JPH11323195A - Photocatalytic coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photocatalytic coating composition the foreign odor of which has been effectively masked without detriment to photocatalytic action and effects based thereon by mixing photocatalytic metal oxide particles with a perfume and a solvent. SOLUTION: 90-20 wt.% photocatalytic metal oxide particles having a mean particle diameter of 1-100 nm, desirably, 1-50 nm are mixed with 10 wt.% or below, desirably, 0.0001-5 wt.% perfume, 10-80 wt.% difficultly decomposable binder, a mixed solvent comprising a water-soluble solvent having a boiling point of 120 deg.C or above, a water-soluble solvent having a boiling point of 120 deg.C or below, and water, and, optionally, 0.0005-2 wt.%, desirably, 0.001-2 wt.% surfactant, and an acid such as nitric acid or propionic acid in such amounts that the total of the photocatalytic metal oxide particles and the difficultly decomposable binder is 0.01-5 wt.% to obtain a photocatalytic coating composition which can give a coating film with a surface which, when excited with light, develops hydrophilicity or improves in its hydrophilicity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides an oxidation-reduction effect by photoexcitation, thereby exerting antibacterial, deodorizing, antifouling and environmental purification effects, or a surface hydrophilizing effect (photocatalytic hydrophilicity) in response to photoexcitation. Photocatalytic coating composition which exerts effects such as anti-fogging, drip-proofing, improved cleaning with water, and self-cleaning by rainfall, and more particularly, a photocatalytic coating excellent in photocatalytic hydrophilicity. Composition.

[0002]

2. Description of the Related Art When a photocatalyst is irradiated with an excitation light source, active oxygen species such as hydroxyl radicals and superoxide ions are generated, and on the basis thereof, redox effects such as oxidative decomposition of organic substances and reduction of metal ions are performed. It is well known that this occurs (see, for example, JP-A-60-187322 and JP-A-60-155).
678). Furthermore, it has been proposed by the present inventors that, when the photocatalytic film is irradiated with an excitation light source, the surface of the film becomes hydrophilic accordingly (Japanese Patent No. 275).
6474). A coating composition comprising photocatalyst particles, a hardly decomposable binder and a solvent has also been proposed as a coating composition for fixing photocatalyst particles to a substrate at room temperature (Japanese Patent Application Laid-Open No. 7-171408).

[0003]

When a coating composition comprising photocatalyst particles, a hardly decomposable binder and a solvent is applied to a large product such as a window glass, a car body, a signboard, etc., particularly, a hardly decomposable binder is used. When a hardly decomposable binder having a hydrolyzable group is used as the agent, the solvent is preferably an organic solvent, but an unpleasant odor is generated at the time of application. Therefore, an object of the present invention is to provide a coating composition capable of effectively masking such off-flavors without impairing the photocatalytic action and effects based thereon.

[0004]

Means for Solving the Problems and Action In the present invention, in order to solve the above-mentioned problems, a perfume is contained in the composition containing photocatalytic metal oxide particles. By adding a fragrance, an unpleasant odor at the time of application with an organic solvent or the like can be effectively masked without impairing the photocatalytic action such as the hydrophilizing action according to the photoexcitation of the photocatalyst shown in the examples.

[0005]

Next, the components of the present invention will be described. The photocatalytic metal oxide is selected from the group consisting of anatase-type titanium oxide, brookite-type titanium oxide, rutile-type titanium oxide, tin oxide, zinc oxide, bismuth trioxide, tungsten trioxide, ferric oxide, and strontium titanate. One or two or more of them can be used. Among them, anatase type titanium dioxide is preferable.

The average particle diameter of the photocatalytic metal oxide particles is 1
To 100 nm, more preferably 1 to 50 nm.
It is. When the particle size is in the above range, the hydrophilicity can be sufficiently exerted, and the surface to which the composition is applied can be prevented from losing transparency due to scattering of visible light by the particles. In particular, when high transparency, smoothness, and durability are required for the photocatalytic hydrophilic film, it is preferable to use a photocatalytic metal oxide having an average particle diameter of 10 nm or less. When long-term storage stability is required for the composition of the present invention, it is preferable to use photocatalytic metal oxide fine particles having an average particle size of 10 nm or more.

Examples of the hardly decomposable binder include silicon-based binders such as hydrolyzable silane, alkyl silicate, polyorganosiloxane, colloidal silica, silanol, lithium silicate, potassium silicate, and water glass; Phosphates such as zinc phosphate, aluminum phosphate, hydroxyapatite, calcium phosphate, heavy phosphates, cement, lime, gypsum, feldspar, glaze, plaster, frit for enamel, layered oxide, clay, borate, Aluminosilicate, borosilicate, organic titanate, alumina, titania, titanium peroxide, organic zirconium compound, zirconium chloride, zirconium nitrate, zirconium chloride oxide,
Inorganic binders such as zirconia, and organic binders such as silicone resin, acrylic silicone, fluorine-based polymer, and fluorine-based monomer can be used. Here, as the hydrolyzable silane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, methyltripropoxysilane, ethyltripropoxysilane, n-propyltrimethoxysilane, n-propyltrimethoxysilane Ethoxysilane, n-propyltripropoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltripropoxysilane, methyltributoxysilane, ethyltributoxysilane, n-propylbutoxysilane,
Isopropylbutoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyl Tripropoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercap Propyltriethoxysilane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, trifluoropropyltriethoxysilane, phenylmethyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyl Hydrolyzable organosilanes such as diethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-
Tetraalkoxysilanes such as propoxysilane, tetrabutoxysilane, tetramethoxysilane and dimethoxydiethoxysilane can be used. As the alkyl silicate, methyl silicate, ethyl silicate, propyl silicate, butyl silicate and the like can be used.
As the polyorganosiloxane, the above-mentioned hydrolyzable silanes, alkyl silicates, (partially) hydrolyzed products thereof, and hydrolyzed / condensed products can be used. As cement, early strength cement, ordinary cement, moderate heat cement,
Sulfate-resistant cement, white cement, oil well cement,
Portland cement such as geothermal well cement, fly ash cement, high sulfate cement, silica cement,
Blended cement such as blast furnace cement and alumina cement can be used. Gypsum plaster, lime plaster, dolomite plaster and the like can be used as plaster. Examples of the fluorine-based polymer include polyvinylidene fluoride, polyvinyl fluoride, polychlorinated ethylene trifluoride, polytetrafluoroethylene, polytetrafluoroethylene-propylene hexafluoride copolymer, and ethylene-polytetrafluoroethylene copolymer. Crystalline fluororesins such as ethylene-ethylene chloride trifluoride ethylene copolymer, ethylene tetrafluoride-perfluoroalkylvinyl ether copolymer, perfluorocyclopolymer, vinyl ether-fluoroolefin copolymer, vinyl ester Non-crystalline fluororesin such as -fluoroolefin copolymer, various fluororubbers and the like can be used.

The ratio of the hardly decomposable binder to the photocatalytic metal oxide is 90/10 to 20/80 in terms of the weight of the photocatalytic metal oxide / hardly decomposable binder. Is preferred. If the amount of the hardly decomposable binder is less than 10%, the adhesive strength between the base material and the photocatalytic metal oxide particles becomes weak, and the binder easily falls off by finger touch or vibration. On the other hand, when the amount of the hardly decomposable binder exceeds 80%, the ratio of covering the surface of the photocatalytic metal oxide particles increases, and the photocatalytic function decreases, resulting in poor practicality. The above ratio is appropriately adjusted according to the purpose of use. For a substrate such as glass that is unlikely to be degraded by the photooxidation action of the photocatalyst, the photocatalytic metal oxide may be 90%, but the composition of the present invention is applied to a painted surface or a resin surface. In this case, it is preferable that the content of the photocatalytic metal oxide be 20 to 50% or that an undercoat layer is provided as described later to suppress deterioration of the substrate surface due to photooxidation. Further, even when the photocatalytic hydrophilic film requires high film strength and smoothness, the content of the photocatalytic metal oxide is preferably in the range of 20 to 50%.

The solvent that can be used in the composition of the present invention is not particularly limited as long as the metal oxide particles of the coating agent and the hardly decomposable binder are dispersed. For example, ketones such as alcohols, ethers, acetone, 2-butanone, methyl propyl ketone, methyl butyl ketone, and dipropyl ketone, and esters such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, amyl acetate, and ethyl butyrate. , Aliphatics such as benzene, toluene, xylene, chloroform, pentane, hexane, and cyclohexane;
Common organic solvents such as aromatic and alicyclic hydrocarbons and petroleum and water are mentioned, and these can be used alone or in combination. Particularly, water and / or a water-soluble solvent are preferable.

Examples of the water-soluble solvent include methanol, ethanol, denatured ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol, pentanol, Hexanol,
Heptanol, octanol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol,
Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoisopropyl ether, Dipropylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol diisopropyl ether, triethylene glycol dimethyl ether, glycerin monomethyl ether, trimethylene glycol, N-methylpyrrolidone, ethyl Alcohols and ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 3,5-dimethyl-1-hexyn-3-ol, diacetone alcohol, and ketone And the like. The water-soluble solvent can improve the leveling property by mixing a water-soluble solvent (a) having a boiling point of 120 ° C. or higher with a water-soluble solvent (b) having a boiling point of lower than 120 ° C.

The content of (a) in the composition of the present invention is 2
Those having 0% by weight or less are preferred. If it exceeds 20% by weight, a uniform thin film can be obtained, but it is not preferable because drying after coating takes time and dripping easily occurs.

The amount of solvent in the composition according to the invention is
The concentration of the total weight of the above-mentioned photocatalyst particles and the hard-to-decompose binder (hereinafter, may be referred to as “solid content”) is set in a range of 0.01 to 5% by weight or less in the composition. You. If the solid content exceeds 5% by weight, the surface to which the composition is applied may have a cloudy appearance or have interference fringes, which is not desirable. A more preferred upper limit is 3% by weight, and a still more preferred upper limit is 1% by weight. If the solid content is less than 0.01% by weight, a sufficient hydrophilic surface may not be efficiently formed. A more preferred lower limit is 0.05% by weight, most preferably 0.1% by weight. In the composition according to the present invention, the amount of the solvent is determined so that the solid concentration is in the above range.

The fragrance which can be used in the composition of the present invention includes: hydrocarbons; limonene, α-pinene, β-pinene, myrcene, terpinolene, oshimene, γ-terpinene, α-
Ferrandrene, p-cymene, β-caryophyllene,
Terpene hydrocarbons such as β-farnesene, alcohols; 3-methyl-1-pentanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 2-ethylhexanol , 1-nonanol, 2-nonanol,
Isononyl alcohol, 1-decanol, undecanol, dodecanol, trans-2-hexenol, cis-3-hexenol, 1-octen-3-ol, 2,
6-dimethyl-2-heptanol, 9-decenol, 4
-Methyl-3-decen-ol, 10-undecenol, trans-2-cis-6-nonadienol, 2,4
-Dimethyl-3-cyclohexene-1-methanol, 4
-Isopropylcyclohexanol, 4-isopropylcyclohexanemethanol, 1- (4-isopropylcyclohexyl) -ethanol, 2,2-dimethyl-3-
(3-methylphenyl) -propanol, pt-butylcyclohexanol, ot-butylcyclohexanol, ambrinol, 1- (2-t-butylcyclohexyloxy) -2-butanol, pentamethylcyclohexylpropanol, Aliphatic alcohols such as-(2,2,6-trimethylcyclohexyl) -3-hexanol, linalool, geraniol, nerol, citronellol, rosinol, myrcenol, lavandulol, tetrahydrogeraniol, tetrahydrolinalool, hydroxycitronellol, dihydromyrcenol , Allosimenol, terpineol, α-terpineol, terpinen-4-ol, 1-menthol,
Borneol, isopulegol, nopol, farnesol, nerolidol, bisabolol, cedrol, patchouli alcohol, terpene alcohols such as vetiverol, santalol, isobornylcyclohexanol,
Sandalore, bagdanol, sandal mysorcoa, bramanol, evanol, polysanthol, synthetic sandals such as 3,7-dimethyl-7-methoxyoctan-2-ol, benzyl alcohol, phenylethyl alcohol, phenoxyethyl alcohol, styraryl alcohol, Anise alcohol, cinnamic alcohol, phenylpropyl alcohol, dimethylbenzylcarbinol, dimethylphenylethylcarbinol, phenylethylmethylethylcarbinol, 3-methyl-5-phenylpentanol, thymol, carvacrol, orcinol monomethyl ether, eugenol , Isoeugenol, aromatic alcohols such as propenyl guaetol, ethers; nerol oxide, miloxide, 1,
8-cineole, rose oxide, limetol, mentfuran, linalool oxide, butyldimethyldihydropyran, acetoxyamyltetrahydropyran, cerylmethylether, methoxycyclododecane, 1-
Methyl-1-methoxycyclododecane, ethoxymethylcyclododecyl ether, tricyclodecenylmethyl ether, rubofix, sedroxide, ambroxane, glycalva, powagiris, anisole, dimethylhydroquinone, paracresyl methyl ether, acetoanisole, anethole, Ethers such as dihydroanethole, estragole, diphenyl oxide, methyl eugenol, methyl isoeugenol, benzyl isoeugenol, phenylethyl isoamyl ether, β-naphthyl methyl ether, β-naphthyl ethyl ether, β-naphthyl isobutyl ether; aldehydes; carbon; Linear aliphatic aldehydes of formulas 6 to 13, trimethylhexyl aldehyde, methyl octylacetaldehyde, methyl nonylacetode Aldehyde, trans-2-hexenal, cis-4-heptenal,
2,6-nonadienal, cis-4-decenal, undecylenaldehyde, trans-2-dodecenal, trimethylundecenal, 2,6,10-trimethyl-
Aliphatic aldehydes such as 5,9-undecadienal, citral, citronellal, hydroxycitronellal, terpene aldehydes such as perilaldehyde, methoxydihydrocitronellal, citronellyloxyacetaldehyde, 2,4-dimethyl-3- Cyclohexenylcarboxyacetaldehyde, isocyclocitral, centenal, mylacaldehyde, liral,
Aldehydes such as Bernaldehyde, Dupical, Maceal, Boronal, Setnal, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, cinnamaldehyde, α-cinnamaldehyde, α-hexylcinnamaldehyde, hydrotropic aldehyde, anisaldehyde, p- Methylphenylacetaldehyde, cuminaldehyde, cyclamenaldehyde, 3- (pt-butylphenyl)-
Propylaldehyde, p-ethyl-2,2-dimethylhydrocinnamaldehyde, 2-methyl-3- (p-methoxyphenyl) -propylaldehyde, pt-butyl-α-methylhydrocinnamic aldehyde, salicylaldehyde, helio Aromatic aldehydes and acetals such as tropine, helional, vanillin, ethyl vanillin, and methyl vanillin; octylaldehyde glycol acetal, acetaldehyde ethyl cis-3-hexenyl acetal, citral dimethyl acetal, citral diethyl acetal, acetaldehyde ethyl linalyl acetal, hydroxycitrone Lal dimethyl acetal, phenylacetaldehyde dimethyl acetal, hydrotropic aldehyde dimethyl acetal, acetaldehyde Le phenylethyl acetal, acetaldehyde phenylethyl propyl acetal, phenylpropyl aldehyde propylene glycol acetal,
4,4,6-trimethyl-2-benzyl-1,3-dioxane, 2,4,6-trimethyl-2-phenyl-1,
Acetals such as 3-dioxane, 2-butyl-4,4,6-trimethyl-1,3-dioxane, tetrahydroindeno-m-dioxin, dimethyltetrahydroindeno-m-dioxin, and calanal; ketones; acetoin, diacetyl , Methyl amyl ketone, ethyl amyl ketone, methyl hexyl ketone, methyl nonyl ketone, methyl heptenone, aliphatic ketones of coabon, camphor, carvone, menthone, d-pulegone, piperiton, fenchon, geranylacetone, cedrill methyl ketone, nootkatone, Ionone, α-ionone, β-ionone, methylionone, α-n-methylionone, β-n-methylionone, α-isomethylionone, β-isomethylionone, allylionone,
Iron, α-iron, β-iron, γ-iron, damascon, α-damascon, β-damascon, δ-damascon, damasenone, dynascon, α-dynascon, β
Terpene ketones such as dynascone, maltol, ethyl maltol, 2,5-dimethyl-4-hydroxyfuranone, sugar lactone, pt-butylcyclohexanone, amylcyclopentanone, heptylcyclopentanone, dihydrojasmon, cis-jasmon, Florex, Pricatone, 4-cyclohexyl-4-methyl-2-pentanone, p-menten-6-ylpropanone, 2,2,5-trimethyl-5-pentylcyclopentanone, ethoxyvinyltetramethylcyclohexanone, dihydropentamethylin Cyclic ketones such as danone, iso-i-super, and trimorphix, acetophenone, p-methylacetophenone, benzylacetone, carone, raspberry ketone, anisylacetone, 4-
Aromatic ketones such as (4-hydroxy-3-methoxyphenyl) -2-butanone, methylnaphthyl ketone, 4-phenyl-4-methyl-2-pentanone, benzophenone, esters; ethyl formate, cis-3-hexenyl formate ,
Formic esters such as linalyl formate, citronellyl formate, geranyl formate, benzyl formate, phenylethyl formate, ethyl acetate, butyl acetate, isoamyl acetate, methyl cyclopentylidene acetate, hexyl acetate, cis-3-hexenyl acetate, trans-2-acetate Hexenyl, isononyl acetate, citronellyl acetate, lavandulyl acetate, geranyl acetate, linalyl acetate, myrcenyl acetate, terpinyl acetate, menthyl acetate, menthanyl acetate, nopyryl acetate, n-bornyl acetate, isobornyl acetate, pt-butylcyclohexyl acetate, o -T-butylcyclohexyl,
Acetic acid, tricyclodecenyl, 2,4-dimethyl-3 acetate
-Cyclohexene-1-methanyl, benzyl acetate, phenylethyl acetate, styryl acetate, cinnamyl acetate, anisyl acetate, paracresyl acetate, heliotropyl acetate,
Acetates such as acetyleugenol, acetylisoeugenol, guayl acetate, ceryl acetate, vetylyl acetate, decahydro β-naphthyl acetate, ethyl propionate, isoamyl propionate, citronellyl propionate, geranyl propionate, linalyl propionate, tapinyl propionate Benzyl propionate, cinnamyl propionate, cyclohexyl allyl propionate, propionate such as tricyclodecenyl propionate, ethyl butyrate, ethyl 2-methylbutyrate, butyl butyrate, isoamyl butyrate, hexyl butyrate, linalyl butyrate,
Geranyl butyrate, citronellyl butyrate, benzyl butyrate, cis-3-hexenyl isobutyrate, citronellyl isobutyrate, geranyl isobutyrate, linalyl isobutyrate, benzyl isobutyrate, phenylethyl isobutyrate, phenoxyethyl isobutyrate, tricyclodecenyl isobutyrate Butyrate esters such as ethyl valerate, ethyl valerate, propyl valerate, citronellyl isovalerate, geranyl isovalerate, benzyl isovalerate, cinnamyl isovalerate, phenylethyl isovalerate, valerate esters, ethyl caproate, capron Allyl acid, ethyl enanthate, allyl enanthate, ethyl caprate, citronellyl tiglate, methyl octynecarboxylate, allyl 2-pentyloxyglycolate, cis-3-
Aliphatic esters such as hexenylmethyl carbonate, ethyl pyruvate, isoamyl pyruvate, ethyl acetoacetate, keto esters such as ethyl levulinate, methyl benzoate, ethyl benzoate, isobutyl benzoate, isoamyl benzoate, Geranyl benzoate, linalyl benzoate,
Benzoic acid esters such as benzyl benzoate, phenylethyl benzoate and methyl dihydroxydimethylbenzoate, methyl phenylacetate, ethyl phenylacetate, isobutyl phenylacetate, geranyl phenylacetate, benzyl phenylacetate, phenylethyl phenylacetate, phenylethyl phenylacetate and p-phenylacetate
Phenylacetic acid esters such as cresyl, methyl cinnamate, ethyl cinnamate, benzyl cinnamate, cinnamyl cinnamate, cinnamate cinnamate, methyl salicylate, ethyl salicylate, isobutyl salicylate, isoamyl salicylate, hexyl salicylate, salicylate cis Salicylates such as -3-hexenyl, benzyl salicylate and phenylethyl salicylate; anisates such as methyl anisate and ethyl anisate; anthranilates such as methyl anthranylate ethyl anthranilate and methyl methyl anthranilate; jasmonic acid Methyl, methyl dihydrojasmonate, ethyl methyl phenylglycidate, ethyl phenylglycidate, glycomel, fractone, fraystone, furtate, divescon, ethyl 2-methyl -6-pentyl-4-oxa -2
Esters and acids such as cyclohexene carbonate; geranilic acid, citronellic acid, benzoic acid, phenylacetic acid, phenylpropionic acid, cinnamic acid, 2-methyl-
Carboxylic acids such as 2-pentenoic acid, lactones; γ-octalactone, γ-nonalactone,
lactones such as γ-decalactone, γ-undecalactone, δ-decalactone, coumarin, dihydrocoumarin, jasmolactone, and jasmine lactone; synthetic musks; muscone, cibetone, cyclopentadecanone, cyclohexadecenone, cyclopentadecalide; 1
2-ketocyclopentadecalide, cyclohexadecalide, cyclohexadecenolide, 12-oxa-16-hexadecanolide, 11-oxa-16-hexadecanolide, 10-oxa-16-hexadecanolide, ethylene brassate, ethylene dodecane Macrocyclic musks such as geoate, musk ketone, muxylol, musk ambrette, musktibeten, nitromusk such as muskmosken, 6-acetylhexamethylindane, 4-acetyldimethyl-t-butylindane, 5-acetyltetramethylisopropylindane, etc. Indan musk, 6
-Tetralin musks such as acetylhexatetralin, hexamethylhexahydrocyclopentabenzopyran, etc .; acetylpyrrole, indole, skatole,
Indolene, 2-acetylpyridine, marimatima, 6
-Methylquinoline, 6-isopropylquinoline, isobutylquinoline, 2-acetylpyrazine, 2,3-dimethylpyrazine, 2-isopropyl-3-methoxypyrazine, 2-isobutyl-3-methoxypyrazine, 2-secondarybutyl-3-methoxy Pyrazine, trimethylpyrazine, geranylnitrile, citronellylnitrile, 5
-Phenyl-3-methyl-2-pentenenitrile, 3,
7-dimethyl-2,6-nonadienenitrile, cinnamonnitrile, cuminnitrile, dodecanenitrile, tridecene-2-nitrile 5-methyl-3-heptanone oxime, dimethylsulfide, 2-methyl-4-propyl-
1,3-oxathiane, allyl isothiocyanate, p-
Mentan-8-thiol-3-one, p-menten-8
-"Single fragrance" which is used by isolating fragrance components such as thiol and β-methylthiopropionate from natural products (isolated fragrance) or chemically synthesizing (synthetic fragrance), rosemary, lemon, `` Natural fragrances '' using ingredients collected from plants such as lime, lime squash, lavender, melissa, mandarin, mint, etc., or from animals such as musk, a plurality of the above-mentioned components, a retaining agent, an antioxidant And a "mixed fragrance" can be used as appropriate. As a retention agent, benzyl benzoate, dimethyl phthalate, diethyl phthalate and the like can be used. Further, as an antioxidant, dibutylhydroxytoluene or the like can be used.
The fragrances applicable to the present invention are not limited to the above-mentioned fragrances. For example, “Basic knowledge of fragrances and incense” edited by Motoki Nakajima (first edition, June 21, 1995, published by Sangyo Tosho Co., Ltd.) P. Synthetic fragrances described in P. 121 to 271; Natural flavors described in 273 to 329;
And P.S. Fragrances using the formulation bases described in 330-326 can also be used.

For example, as a hardly decomposable binder, a silicon-based binder, particularly, a hydrolyzable silane or an alkyl silicate is used.
In the case of containing a polyorganosiloxane, the contact angle of the coating film with water may increase due to the remaining unreacted hydrolyzable group (alkoxy group). However, it has been found that the contact angle of the coating film can be reduced by adding the above fragrance to the composition. Furthermore, among the above fragrances,
It has been found that the inclusion of at least one of alcohols and ketones improves the photocatalytic hydrophilizing action. Examples of the fragrance having a particularly high effect of improving the photocatalytic hydrophilicity include aliphatic alcohols, terpene-based alcohols, and terpene-based ketones.

The content of the fragrance in the present invention is preferably 10% by weight or less based on the composition. If the fragrance exceeds 10% by weight, the fragrance is too strong or the drying time after application of the composition of the present invention is undesirably increased. A more preferable concentration of the fragrance is 0.0001 to 5% by weight, further preferably 0.001 to 2% by weight, particularly preferably 0.01 to 1% by weight.

The composition of the present invention may further contain a surfactant. Examples of the surfactant include polyhydric alcohol-type nonionic surfactants (glycerol fatty acid monoester, sorbitan ester, sugar fatty acid ester, etc.) and polyethylene glycol-type nonionic surfactants (polyoxyalkylene oxide adducts of higher alcohols) A polyoxyalkylene oxide adduct of an alkylphenol, a polyoxyalkylene oxide adduct of a fatty acid, a polyoxyalkylene oxide adduct of a higher aliphatic amine, a pluronic nonionic surfactant,
Polyoxyalkylene oxide adducts of polyhydric alcohol type nonionic surfactants, polyether-modified organosiloxanes, etc.), nonionic surfactants such as fatty acid alkanolamides, perfluoroalkylsulfonic acid salts, perfluoroalkylcarboxylic acid salts Perfluoroalkylethylene oxide adducts, perfluoroalkyltrimethylammonium salts, perfluoroalkylaminosulfonates, perfluoroalkyl group-containing oligomers (eg, “MegaFac” manufactured by Dainippon Ink and Chemicals, Inc.), Fluoroalkenyloxybenzenesulfonate, sodium perfluoroalkenyloxybenzenesulfonylsarcosine, perfluoroalkenylpolyoxyethylene ether, perfluoroalkenyloxyben Persulfonalkylammonium iodide, perfluoroalkenyloxybenzamide alkylammonium iodide, perfluoroalkenyloxyaralkylbetaine, perfluoroalkenyloxyaralkylphosphonic acid, diglycerin tetrakis (perfluoroalkenylpolyoxyethylene ether) (for example, ), Fatty acid salts (such as fatty acid soaps), sulfate salts (α-olefin sulfate salts, higher alcohol sulfate salts, sulfuric acid salts of fatty acid esters, and sulfuration). Oil, sulfate of higher alcohol AOA, sulfate of alkylphenol AOA, etc., sulfonate (α-olefin sulfonate, α-sulfonated fatty acid salt, α-sulfone) Fatty acid ester salt, alkylbenzene sulfonate, Igepon A type, aerosol OT type, polystyrene sulfonate, etc.), phosphate ester salt (phosphate ester salt of higher alcohol, phosphate ester of higher alcohol AOA, etc.) Cationic surfactants such as anionic surfactants, amine salt-type cationic surfactants (such as hydrochlorides of higher aliphatic amines), and quaternary ammonium salt-type surfactants (such as alkyldimethylbenzylammonium salts);
Amino acid-type amphoteric surfactants (such as sodium laurylaminopropionate), betaine-type amphoteric surfactants (such as lauryldimethylbetaine), sulfate ester-type amphoteric surfactants, sulfonate-type amphoteric surfactants, and phosphate ester salts And amphoteric surfactants such as amphoteric surfactants.

According to a preferred embodiment of the present invention, as the surfactant, a nonionic surfactant or a fluorine-based surfactant can be used alone or in combination.

In particular, a fluorine-based surfactant not only exerts an excellent effect of improving the leveling property of a liquid at the time of coating, but also inhibits the expression of hydrophilicity by photoexcitation of a photocatalyst more than other surfactants. Because it is difficult, it can be suitably used.

The content of the surfactant in the present invention is preferably about 0.0005 to 2% by weight based on the composition.
If the surfactant concentration is less than 0.0005% by weight, sufficient leveling properties cannot be obtained, which is not preferable. When the amount of the surfactant exceeds 2% by weight, not only stickiness occurs on the surface after coating and drying, but also after the photocatalytic hydrophilic film is formed, the durability of the film is reduced and the film is not cured until the hydrophilicity is developed. It takes a long time, which is not preferable. A more preferred concentration of the surfactant is 0.001-2% by weight, further preferably 0.01-2% by weight, particularly preferably 0.05-1.
0% by weight.

[0020] The composition according to the invention can comprise an acid. The addition of this acid increases the polarity of the surface to which the composition according to the invention has been applied and makes it more hydrophilic.
Examples of acids which can be added to the composition according to the invention include nitric acid, sulfuric acid, hydrochloric acid, boric acid, propionic acid, acetic acid, maleic acid, adipic acid, fumaric acid, phthalic acid, valeric acid, citric acid, lactic acid, butyric acid , Malic acid, picric acid, formic acid, carbonic acid, phenol and the like.

When the hardly decomposable binder is a silicon compound, the composition according to the present invention may contain a silane hydrolysis catalyst. The presence of the catalyst promotes hydrolysis of the silane compound in the method for applying the composition according to the present invention described below. Examples of preferred catalysts include pH
2 to 5 of the above acids.

When the hardly decomposable binder is a silicon compound, the composition according to the present invention may comprise a polymerization curing catalyst. Examples of preferred polymerization curing catalysts include aluminum chelate and aluminum acetylacetonate.
Aluminum compounds such as aluminum, aluminum perchlorate, aluminum chloride, aluminum isobutoxide, and aluminum isopropoxide; tetraisopropyl titanate, tetrabutyl titanate, diisopropoxybis (ethylacetoacetate) titanium, Titanium compounds such as isopropoxybis (acetylacetate) titanium; zirconium nitrate, zirconium chloride,
Like zirconium oxychloride, tetra-n-butoxyzirconium, tri-n-butoxy-ethylacetoacetate zirconium, g-n-butoxybis (ethylacetoacetate) zirconium, n-butoxystris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium Zirconium compounds: lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate,
Basic compounds such as sodium formate, potassium acetate, potassium formate, potassium propionate, tetramethylammonium chloride, tetramethylammonium hydroxide; n-hexylamine, tributylamine, diazabicroundecene, ethylenediamine, hexanediamine, Diethylenetriamine, tetraethylenepentamine, triethylenetetramine, ethanolamines, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ-
Amine compounds such as (2-aminoethyl) -aminopropylmethyldimethoxysilane; tin acetylacetona
And tin-containing compounds such as dibutyltin octylate; metal-containing compounds such as cobalt octylate, cobalt acetylacetonate and iron acetylacetonate; phosphoric acid;
Examples include acidic compounds such as nitric acid, phthalic acid, p-toluenesulfonic acid, and trichloroacetic acid.

The composition according to the present invention is preferably weakly acidic, neutral or basic when stored in a tin container or a container made of a resin-lined metal, or when applied on a metal member. . Particularly when an acid is added as described above, it is preferable to add a pH adjuster.

When the hardly decomposable binder is a silicon compound, an organic titanate, an organic zirconium compound, or the like, β-diketones such as acetylacetone and diols such as 1,3-butanediol may be added as a chelating agent. ,
It is effective for improving storage stability.

The composition according to the invention, together with a propellant,
An aerosol spray can be obtained by enclosing in a tin container, a lining metal container, or a resin container. Examples of the propellant that can be used in the present invention include LPG, dimethyl ether, nitrogen gas, air, carbon dioxide, and the like. These propellants can be used alone or in combination of two or more. The propellant may be mixed with the coating composition, or the composition of the present invention and the propellant may be separately sealed in a double container.

The composition according to the present invention may contain an inorganic oxide in addition to the hardly decomposable binder. As inorganic oxides, ceria, zirconia, alumina, amorphous titanium oxide, tin oxide, magnesia, calcia, yttria, manganese oxide, chromia, vanadium oxide, copper oxide, cobalt oxide, nickel oxide, ruthenium oxide, hafnia, strontium oxide, One or more kinds selected from the group of silver oxide are exemplified. These inorganic oxides improve the strength of the coating as a filler. Further, when zirconia is added, the water resistance is improved. When alumina, ceria, and yttria are added, the hydrophilicity in a dark place is improved. The addition of ruthenium oxide or copper oxide improves the redox power.
The addition of silver oxide or copper oxide improves antibacterial properties.

The composition according to the present invention may contain an organic binder for fixing the photocatalytic metal oxide particles and the inorganic oxide to the surface of the substrate. Examples of the organic binder include a water-soluble polymer, carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, xanthan gum, guar gum, agar, dextrin, starch, pectin, sodium alginate, gum arabic, gelatin, lignin sulfonate , Polyethylene glycol, polypropylene glycol, carboxyvinyl polymer, acrylate polymer, polyacrylate, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl acetate saponified product, butyral resin, acrylate polymer, Isobutyl maleic acid copolymer,
Acrylic acid / methacrylic acid copolymer, acrylic acid / maleic acid copolymer, methyl vinyl ether / maleic anhydride copolymer, urethane resin, acrylic resin, and the like can be used.

The composition according to the invention comprises silver, copper, palladium, platinum, rhodium, platinum, ruthenium, gold, zinc, cobalt, iron, nickel, sodium, lithium,
One or more selected from the group consisting of strontium, potassium, calcium, magnesium and compounds of these metals may be added. Antibacterial properties can be imparted by adding at least one selected from the group consisting of silver, copper, zinc and compounds of these metals. By adding at least one selected from the group consisting of palladium, platinum, rhodium, platinum, ruthenium, gold, cobalt, iron, nickel or a compound of these metals, it is possible to improve the oxidation-reduction catalytic performance of the optical semiconductor by photoexcitation. it can. By adding at least one selected from the group consisting of sodium, lithium, strontium, potassium, calcium, magnesium and a compound of these metals, the hydrophilicity of the optical semiconductor according to photoexcitation can be improved.

The composition according to the present invention is obtained by adding at least one selected from the group consisting of layered oxides, apatites, zeolites, activated carbon, metal oxide gels, metal hydroxide gels, hydroxyapatite and metal phosphates. Is also good. By doing so, odors such as methyl mercaptan, ammonia, aldehydes, etc., and substances such as ethylene, which lose freshness of fruits and vegetables, NOx, S
In the decomposition reaction of harmful gas such as Ox, the adsorptivity to the member surface of the present invention is increased, and the decomposition of the above-mentioned substance by the redox catalyst function of the optical semiconductor is further promoted.

The composition according to the present invention can include a substance having a refractive index of 2 or less. By adding a substance having a refractive index of 2 or less, there is obtained an advantage that reflection of visible light can be effectively prevented on the applied surface. Substances having a refractive index of 2 or less which can be added to the composition according to the present invention include silica (refractive index: 1.5), tin oxide (1.9), calcium carbonate (1.6), calcium hydroxide (1.6). 1.6), magnesium carbonate (1.5), strontium carbonate (1.5), dolomite (1.7), calcium fluoride (1.4), magnesium fluoride (1.4) ), Alumina (1.6), silica sand (1.6), zeolite (1.5), montmorillonite (1.5), kaolin (1.6), sericite (1.6) ), Ferric oxide (1.8) and yttrium oxide (1.9).

The composition according to the invention may further comprise, if necessary, pigments, dyes, plasticizers, antioxidants, ultraviolet absorbers,
It is possible to add a light stabilizer or the like.

The method of applying the composition of the present invention to the surface of a substrate may be appropriately selected. Examples thereof include spray coating, dip coating, flow coating, spin coating, roll coating, brush coating, and sponge coating. Such methods can be suitably used.

The product form of the coating composition of the present invention may be aerosol spray, hand spray, or a non-woven fabric or sponge for application, which is integrated with the bottle for easy use by the user. And the form of a container in which water is leached. Also,
A product obtained by impregnating a nonwoven fabric, sponge, cloth, paper, or the like with the present composition can be sealed in a pack formed of a resin or a laminate film to obtain a product.

The composition according to the present invention is applied to the surface of a substrate whose surface is to be made hydrophilic or anti-fog, and then dried or cured to form a thin film. Drying or curing can be performed by heating, leaving at room temperature, irradiating with ultraviolet rays, or the like.

In order to form a good photocatalytic hydrophilic coating, the surface of the substrate to which the composition according to the present invention is applied is preferably clean. Especially in the case of existing base materials such as windowpanes and outer walls of vehicle enclosures and buildings, use of cleaning agents in advance, etc.
It is desirable to wash by a known method.

Before applying the composition according to the invention, an undercoat layer can be provided on the surface of the substrate. By providing the undercoat layer, the wettability of the composition according to the present invention can be improved and the composition can be uniformly applied to the surface of the substrate, and as a result, a favorable photocatalytic hydrophilic coating can be formed. The undercoat layer has an effect of firmly adhering the substrate and the photocatalytic hydrophilic film. Further, the photocatalyst contained in the photocatalytic hydrophilic film may exert an oxidizing effect by photoexcitation, and the oxidizing effect may attack the substrate surface in some cases. For example, when a painted surface or a resin is the base material, the surface may be deteriorated by the oxidizing action of the photocatalyst.
The undercoat layer is located between the photocatalytic hydrophilic coating and the substrate, and prevents the oxidizing action of the photocatalyst from damaging the member surface. The undercoat layer preferably contains at least the hardly decomposable binder and / or the inorganic oxide fine particles. The undercoat layer is not essential even if the base material is a painted surface or a resin. As described above, in the composition of the present invention, the photooxidation effect can be suppressed by setting the content of the photocatalytic metal oxide in the solid content to 20 to 50%.

Substrates which can be coated with the coating composition of the present invention include, for antifogging applications, transparent substrates such as glass, transparent plastic, lenses, prisms and mirrors. More specifically, mirrors such as bathroom mirrors, bathroom mirrors, vehicle back mirrors, dental tooth mirrors, road mirrors; spectacle lenses, optical lenses, camera lenses, endoscope lenses, illumination lenses, semiconductors Lenses such as manufacturing lenses; prisms; windows of buildings and watchtowers; vehicles such as cars, railcars, aircraft, ships, submersibles, snow vehicles, lowway gondolas, amusement park gondolas, and spaceships. Windshields for vehicles such as cars, railcars, aircraft, ships, submersibles, snowmobiles, snowmobiles, motorbikes, gondolaes in lowway, gondolaes in amusement parks;
Protective or sports goggles or masks (including diving masks) shields; helmet shields; glass for frozen food display cases; cover glass for measuring instruments; Films and patches that can be attached.

As a substrate which can be coated with the coating composition of the present invention, for outdoor use where self-purification by rainfall can be expected, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete,
Fibers, fabrics, papers, combinations thereof, laminates thereof, coatings thereof, and the like. More specifically, building exteriors such as exterior walls and roofs; window frames; exterior and painting of vehicles such as automobiles, rail vehicles, aircraft, ships, bicycles, and motorcycles;
Window glass; signs, traffic signs, soundproof walls, vinyl houses,
Insulators, vehicle covers, tent materials, reflectors, shutters, screen doors,
Covers for solar cells, covers for heat collectors such as solar water heaters,
Street lamps, pavements, outdoor lighting, stones and tiles for artificial waterfalls and artificial fountains, bridges, greenhouses, exterior wall materials, sealers and garages between walls and glass
Drains, verandas, vending machines, air conditioner outdoor units, outdoor benches, various display devices, shutters, toll booths, fee boxes, roof gutters, vehicle lamp protection covers, dustproof covers
And painting, painting of machinery and articles, exterior and painting of advertising towers, structural members, and films that can be attached to those articles,
Emblems and the like.

The substrate on which the coating composition of the present invention can be used is, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete, or fiber in applications where cleaning by water washing can be expected. ,
Fabrics, papers, combinations thereof, laminates thereof, coatings thereof, and the like. More specifically, not only the above-mentioned outdoor use members are included, but also other materials such as building interior materials, window glass, housing equipment, toilet bowls, bathtubs, washbasins, lighting fixtures, kitchenware, tableware, dish dryers, Sinks, cooking ranges, kitchen hoods, ventilation fans, window rails, window frames, tunnel walls, tunnel lighting, films and patches that can be attached to these items.

As the substrate on which the coating composition of the present invention can be used, in applications where drying can be expected to be accelerated, for example, window sashes, radiating fins for heat exchangers, pavements,
Bathroom mirror, vinyl house ceiling, vanity,
Films and patches that can be attached to automobile bodies and their articles.

The coating composition of the present invention has a wide range of uses other than those described above, such as prevention of snow accumulation and prevention of air bubble adhesion. In particular, when a surface layer having a surface roughness of 1 μm or less is provided, remarkably excellent characteristics are obtained. For example, a roofing material for a snowy country, an antenna, a transmission line, a film that can be attached to those articles, an emblem, and the like can be obtained. It is applicable to the base material including.

The thickness of the surface layer formed by a coating film on the member surface is preferably 0.4 μm or less. Then, cloudiness due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. Further, the thickness of the surface layer is set to 0.
It is more preferable that the thickness be 2 μm or less. Then, it is possible to prevent the surface layer from being colored by light interference. Also, the thinner the surface layer, the better its transparency. Furthermore,
When the film thickness is reduced, the wear resistance of the surface layer is improved.

Photoexcitation of the optical semiconductor is performed by irradiating the optical semiconductor with light having an energy (ie, shorter wavelength) than the energy gap between the conduction electron band and the valence band of the optical semiconductor crystal. More specifically, when the optical semiconductor is an anatase type titanium oxide, the wavelength is 387 nm or less, when rutile titanium oxide is 413 nm or less, when tin oxide is 344 nm or less, and when zinc oxide is 387 nm. A light beam containing the following light is irradiated. In the case of the above-mentioned optical semiconductor, since it is optically excited by an ultraviolet light source, as a light source, indoor lighting such as a fluorescent lamp, an incandescent lamp, a metal halide lamp, and a mercury lamp, sunlight, and those light sources are provided by low-loss fibers. A guided light source or the like can be used. The illuminance of light required for photoexcitation of the optical semiconductor required for hydrophilizing the surface of the composite material is 0.0001 mW / c.
m ² or more, preferably 0.001 mW / cm ² or more, more preferably 0.01 mW / cm ² or more.

[0044]

EXAMPLES (Examples 1 to 6) Aerosol spray compositions were prepared as follows. Photocatalytic coating agent, ST
To 1 part by weight of -K03 (manufactured by Ishihara Sangyo Co., Ltd.) diluted with 98.7 parts by weight of 1-propanol, 0.3 part by weight of a compounded flavor (manufactured by Takasago International Corporation) was added. Fill this mixture with a propellant (dimethyl ether) into a spray can,
An aerosol spray composition was obtained. The mixture of the preparation liquid and the propellant was prepared liquid: propellant = 50: 50 (weight). Table 1 below shows the types of used fragrances.

Comparative Example 1 As a comparative example, the following aerosol spray composition was prepared. 1 part by weight of a photocatalyst coating agent, ST-K03 (manufactured by Ishihara Sangyo Co., Ltd.)
It was diluted with 99 parts by weight of propanol. Fill this mixture with a propellant (dimethyl ether) into a spray can,
An aerosol spray composition was obtained. The mixture of the preparation liquid and the propellant was prepared liquid: propellant = 50: 50 (weight).

(Evaluation 1) An aerosol was sprayed for 30 seconds, and the subject smelled downwind. subject;
n = 13 (10 men, 3 women) Next, the taste of the fragrance was evaluated on a 5-point scale. Table 1 shows the results.

[0047]

[Table 1]

Subsequently, the subject was asked to evaluate the intensity of the fragrance irritation on a 5-point scale. Table 2 shows the results.

[0049]

[Table 2]

As shown in Tables 1 and 2, it was confirmed that the addition of the fragrance can reduce the unpleasant odor and the pungent odor due to the organic solvent.

Examples 7 to 12 Spray compositions were prepared as follows. Photocatalytic coating agent, ST-K0
3 (manufactured by Ishihara Sangyo Co., Ltd.) and 4 parts by weight of 1-propanol.
0.3 parts by weight of a fragrance (manufactured by Takasago International Corporation) was added to 7 parts by weight and 10 parts by weight of propylene glycol monomethyl ether (PGM) to obtain a spray composition. In addition, the kind of the used fragrance is the same as that of Examples 1-6.

(Comparative Example 2) Photocatalytic coating agent, ST
4 parts by weight of -K03 (Ishihara Sangyo Co., Ltd.) was diluted with 86 parts by weight of 1-propanol and 10 parts by weight of PGM to obtain a spray composition.

(Evaluation 2) By adding a fragrance,
It was examined whether hydrophilicity was inhibited. Wash in advance
Spray composition applied to floated glass sheet 25g
/ M ^TwoIt sprayed so that it might become. Dry at room temperature for about 1 hour
Thereafter, the contact angle with water was measured. After that, BLB light
Irradiation was performed, and the change over time in the contact angle was measured. For measuring contact angle
Is a contact angle meter, CA-X150 type (manufactured by Kyowa Interface Science Co., Ltd.)
It was used. The UV intensity of the BLB light is 1.0 mW /
cm^Two(Wavelength 360 nm). The results are shown in Table 3.
You.

[0054]

[Table 3]

As shown in Table 3, it was confirmed that the addition of the fragrance did not impair the hydrophilic property. In addition, Examples 7 to 12 in which a fragrance was added were compared to Comparative Example 2 in which no fragrance was added.
The contact angle with water was low at the initial stage and after 2 hours, and it was confirmed that the one to which the fragrance was added was hydrophilized earlier.

(Examples 13 to 29) 4 parts by weight of a photocatalyst coating agent, ST-K03 (manufactured by Ishihara Sangyo Co., Ltd.) was diluted with 96 parts by weight of a mixed solvent (90 parts by weight of 1-propanol and 10 parts by weight of PGM). And 0.1 parts by weight of various fragrances shown in Table 4 were added to obtain a coating composition. For Example 29, a mixture of benzyl benzoate and β-citronellol, which are used as retention agents, was added to 0.1%.
One part by weight was added.

[0057]

[Table 4]

(Comparative Example 3) Photocatalytic coating agent, ST
4 parts by weight of -K03 (Ishihara Sangyo Co., Ltd.) was diluted with 96 parts by weight of a mixed solvent (90 parts by weight of 1-propanol and 10 parts by weight of PGM) to obtain a coating composition.

(Evaluation 3) The hydrophilic properties of the coating films of the various coating compositions were evaluated. Comparative Example 3, Example 13
To 29 were coated on a washed slide glass by flow coating, and samples # 3-1 and # 1 were formed.
3-1 and # 14-1 to # 29-1 were produced. After drying the sample at room temperature for 1 hour, the contact angle with water was measured. afterwards,
Irradiation with a BLB light was performed to measure the change over time in the contact angle.
The ultraviolet intensity of the BLB light was 1.0 mW / cm ² (wavelength 360 nm). Figure 1 shows the change over time in the contact angle of the coating film
It is shown in FIG. Samples # 13-1 (2-ethylhexanol), # 14-1 (geraniol), # 15-1 (β-
The contact angle of (Citronellol) # 24-1 ((+)-camphor) is lower than that of Comparative Sample # 3-1 not only before irradiation but also during irradiation, and these fragrances have an effect of improving the hydrophilizing action. Was found to have. Samples # 16-1 to # 16
23-1, # 25-1 to # 29-1 had lower contact angles before UV irradiation than Comparative Sample # 3-1; however, UV irradiation showed the same contact angle as # 3-1. . It was found that the fragrances listed in Table 4 did not interfere with the photocatalytic hydrophilizing action. It has also been found that addition of a retention agent is possible.

(Evaluation 4) Comparative Example 3, Examples 13, 15,
Films 21 and 28 were formed on a washed slide glass by flow coating, and dried at room temperature for 1 hour. After immersing the formed slide glass in acetone for 1 hour, the slide glass is washed with clean acetone, dried at room temperature, and samples # 3-2, # 13-2, and # 13-2.
15-2, # 21-2 and # 28-2 were obtained. After measuring the contact angle with water for each sample, the sample was irradiated with a BLB light, and the change over time in the contact angle was measured. The ultraviolet intensity of the BLB light was 1.0 mW / cm ² (wavelength 360 nm). FIG. 6 shows the change with time of the contact angle of the coating film.

Samples # 21-2 (butyl acetate), # 28-
The contact angle of 2 (limonene) changed in the same manner as Comparative Sample # 3-2. It was presumed that the perfume was removed by washing the coating film with acetone. Sample # 13-
2 (2-ethylhexanol) and # 15-2 (β-citronellol)
It exhibited better hydrophilic properties than Comparative Sample # 3-2.

It has been found that the effect of improving the photocatalytic hydrophilizing effect can be obtained by adding a fragrance belonging to an aliphatic alcohol, a terpene alcohol or a terpene ketone to the above photocatalytic coating composition. . Although the mechanism is unknown at present, the excellent hydrophilicity was maintained even when the coating film was washed with acetone, suggesting that these fragrances may affect the structure of the coating film.

[0063]

According to the present invention, it is possible to provide a photocatalytic coating composition capable of effectively masking such off-flavors without impairing the photocatalytic action and effects based thereon.

[Brief description of the drawings]

FIG. 1 is a graph showing the change over time in the contact angle of water on the surfaces of samples # 3-1 and # 13-1 to # 17-1.

FIG. 2 is a graph showing the change over time in the contact angle of water on the surfaces of samples # 3-1 and # 18-1 to # 21-1.

FIG. 3 is a graph showing the change over time in the contact angle of water on the surfaces of samples # 3-1 and # 22-1 to # 25-1.

FIG. 4 is a graph showing the change over time in the contact angle of water on the surfaces of samples # 3-1 and # 26-1 to # 28-1.

FIG. 5 is a graph showing the change over time in the contact angle of water on the surfaces of samples # 3-1 and # 29-1.

FIG. 6 shows samples # 3-2, # 13-2, # 15-2, and #
It is the graph which investigated the contact angle with water of the surface of 21-2 and # 28-2 with time.

──────────────────────────────────────────────────の Continuation of front page (51) Int.Cl. ⁶ Identification code FI C09D 1/00 B01D 53/36 J (72) Inventor Shin Hayakawa 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka TOTO Equipment Co., Ltd.

Claims (23)

[Claims] 1. A photocatalytic coating composition comprising photocatalytic metal oxide particles and a fragrance. 2. A photocatalytic coating composition comprising photocatalytic metal oxide particles, a solvent, and a fragrance. 3. A photocatalytic coating composition comprising photocatalytic metal oxide particles, a hardly decomposable binder, and a fragrance. 4. A photocatalytic coating composition comprising photocatalytic metal oxide particles, a hardly decomposable binder, a solvent, and a fragrance. 5. The coating composition according to claim 1, wherein the surface of the coating film exhibits hydrophilicity in response to photoexcitation and / or the hydrophilicity of the coating film surface increases in response to photoexcitation. The photocatalytic coating composition according to any one of claims 4 to 4. 6. The photocatalytic coating composition according to claim 1, wherein the coating composition is spray-coated on a substrate surface. 7. An aerosol spray composition comprising the composition according to claim 1 and a propellant. 8. The coating composition according to claim 1, wherein the coating composition is spread on the surface of a substrate and coated.
6. The photocatalytic coating composition according to any one of items 5 to 5. 9. The composition according to claim 1, wherein the content of the fragrance is 10% by weight or less. 10. The content of the fragrance is 0.0001-5.
The composition according to any one of claims 1 to 9, wherein the composition is% by weight. 11. The method according to claim 1, wherein the total content of the photocatalytic metal oxide particles and the hardly decomposable binder is 0.01 to 5% by weight. The composition according to Item. 12. The method according to claim 2, wherein the solvent is an organic solvent.
The composition according to any one of claims 1 to 11. 13. The composition according to claim 2, wherein the solvent is water and / or a water-soluble solvent. 14. The composition according to claim 13, wherein the water-soluble solvent is a mixed solvent of a water-soluble solvent having a boiling point of less than 120 ° C. and a water-soluble solvent having a boiling point of 120 ° C. or more. 15. The composition according to claim 1, wherein the metal oxide is an anatase type titanium dioxide. 16. The composition according to claim 3, wherein the hardly decomposable binder is a silicon-based binder. 17. The method according to claim 16, wherein the silicon-based binder contains at least one selected from a hydrolyzable silane, an alkyl silicate, a polyorganosiloxane, and colloidal silica. Composition. 18. The composition according to claim 1, wherein the fragrance contains at least one of alcohols and ketones. 19. The fragrance according to claim 1, wherein the fragrance contains at least one selected from the group consisting of aliphatic alcohols, terpene alcohols, and terpene ketones. A composition according to claim 1. 20. A method for hydrophilizing the surface of a member, comprising a step of applying the composition according to any one of claims 1 to 19 to the surface of the member, and a step of drying or curing the composition. . 21. An automobile body, a painted surface,
21. A resin product, glass, or stone.
The method described in. 22. A member having the composition according to claim 1 applied to the surface. 23. The vehicle according to claim 23, wherein the member is an automobile body, a painted surface,
23. A resin product, glass, or stone.
A member according to claim 1.