

The coating film described above is applied onto the primer layer or other predetermined layer by, for example, spraying, flow coating, roll coating, brushing, dip coating, spin coating, screen printing, casting. , gravure printing method, and flexographic printing method can be applied to form the composite coating film of the present embodiment.

[Painted products]
The coated product of this embodiment includes a substrate and the above-described coating or the above-described composite coating. The above coating film or the above composite coating film may be in a state formed on at least part of the surface of the substrate.

The coated product of the present embodiment can be obtained, for example, by applying a water-based paint containing the water-based composition described above to the surface of various substrates and drying it.

Moreover, the coated product of the present embodiment can also have a form comprising a base material and the composite coating film described above. A coated product comprising the composite coating film is formed by applying an undercoat layer containing the above-described polymer and an anti-algae and / or anti-mold agent to the surface of various substrates and drying, and then further undercoating. It can be obtained by applying the water-based paint to the surface of the layer and drying it.

The substrate used for the coated product of the present embodiment is not particularly limited as long as a coating film can be formed on the surface thereof, and may be either an organic substrate or an inorganic substrate. Organic substrates are preferred from the viewpoint of improving properties.

Examples of materials for the substrate include, but are not limited to, organic substrates such as synthetic resins and natural resins; and inorganic substrates such as metals, ceramics, glass, stone, cement, and concrete.
These may be used individually by 1 type, and may use 2 or more types together.

Examples of the synthetic resin include, but are not limited to, thermoplastic resins and curable resins (thermosetting resins, photo-curable resins, moisture-curable resins, etc.).

Specific examples of synthetic resins include, but are not limited to, silicone resins, acrylic resins, methacrylic resins, fluorine resins, alkyd resins, aminoalkyd resins, vinyl resins, polyester resins, styrene-butadiene resins, Polyolefin resin, polystyrene resin, polyketone resin, polyamide resin, polycarbonate resin, polyacetal resin, polyether ether ketone resin, polyphenylene oxide resin, polysulfone resin, polyphenylene sulfone resin, polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, Urea resins, phenol resins, melamine resins, epoxy resins, urethane resins, silicone-acrylic resins and the like can be used.

Examples of natural resins include, but are not limited to, cellulose-based resins, isoprene-based resins such as natural rubber, and protein-based resins such as casein.

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

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

The coating film obtained by the water-based paint of the present embodiment does not impair the appearance even on a dark-colored substrate, and can maintain a high level of appearance, stain resistance, sealing stain resistance, and biological stain resistance over a long period of time. It can also be suitably used in environments where it was difficult to use.

From this point of view, the coated product of the present embodiment is not limited to the following, but for example, building materials, building exteriors, building interiors, window frames, window glass, various lenses, structural members, building equipment such as houses, Vehicle lighting covers and window glass, exteriors of machinery and articles, dustproof covers and coatings, display devices and their covers, traffic signs, various display devices, displays such as advertising towers, sound insulation walls for roads and railways, etc. , exterior and painting of bridges and guardrails, interior and painting of tunnels, insulators, solar cell covers, solar water heater heat collection covers, etc. Exterior parts of electronic and electric equipment used outside, especially exterior parts of transparent materials, vinyl houses, greenhouses, etc. is mentioned.

As a method for producing a coated product of the present embodiment, for example, the above-described water-based paint or the above-described water-based composition is applied to at least a part of the surface of the substrate, and if necessary, drying etc. is performed. Examples include, but are not limited to, methods of forming a film. For example, the coating film of the present embodiment may be applied onto a substrate, then peeled from the substrate and adhered to another substrate. Alternatively, the coating film of the present embodiment may be applied onto a base material and then adhered to another base material while being in close contact with the base material.

The water-based composition of the present embodiment may be blended in various water-based paints. Such a water-based paint can form a coating film excellent in appearance, stain resistance, sealing stain resistance, biological stain resistance, transparency, weather resistance, and the like. Thus, the coating film of the present embodiment is excellent in appearance, stain resistance, sealing stain resistance, biological stain resistance, transparency, weather resistance, etc., and includes exterior paints for buildings. It can be used for a wide range of purposes.

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

A base material used for the measurement of properties described later was produced as follows.
[Preparation of 7 cm × 15 cm base material pre-coated with enamel paint]
(Preparation of pigment dispersion)
Dispersant (manufactured by BASF Japan, "Pig.Disperser MD20") 5.35 g, ammonia water 0.5 g, propylene glycol 23.5 g, water 147.5 g, titanium oxide (chlorinated rutile type titanium oxide; manufactured by Ishihara Sangyo Co., Ltd. , "Tipake CR-97") 333.5 g, and antifoaming agent (modified silicone; manufactured by San Nopco, "SN Deformer 1310") 2.85 g of a tabletop sand mill (manufactured by Campe Papio, batch type desktop sand mill ) for 20 minutes to obtain a pigment dispersion.

(Preparation of enamel paint X not containing anti-algae and anti-mold agents)
10.0 g of 2,2,4-trimethyl-1,3-butanediol isobutyrate (manufactured by Chisso, "CS-12") was added to 109.0 g of the polymer emulsion obtained in [Production Example 1] described later. , 10.0 g of a mixture of 50 parts by mass of ethylene glycol monobutyl ether and 50 parts by mass of water, 51.4 g of the pigment dispersion obtained as described above, and a thickener (manufactured by Asahi Denka Kogyo Co., Ltd., "Adekanol UH- 438”) was added and mixed for 1 hour to obtain an enamel paint X.
(Preparation of 7 cm × 15 cm base material pre-coated with enamel paint X)
The enamel paint X obtained as described above was coated on a 7 cm x 15 cm sulfate alumite plate using a wire coater No. 1. 50 and dried at 23° C. and 50% relative humidity for 48 hours to give a 7 cm×15 cm substrate precoated with enamel paint X.

(Preparation of enamel paint Y containing anti-algae and anti-mold agent)
10.0 g of 2,2,4-trimethyl-1,3-butanediol isobutyrate (manufactured by Chisso, "CS-12") was added to 109.0 g of the polymer emulsion obtained in [Production Example 1] described later. , 10.0 g of a mixture of 50 parts by mass of ethylene glycol monobutyl ether and 50 parts by mass of water, 51.4 g of the pigment dispersion obtained as described above, a thickener (manufactured by Asahi Denka Kogyo Co., Ltd., "Adekanol UH-438 ”) 0.5 g of a 10% by mass aqueous solution, anti-algae and anti-mold agent N-35 (manufactured by Nippon Soda Co., Ltd., solid content 35% by mass) 0.9 g, anti-algae and anti-mold agent AF-40 (manufactured by Nippon Soda, solid content 40 mass %) was added and mixed for 1 hour to obtain an enamel paint Y.
(Preparation of 7 cm × 15 cm base material pre-coated with enamel paint Y)
The enamel paint Y obtained as described above was coated on a 7 cm x 15 cm sulfate anodized plate using a wire coater No. 1. 50 and dried at 23° C. and 50% relative humidity for 48 hours to give a 7 cm×15 cm substrate precoated with enamel paint Y.

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

(2. Number average particle size of aqueous dispersion of inorganic oxide C and polymer A having photocatalytic activity)
The water dispersion of the sample is diluted by adding ion-exchanged water so that the loading index is 1.5 to 3.0, and the number is measured using a wet particle size analyzer (manufactured by Nikkiso Co., Ltd., "Microtrac UPA-9230"). Average particle size was measured. Measurement conditions are shown below.
・Loading index: 1.5 to 3.0
・Measurement time: 60 seconds ・Number of measurements: 3 times

(3. Glass transition temperature)
Using "DCS6220" manufactured by Seiko Instruments Inc., the temperature of the measurement sample was increased at a temperature increase rate of 10° C./min, and the glass transition temperature was obtained from the inflection point of the obtained DSC curve. In addition, the measurement conditions are shown below.
- Measurement cell: aluminum container - Preparation of measurement sample: Put 40 mg of the polymer emulsion obtained in [Production Example 1] described later in an aluminum container and dry it at 130 ° C. for 1 hour to prepare a measurement sample. made.
Various properties were measured by the following 4 to 13.

(4. Color difference before and after painting)
A water-based ceramic silicon SR-422 (manufactured by SK-KAKEN) was coated on a 7 cm×15 cm sulfuric acid alumite plate with a wire coater No. 1. 50 and dried at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a 7 cm×15 cm substrate coated with aqueous ceramic silicone. The water-based composition was applied to the water-based ceramic silicone-coated substrate using a spray so that the coating amount of the water-based composition was 17.0 g/m ² . The base material coated with the water-based composition was kept horizontal and allowed to stand for 48 hours at a temperature of 23° C., a relative humidity of 50% and an illumination of 20000 lux to prepare a test panel. For the test panel, the color difference before and after coating was measured using BYK Gardner's "Color Guide". If the color difference is 4.0 or less, it indicates that the change in color difference on a dark background is small and good.

(5. Weather resistance test: gloss retention rate after 3000 hours)
A base material of 7 cm×15 cm pre-coated with the enamel paint Y prepared as described above was coated with a spray so that the coating amount of the water-based composition was 17.0 g/m ² . The coated base material was kept horizontal and allowed to stand for 48 hours at a temperature of 23° C., a relative humidity of 50% and an illumination of 20000 lux to prepare a test panel. An exposure test (black panel temperature of 63° C., rainfall of 18 minutes/2 hours) was performed using “Sunshine Weather Meter” manufactured by Suga Shikenki. The 60° glossiness of the test plate before the exposure test and the 60° glossiness of the test plate after 3000 hours of the exposure test were measured using a gloss meter (manufactured by BYK Gardner, "Micro Trigloss μ").
Then, based on the following formula, the gloss retention rate of the test plate after 3000 hours of the exposure test was calculated. The result of evaluating only the base material pre-coated with the enamel paint Y is 80% of the gloss retention after 3000 hours of exposure, and when the value of the gloss retention is greater than this value, the weather resistance is good. indicates that
Gloss retention rate (%) = 60° glossiness after 3000 hours of exposure test/60° glossiness before exposure test x 100

(6. Stain resistance)
A base material of 7 cm×15 cm pre-coated with the enamel paint Y prepared as described above was coated with a spray so that the coating amount of the water-based composition was 17.0 g/m ² . The coated base material was kept horizontal and allowed to stand for 48 hours at a temperature of 23° C., a relative humidity of 50% and an illumination of 20000 lux to prepare a test panel. The test plate was attached to a fence facing a general road (about 500 to 1000 trucks/day) and left to stand for 6 months or 1 year.
The degree of contamination of the test plate after standing was visually evaluated based on the following criteria.
The results of evaluating only the base material pre-coated with the enamel paint Y were "x" for both 6 months and 1 year.
[Evaluation criteria]
◯: Almost no dirt was observed.
Δ: Slight dirt was observed, but it was practically acceptable.
x: A large amount of dirt was confirmed.

(7. Sealing contamination)
A base material of 7 cm×15 cm pre-coated with the enamel paint Y prepared as described above was coated with a spray so that the coating amount of the water-based composition was 17.0 g/m ² . The coated base material was kept horizontal and allowed to stand for 48 hours at a temperature of 23° C., a relative humidity of 50% and an illumination of 20000 lux to prepare a test panel. One-component silicone sealant 8060 Pro (manufactured by Cemedine Co., Ltd.) was applied to the test plate so that the dried sealant had an area of 1 cm x 2 cm and a height of 1 cm. dried for days.
The test plate was attached to a fence facing a general road (approximately 500 to 1000 truck traffic per day) and allowed to stand for a predetermined period of time.
The degree of contamination of the test plate after standing was measured by measuring the color difference (L value) before and after standing using BYK Gardner's "Color Guide".
It was evaluated based on the following criteria.
◎: L value difference of 2 or less after 8 weeks of standing, L value difference of 3 or less after 12 weeks of standing ○: L value difference of 2 or less after 8 weeks of standing, 12 weeks of standing The difference in L value is more than 3 and 4 or less △: The difference in L value is 2 or less after standing for 8 weeks, the difference in L value is greater than 4 after standing for 12 weeks ×: The difference in L value is greater than 4 after standing for 8 weeks more than 2 differences

(8. Biofouling resistance)
<Biofouling resistance without anti-algae and anti-mold agents in the undercoat layer>
A 7 cm×15 cm base material pre-coated with the enamel paint X was coated with a water-based composition using a spray so that the coating amount was 17.0 g/m ² . The coated base material was kept horizontal and allowed to stand for 48 hours at a temperature of 23° C., a relative humidity of 50% and an illumination of 20000 lux to prepare a test panel.
In Kasama City, Ibaraki Prefecture, the test plate was attached to a fence facing the north side of a building surrounded by trees, at an angle of 45° from the horizontal surface, and the painted surface was facing upwards. It was left undisturbed for a month.
The degree of contamination of the test plate after standing was visually evaluated based on the following criteria.
The result of evaluating only the base material pre-coated with the enamel paint X was the evaluation of "x".
[Evaluation criteria]
◯: Almost no algae or mold stains were observed.
Δ: Although some algae and mold stains were observed, there was no practical problem.
x: A large amount of algae and mold stains were observed.

<Biofouling resistance including an anti-algae and anti-mold agent in the undercoat layer>
A base material of 7 cm×15 cm pre-coated with enamel paint Y containing an anti-algae and anti-fungal agent was coated with a spray so that the coating amount of the water-based composition was 17.0 g/m ² . The coated base material was kept horizontal and allowed to stand for 48 hours at a temperature of 23° C., a relative humidity of 50% and an illumination of 20000 lux to prepare a test panel.
In Kasama City, Ibaraki Prefecture, the test panel was attached to a fence facing the north side of a building surrounded by trees, at an angle of 45° from the horizontal plane, with the painted surface facing upwards. left undisturbed.
The degree of contamination of the test plate after standing was visually evaluated based on the following criteria.
In addition, the result of evaluating only the base material pre-coated with the enamel paint Y containing the anti-algae and anti-mold agent was the evaluation of "O" for 1 year.
[Evaluation criteria]
◯: Almost no algae or mold stains were observed.
Δ: Although some algae and mold stains were observed, there was no practical problem.
x: A large amount of algae and mold stains were observed.

(9. Number average particle size of inorganic oxide B having no photocatalytic activity)
Inorganic oxide B having no photocatalytic activity was diluted with water and dried on a collodion membrane. This collodion film was photographed using a transmission electron microscope (manufactured by Hitachi Ltd., H-7100) at an acceleration voltage of 75 kV and a magnification of 100,000. The particle diameter of the inorganic oxide B was measured from the image of the particles contained in the photographed field using image analysis software Azokun (manufactured by Asahi Kasei Engineering Co., Ltd.). The particle diameter of each particle of 90 or more and 150 or less was measured, and the number average particle diameter of the inorganic oxide B was calculated by taking the arithmetic mean of these particle diameters.

(10. Cracks in coating film)
A water-based ceramic silicon SR-422 (manufactured by SK-KAKEN) was coated on a 7 cm×15 cm sulfuric acid alumite plate with a wire coater No. 1. 50 and dried at a temperature of 23° C. and a relative humidity of 50% for 48 hours to obtain a 7 cm×15 cm substrate coated with aqueous ceramic silicone. The water-based composition was applied to the base material coated with water-based ceramic silicon using a spray so that the coating amount of the water-based composition was 17.0 g/m ² to form a coating film. The base material on which the coating film of the water-based composition was formed was held horizontally and allowed to stand for 48 hours at a temperature of 23° C., a relative humidity of 50% and an illumination of 20000 lux to prepare a test panel. Using a microscope (manufactured by Keyence Corporation, VHX-5000), cracks in the coating film were photographed at a magnification of 1000. Using the image analysis software Azokun (manufactured by Asahi Kasei Engineering Co., Ltd.), the percentage of the area of the field of view corresponding to the cracks in the photographed photograph was calculated. The smaller this area, the better the cracking of the coating film.

(11. Water retention of coating film)
2 g of the aqueous composition was dried at 50° C. for 2 hours to form a coating film. The dried coating film was further dried for 3 hours under reduced pressure using a vacuum dryer at 40° C. to obtain a dried coating film. This dried coating film was aged for 2 hours at 20° C. and 15% humidity to obtain a measurement sample. 10 mg of the measurement sample was measured under the following conditions using a differential thermogravimetry (STA-7200, manufactured by Hitachi High-Tech Science). The weight loss rate of the coating film from 40°C to 150°C was calculated. Since the weight loss rate corresponds to the amount of water attached to the dried coating film due to moisture in the air, the lower the weight loss rate, the better the water retention of the coating film.
Temperature rising conditions: Hold at 40°C for 5 minutes.
The temperature was raised from 40°C to 600°C at a rate of 10°C/min.

(12. Film thickness)
A 7 cm×15 cm acrylic plate (trade name “Delaglas K”, manufactured by Asahi Kasei Corporation, thickness 2 mm) was coated with a spray so that the coating amount of the water-based composition was 17.0 g/m ² . A coating was formed. The base material on which the coating film was formed was kept horizontal and allowed to stand for 48 hours at a temperature of 23° C., a relative humidity of 50% and an illumination of 20,000 lux to prepare a test panel. Using a reflection spectroscopic film thickness meter FE-3000 manufactured by Otsuka Electronics Co., Ltd., the film thickness of the coating film on the test plate was determined.

(13. Crack width)
A base material of 3 cm x 3 cm pre-coated with the enamel paint Y prepared as described above was sprayed with a water-based composition so that the coating amount of the water-based composition was 17.0 g/m ² . was applied to form a coating film. The base material on which the coating film was formed was kept horizontal and allowed to stand for 48 hours at a temperature of 23° C., a relative humidity of 50% and an illumination of 20,000 lux to prepare a test panel. Gold was coated to 3 to 9 nm on the test plate using a sample coater MP-19010NCTR manufactured by JEOL Ltd. The surface of the coating film was observed using a desktop scanning electron microscope JCM-5000 manufactured by JEOL Ltd. The observation magnification was set to 500 times for a test plate with a crack width exceeding 5 μm, 1000 times for a test plate having a crack width of more than 3 μm and 5 μm or less, and 3000 times for a crack width of 3 μm or less. For the evaluation, each test plate was observed for 4 fields of view, and the width of 5 points was measured for 1 field of view. The range between the minimum value and the maximum value of the crack width was determined for 18 places with the smallest crack width out of 20 places in total.

(14. Appearance of coating film)
100 g of the aqueous composition was placed in a 100 ml plastic container and shaken vigorously for 30 seconds. After that, the plastic container containing the water-based composition was allowed to stand for 10 minutes. A base material of 7 cm×15 cm pre-coated with enamel paint Y containing an anti-algae and anti-fungal agent was coated with a spray so that the coating amount of the water-based composition was 17.0 g/m ² . The coated base material was kept horizontal and allowed to stand for 48 hours at a temperature of 23° C., a relative humidity of 50% and an illumination of 20000 lux to prepare a test panel. The appearance of the test plate after standing was visually evaluated based on the following criteria.
[Evaluation criteria]
◯: Almost no crater or repellency was observed.
Δ: Although some craters and repelling were observed, there was no practical problem.
x: Many craters and cissing were confirmed.

In Preparation Example 1 below, a polymer emulsion for the enamel paint was prepared.
[Production Example 1]
(Synthesis of polymer emulsion)
292.0 g of ion-exchanged water and a reactive emulsifier (manufactured by ADEKA, "Adekari Soap SR-1025"; aqueous solution with a solid content of 25% by mass) were placed in a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer. 8.0 g was added and the temperature in the reactor was increased to 80° C. while stirring. Into this reactor was added 10.0 g of a 2% by mass ammonium persulfate aqueous solution, and after 5 minutes, 10.0 g of methyl methacrylate, 5.0 g of cyclohexyl methacrylate, 75.0 g of n-butyl acrylate, and methacrylic acid were added. 5.0 g, 2-hydroxyethyl methacrylate 10.0 g, reactive emulsifier (manufactured by ADEKA, "ADEKARI SOAP SR-1025"; solid content 25% by mass aqueous solution) 4.0 g, 2% by mass aqueous ammonium persulfate solution 15 0 g and 49.0 g of ion-exchanged water was added dropwise over 60 minutes while the temperature in the reactor was maintained at 80°C. After that, the temperature in the reactor was maintained at 80° C. and stirring was continued for 60 minutes.
Next, 70.0 g of methyl methacrylate, 90.0 g of cyclohexyl methacrylate, 232.0 g of n-butyl acrylate, 8.0 g of methacrylic acid, a reactive emulsifier (manufactured by ADEKA, "Adekari Soap SR-1025"; solid 25% by mass aqueous solution) 16.0 g, 60.0 g of 2% by mass ammonium persulfate aqueous solution, and 196.0 g of ion-exchanged water; 1.0 g of 3-methacryloxypropyltrimethoxysilane; A mixture of 20.0 g and 20.0 g of methyltrimethoxysilane was dropped from separate dropping tanks over 160 minutes. After that, the temperature in the reactor was maintained at 80° C. and stirring was continued for 120 minutes.
After cooling to room temperature, the hydrogen ion concentration of the reaction solution in the reactor was measured and found to be pH 2.2. After adjusting the pH to 8.0 by adding a 25% mass aqueous ammonia solution to the reaction solution, the reaction solution was filtered through a 100-mesh wire mesh to obtain the above polymer emulsion for enamel paint.
The solid content of the resulting polymer emulsion was 44.5% by mass. The glass transition temperature of the polymer contained in this polymer emulsion was -5°C, as determined from the inflection point of the DSC curve according to the method described above.

In Preparation Examples 2 to 8 below, aqueous polymer dispersions were prepared.
[Production Example 2]
(Synthesis of Aqueous Dispersion AD-1 of Polymer A-1)
A reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirring device was charged with 1364.2 g of ion-exchanged water and a reactive emulsifier (manufactured by ADEKA, "Adekari Soap SR-1025"; aqueous solution with a solid content of 25% by mass). 28.8 g was added and the temperature in the reactor was increased to 80° C. while stirring. Into this reactor was added 10.0 g of a 2% by mass ammonium persulfate aqueous solution, and after 5 minutes, 40.0 g of methyl methacrylate, 36.0 g of n-butyl acrylate, 4.0 g of acrylic acid, and a reactive emulsifier were added. (Manufactured by ADEKA, "ADEKARIA SOAP SR-1025"; solid content 25% by mass aqueous solution) 3.2 g, 12.0 g of 2% by mass ammonium persulfate aqueous solution, and 34.8 g of ion-exchanged water. It was added dropwise over 60 minutes while the temperature in the reactor was maintained at 80°C. After that, the temperature in the reactor was maintained at 80° C. and stirring was continued for 60 minutes.
Next, 250.0 g of methyl methacrylate, 66.0 g of n-butyl acrylate, 4.0 g of acrylic acid, and a reactive emulsifier (manufactured by ADEKA, "ADEKARI SOAP SR-1025"; solid content 25% by mass aqueous solution) 12 8 g, 48.0 g of a 2% by mass ammonium persulfate aqueous solution, and 149.2 g of ion-exchanged water were added dropwise from the dropping tank over 160 minutes. After that, the temperature in the reactor was maintained at 80° C. and stirring was continued for 120 minutes.
After cooling to room temperature, a 25% mass aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0. Total solids content was 412.6 g. The reaction solution was filtered through a 100-mesh wire mesh. The solid content of the reaction product 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 30 nm.

[Production Example 3]
(Synthesis of Aqueous Dispersion AD-2 of Polymer A-2)
A reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirring device was charged with 1364.2 g of ion-exchanged water and a reactive emulsifier (manufactured by ADEKA, "Adekari Soap SR-1025"; aqueous solution with a solid content of 25% by mass). 28.8 g was added and the temperature in the reactor was increased to 80° C. while stirring. Into this reactor was added 10.0 g of a 2% by mass ammonium persulfate aqueous solution, and after 5 minutes, 40.0 g of methyl methacrylate, 36.0 g of n-butyl acrylate, 4.0 g of acrylic acid, and a reactive emulsifier were added. (Manufactured by ADEKA, "ADEKARIA SOAP SR-1025"; solid content 25% by mass aqueous solution) 3.2 g, 12.0 g of 2% by mass ammonium persulfate aqueous solution, and 34.8 g of ion-exchanged water. It was added dropwise over 60 minutes while the temperature in the reactor was maintained at 80°C. After that, the temperature in the reactor was maintained at 80° C. and stirring was continued for 60 minutes.
Next, 250.0 g of methyl methacrylate, 66.0 g of n-butyl acrylate, 4.0 g of acrylic acid, and a reactive emulsifier (manufactured by ADEKA, "ADEKARI SOAP SR-1025"; solid content 25% by mass aqueous solution) 12 .8 g, 48.0 g of a 2% by mass ammonium persulfate aqueous solution, and 149.2 g of ion-exchanged water; A mixture of 20.0 g of methoxysilane was added dropwise over 160 minutes from separate dropping tanks. After that, the temperature in the reactor was maintained at 80° C. and stirring was continued for 120 minutes.
After cooling to room temperature, a 25% by mass aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0. Total solids content was 436.2 g. The reaction solution was filtered through a 100-mesh wire mesh. The solid content of the reaction product was adjusted to 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion AD-2 of the polymer A-2 having a number average particle diameter of 30 nm.
The amount of dimethyldimethoxysilane used in synthesizing the aqueous dispersion was 2.8% by mass in the polymer A-2 when converted to a hydrolyzed condensate.

[Production Example 4]
(Synthesis of Aqueous Dispersion AD-3 of Polymer A-3)
850.0 g of ion-exchanged water and 40.0 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid were added to a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirring device, and then the contents of the reactor were stirred under stirring. The temperature was warmed to 80°C. A mixed liquid consisting of 85.5 g of dimethyldimethoxysilane and 193.0 g of methyltrimethoxysilane was added dropwise into the reactor over 120 minutes while the temperature in the reactor was maintained at 80°C.
After that, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes.
Next, after adding 14.8 g of a 10 mass % dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80°C and stirring was continued for 120 minutes. After adding 6.6 g of a 2 mass % ammonium persulfate aqueous solution thereto, 22.5 g of methyl methacrylate, 11.2 g of n-butyl acrylate, 20.0 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, and A mixture of 1.1 g of 3-methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, and 1.2 g of a reactive emulsifier (manufactured by ADEKA, "Adekari Soap SR-1025"; solid content 25% by mass aqueous solution). , Reactive emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., "Aqualon KH-1025"; solid content 25% by mass aqueous solution) 1.2 g, 2% by mass ammonium persulfate aqueous solution 30.0 g, and ion-exchanged water 286.4 g and the mixed solution were simultaneously added dropwise over 120 minutes while the temperature in the reactor was maintained at 80°C.
Furthermore, after the temperature in the reactor was maintained at 80° C. and stirring was continued for 60 minutes, the mixture was cooled to room temperature, and a 25 mass % aqueous ammonia solution was added to the reaction liquid to adjust the pH to 8.0. Total solids content was 211.4 g. The reaction solution was filtered through a 100-mesh wire mesh. The solid content of the reaction product 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 15 nm.
The amount of dimethyldimethoxysilane used in synthesizing the aqueous dispersion was 25.0% by mass in polymer A-3 when converted to a hydrolyzed condensate.

[Production Example 5]
(Synthesis of Aqueous Dispersion AD-4 of Polymer A-4)
850.0 g of ion-exchanged water and 40.0 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid were added to a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirring device, and then the contents of the reactor were stirred under stirring. The temperature was warmed to 80°C. A mixture of 109.0 g of dimethyldimethoxysilane, 29.5 g of phenyltrimethoxysilane, and 136.5 g of methyltrimethoxysilane was added to the reactor for 120 minutes while maintaining the temperature of the reactor at 80°C. dripped over.
After that, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes.
Next, after adding 14.8 g of a 10.0% by mass aqueous solution of dodecylbenzenesulfonic acid, the temperature in the reactor was maintained at 80° C. and stirring was continued for 120 minutes. After adding 6.6 g of a 2 mass % ammonium persulfate aqueous solution thereto, 1.0 g of methyl methacrylate, 1.0 g of n-butyl acrylate, 29.5 g of phenyltrimethoxysilane, 27.8 g of tetraethoxysilane, and A mixture of 1.1 g of 3-methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, and 4.5 g of a reactive emulsifier (manufactured by ADEKA, "Adekari Soap SR-1025"; solid content 25% by mass aqueous solution). , Reactive emulsifier (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "Aqualon KH-1025"; solid content 25% by mass aqueous solution) 2.3 g, 2% by mass ammonium persulfate aqueous solution 30.0 g, and ion-exchanged water 256.4 g and the mixed solution were simultaneously added dropwise over 120 minutes while the temperature in the reactor was maintained at 80°C.
Furthermore, after the temperature in the reactor was maintained at 80° C. and stirring was continued for 60 minutes, the mixture was cooled to room temperature, and a 25 mass % aqueous ammonia solution was added to the reaction liquid to adjust the pH to 8.0. Total solids content was 192.4 g. The reaction solution was filtered through a 100-mesh wire mesh. The solid content of the reaction product 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 20 nm.
The amount of dimethyldimethoxysilane used in synthesizing the aqueous dispersion was 35.0% by mass in polymer A-4 when converted to a hydrolyzed condensate.

[Production Example 6]
(Synthesis of Aqueous Dispersion AD-5 of Polymer A-5)
1000.0 g of ion-exchanged water and 40.0 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid were charged into a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirring device, and then the contents of the reactor were stirred under stirring. The temperature was warmed to 80°C. A mixture of 220.0 g of dimethyldimethoxysilane, 5.0 g of phenyltrimethoxysilane, and 106.0 g of methyltrimethoxysilane was added to this reactor for 120 minutes while maintaining the temperature in the reactor at 80°C. dripped over.
After that, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes.
Next, after adding 14.8 g of a 10.0% by mass aqueous solution of dodecylbenzenesulfonic acid, the temperature in the reactor was maintained at 80° C. and stirring was continued for 120 minutes. After adding 6.6 g of a 2% by mass ammonium persulfate aqueous solution thereto, 1.0 g of methyl methacrylate, 1.0 g of n-butyl acrylate, 5.0 g of phenyltrimethoxysilane, 10.0 g of tetraethoxysilane, and A mixture of 1.1 g of 3-methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, and 4.5 g of a reactive emulsifier (manufactured by ADEKA, "Adekari Soap SR-1025"; solid content 25% by mass aqueous solution). , Reactive emulsifier (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "Aqualon KH-1025"; solid content 25% by mass aqueous solution) 2.3 g, 2% by mass ammonium persulfate aqueous solution 30.0 g, and ion-exchanged water 256.4 g and the mixed solution were simultaneously added dropwise over 120 minutes while the temperature in the reactor was maintained at 80°C.
Furthermore, after the temperature in the reactor was maintained at 80° C. and stirring was continued for 60 minutes, the mixture was cooled to room temperature, and a 25 mass % aqueous ammonia solution was added to the reaction liquid to adjust the pH to 8.0. Total solids content was 208.9 g. The reaction solution was filtered through a 100-mesh wire mesh. The solid content of the reaction product was adjusted to 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion AD-5 of the polymer A-5 having a number average particle diameter of 35 nm.
The amount of dimethyldimethoxysilane used in synthesizing the aqueous dispersion was 65.0% by mass in the polymer A-5 when converted to a hydrolyzed condensate.

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

[Production Example 8]
(Synthesis of inorganic oxide C-2 with photocatalytic activity)
<Silica-modified anatase-type titanium oxide>
Aggregated metatitanic acid produced by heating and hydrolyzing a titanium sulfate solution obtained by reacting titanium ore with sulfuric acid was made into an aqueous slurry of 30% by mass in terms of TiO ₂ . Aqueous ammonia was added to this slurry to neutralize it to pH 7, after which sulfate ions were removed by filtration and washing to obtain a dehydrated cake.
The resulting dehydrated cake was peptized by adding nitric acid to obtain an acidic titanium oxide sol having a pH of 1.5 and comprising fine titanium oxide particles having an anatase crystal structure (number average particle diameter of primary particles: 7 nm).
After diluting the obtained acidic titanium oxide sol with pure water to obtain 600 mL of titanium oxide sol having a TiO ₂ equivalent concentration of 200 g/L, the temperature was raised to 70° C. to obtain sodium silicate having a SiO ₂ equivalent concentration of 432 g/L. 20.8 mL of aqueous solution was added to the reactor at the same time as the 20% sulfuric acid. It was then aged for 30 minutes.
Next, a 10% aqueous sodium hydroxide solution was added to adjust the pH of the reaction solution to 8, and then a 2% aqueous sulfuric acid solution was added to adjust the pH of the reaction solution to 6. The reaction solution was filtered and washed to remove the wet cake. Obtained.
After repulping this wet cake in pure water, it is ultrasonically dispersed, and anatase-type titanium oxide sol (inorganic oxide C-2 having photocatalytic activity) stable in the neutral range of pH 7.5 with a solid content of 20% by mass. Aqueous dispersion) was obtained.
In this anatase-type titanium oxide sol, aggregated silica is adhered in a porous state on the surface of the titanium oxide fine particles, and the content thereof is 7 parts by mass in terms of SiO ₂ with respect to 100 parts by mass of TiO ₂ . rice field.

[Example 1]
3.839 g of a water dispersion of polymer A-3 AD-3 (solid content: 10.0% by mass) was added with a water-dispersed colloidal silica B-1 having a number average particle size of 53 nm as measured by a transmission electron microscope (manufactured by Nissan Chemical Industries, Ltd., "Snowtex 30L"; solid content 30% by mass) 3.839 g, 1.324 g (solid content 29% by mass) of an aqueous dispersion of inorganic oxide C-1 having photocatalytic activity, and ethanol to reduce the solid content to 10.8%. Fluorocarbon surfactant D-1 (manufactured by DIC, "Megafac F-444") 0.576 g adjusted to 0% by mass, and fading dye E adjusted to a solid content of 1.0% by mass with ion-exchanged water -2 (manufactured by Hodogaya Chemical Industry Co., Ltd., "Acid Red") 0.960 g, antifoaming agent F-1 (manufactured by San Nopco, "SN Deformer AP") 0.013 g, ethanol 10.0 g, and ion-exchanged water By mixing and stirring 79.450 g, a water-based composition G-1 having a solid content of 2.0% by mass was obtained.
Next, on one side of the base material pre-coated with water-based ceramic silicon SR-422 (the side pre-coated with water-based ceramic silicon) and one side of the base material pre-coated with enamel paint (the side pre-coated with enamel paint) , Water-based composition G-1 was applied using a spray so that the coating amount was 17.0 g/m ² to form a coating film.
The coated substrate was kept horizontal and left for 48 hours at a temperature of 23 ° C., a relative humidity of 50%, and an illumination of 20000 lux. 1 and a test plate I-1 in which a coating film was formed on a substrate coated with an enamel paint.
Table 1 shows various physical properties and characteristic evaluation results of the water-based composition G-1, the coating film and test plate H-1, and the coating film and test plate I-1.

[Examples 2 to 14]
By the same procedure as in Example 1, water-based compositions G-2 to G-14, coating films and test plates H-2 to H-14, and coating films and test plates I at the mass ratios shown in Tables 1 and 2 -2 to I-14 were produced, and their various physical properties were measured and evaluated. Results are shown in Tables 1 and 2.

[Comparative Examples 1 to 5]
By the same procedure as in Example 1, water-based compositions G-15 to G-19, coating films and test plates H-15 to H-19, and coating films and test plates I-15 at the mass ratios shown in Table 3 I-19 was prepared, and various physical properties thereof were measured and characteristics were evaluated. Table 3 shows the results.

Inorganic oxide B having no photocatalytic activity, fluorocarbon surfactant D, discoloring dye E, and antifoaming agent F in Tables 1 to 3 were as follows.

B-1: Water-dispersed colloidal silica with a number average particle size of 53 nm as measured by a transmission electron microscope (manufactured by Nissan Chemical Industries, Ltd., "Snowtex 30L"; solid content 30% by mass, particle size by BET method: 45 nm)
B-2: Water-dispersed colloidal silica with a number average particle size of 62 nm as measured by a transmission electron microscope (manufactured by Nissan Chemical Industries, Ltd., "Snowtex XL"; solid content: 40% by mass, particle size by BET method: 55 nm)
B-3: Water-dispersed colloidal silica with a number average particle size of 98 nm as determined by a transmission electron microscope (manufactured by Nissan Chemical Industries, Ltd., "Snowtex ZL"; solid content 40% by mass, particle size determined by the BET method: 79 nm)
B-4: Water-dispersed colloidal silica with a number average particle size of 110 nm as determined by a transmission electron microscope (manufactured by Nissan Chemical Industries, Ltd., "Snowtex MP-1040"; solid content 40% by mass, particle size determined by centrifugal sedimentation method: 130 nm)
B-5: Water-dispersed colloidal silica with a number average particle size of 12 nm as determined by a transmission electron microscope (manufactured by Nissan Chemical Industries, Ltd., "Snowtex NS"; solid content 20% by mass, particle size determined by centrifugal sedimentation method: 130 nm)
B-6: Water-dispersed colloidal silica with a number average particle size of 180 nm as determined by a transmission electron microscope (manufactured by Nissan Chemical Industries, Ltd., "Snowtex MP-2040"; solid content 40% by mass, particle size determined by centrifugal sedimentation method: 180 nm)
B-7: Water-dispersed colloidal silica having a number average particle size of 25 nm as determined by a transmission electron microscope (manufactured by Nissan Chemical Industries, Ltd., "Snowtex 50"; solid content 48% by mass, particle size determined by the BET method: 25 nm)
B-8: Water-dispersed colloidal silica with a number average particle size of 37 nm as determined by a transmission electron microscope (manufactured by Nikki Shokubai Kasei Co., Ltd., "Cataloid SI-45P"; solid content 40% by mass, particle size determined by the BET method: 35 nm)

D-1: A fluorocarbon surfactant whose solid content was adjusted to 10.0% by mass with ethanol (manufactured by DIC, "Megafac F-444")
D-2: Fluorocarbon surfactant (manufactured by AGC Seimi Chemical Co., Ltd., "Surflon S-232"; solid content 30% by mass)
D-3: Polyether-modified silicone-based surfactant adjusted to a solid content of 10.0% by mass with ethanol (manufactured by Shin-Etsu Chemical Co., Ltd., "KF-643")

E-1: A fading dye whose solid content was adjusted to 1.0% by mass with ion-exchanged water (manufactured by Kishida Chemical Co., Ltd., "Methylene Blue")
E-2: Fading dye whose solid content was adjusted to 1.0% by mass with ion-exchanged water (manufactured by Hodogaya Chemical Industry Co., Ltd., "Acid Red")

F-1: Mineral oil-based antifoaming agent (manufactured by San Nopco, "SN Deformer AP")
F-2: Mineral oil-based antifoaming agent (manufactured by San Nopco, "SN Deformer VL")
F-3: Mineral oil-based antifoaming agent (manufactured by San Nopco, "Nopco 8034L")

All of the water-based compositions of the examples do not impair the appearance even on dark-colored substrates, have good cracking of the coating film and good water retention of the coating film, and maintain the appearance, stain resistance, sealing stain resistance, and It was confirmed that a coating film capable of maintaining a high level of biofouling resistance can be formed.

The water-based composition, water-based paint, coating film, composite coating film, and coated product of the present invention are industrially used as various members such as architectural exterior applications, exterior display applications, automotive parts, and optical components such as displays and lenses. have the availability of

Claims (8)

Containing an inorganic oxide B having no photocatalytic activity, an inorganic oxide C having photocatalytic activity, and a fluorocarbon surfactant D,
The inorganic oxide B having no photocatalytic activity has a number average particle size of more than 30 nm and 160 nm or less,
In terms of solid content, it contains 50 to 94 parts by mass of an inorganic compound B that does not have photocatalytic activity and 6 to 21 parts by mass of an inorganic oxide C that has photocatalytic activity (however, polymer A and an inorganic compound that does not have photocatalytic activity The total amount of oxide B and inorganic oxide C having photocatalytic activity shall be 100 parts by mass), water-based composition. Contains 0 to 27 parts by mass of polymer A in terms of solid content (however, the total amount of polymer A, inorganic oxide B having no photocatalytic activity, and inorganic oxide C having photocatalytic activity is 100 parts by mass. ), the water-based composition according to claim 1. 3. The water-based composition according to claim 1, further comprising a fading dye E. A water-based paint containing the water-based composition according to any one of claims 1 to 3. A coating film obtained from the water-based coating composition according to claim 4. A composite coating film comprising at least two layers of the coating film according to claim 5 and a coating film comprising an undercoat layer,
A composite coating film, wherein the coating film comprising the undercoat layer contains a polymer and an anti-algae and/or anti-mold agent. A painted product comprising a substrate and the coating of claim 5 or the composite coating of claim 6. 8. The painted product of Claim 7, wherein the substrate is an organic substrate.