JP3250607B2 - Method for forming photocatalytic hydrophilic film, substrate cleaning agent for forming photocatalytic hydrophilic film, and photocatalytic hydrophilic film forming material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a coating film capable of making a substrate surface highly hydrophilic and maintaining it. Particularly, the present invention relates to a suitable method for forming the coating film on an existing substrate. Furthermore, the present invention relates to a suitable method for forming the coating film on a base material such as an existing bathroom member, an air conditioner outdoor unit, and a toilet on which dirt caused by a hardly soluble calcium salt is adhered. Furthermore, suitable for forming the above-mentioned coating film on an existing window glass, a window frame, a substrate to which dirt caused by a silicone sealing material is attached such as an outer wall, or a window glass to which permanent dirt is attached. About the method. In addition, the present invention, particularly to make the existing substrate surface highly hydrophilic, and forming a coating film that can be maintained, a cleaning agent for cleaning the surface,
It relates to a coating composition.

[0002]

2. Description of the Related Art The present inventors have proposed PCT / WO96 / 29.
As disclosed in Japanese Patent No. 375, when a photocatalyst-containing layer is formed on a substrate surface, the layer surface exhibits a high degree of hydrophilicity of 10 ° or less in terms of a contact angle with water in response to photoexcitation of the photocatalyst. Further, it has been found that such effects as anti-fogging and improving visibility of transparent members such as glass, lenses, mirrors, etc., and improving water washability and rain washability of the article surface can be obtained.

[0003]

However, in particular, when the above-mentioned layer is formed on an existing base material, since the surface of the existing base material is already contaminated, the surface becomes transparent due to the influence of the contaminant. Properties, design properties and hydrophilicity were sometimes impaired. An object of the present invention has been made in view of the above circumstances, and a method for forming a photocatalytic hydrophilic film in which the transparency, design, and hydrophilicity of the surface are not impaired by the influence of dirt on an existing substrate. Is to provide. Another object of the present invention is to provide a photocatalytic hydrophilic film forming material as well as a detergent for forming a photocatalytic hydrophilic film without impairing the surface transparency, design and hydrophilicity. is there.

[0004]

In order to solve the above-mentioned problems, the present invention is characterized in that after performing a step of cleaning the surface of a substrate, a photocatalytic hydrophilic coating liquid is applied and cured. The present invention provides a method for forming a photocatalytic hydrophilic coating. By cleaning the surface of the base material, dirt on the existing base material can be removed, so that it is possible to prevent the hydrophilicity of the surface from being impaired by the influence of the dirt on the existing base material.

[0005] In one embodiment of the present invention, the photocatalytic hydrophilic coating liquid has an average composition formula of Si _{x q} O _{(4-q) / 2.}
(Where X is an alkoxy group or a halogen atom, and q is a number satisfying 0 <q <4). It contains an amorphous silica coating and photocatalytic oxide particles dispersed in the coating-forming element to hydrophilize the surface of the coating in response to photoexcitation. When a coating film is formed on the surface of the substrate with the coating liquid, a curing reaction of the amorphous silica causes the film to be heated from room temperature to 150 ° C.
At a low temperature of about ° C., a film containing photocatalytic oxide particles and amorphous silica is formed on the surface of the substrate. Therefore, the photocatalytic hydrophilic film can be easily formed on the existing base material.

[0006] In another aspect of the present invention, the photocatalytic hydrophilic co - coating solution, the average composition formula R _p SiX _q O
_{(4-pq) / 2} (wherein R is one or more monovalent organic groups)
X is an alkoxy group or a halogen atom, and p and q are 0 <p.
<2, 0 <q <4), a film-forming element comprising a siloxane represented by the following formula: which, when cured, forms a silicone resin film; The organic group dispersed in the silicon film on the surface of the film by photoexcitation is at least partially replaced with a hydroxyl group by photocatalysis, and the surface of the film is hydrophilized by photoexcitation. To contain photocatalytic oxide particles. When a coating film is formed on the surface of the substrate with the coating liquid, a coating containing photocatalytic oxide particles and silicone is formed on the surface of the substrate at a low temperature of from room temperature to about 150 ° C. due to a siloxane curing reaction. Become so. Therefore, the photocatalytic hydrophilic film can be easily formed on the existing base material.

In another aspect of the present invention, there is provided a method for forming a photocatalytic hydrophilic coating on a surface of a substrate to which dirt caused by a silicone sealing material has adhered, the method comprising: A photocatalyst characterized by applying a photocatalytic hydrophilic coating liquid and curing after performing a step of removing colored stain components by washing with a cleaning liquid and a step of coating the remaining silicone with a primer. The present invention provides a method for forming a hydrophilic hydrophilic film. By coating the remaining silicone with a primer to make the surface hydrophilic, the photocatalytic hydrophilic coating liquid becomes wet on the substrate surface, and a uniform photocatalytic hydrophilic coating is formed. As a result, it is possible to prevent the hydrophilicity of the surface from being impaired due to the influence of silicone contamination on the existing base material.

In another aspect of the present invention, there is provided a method of forming a photocatalytic hydrophilic film on a surface of a substrate to which dirt caused by a silicone sealing material has adhered. A photocatalytic property characterized by applying a photocatalytic hydrophilic coating liquid and curing after performing a step of removing colored stain components by washing with a cleaning liquid, and a step of irradiating a residual silicon surface with ultraviolet rays. Provided is a method for forming a hydrophilic coating. By coating the residual silicone by irradiating ultraviolet rays to make the surface hydrophilic,
The photocatalytic hydrophilic coating liquid wets the surface of the substrate, and a uniform photocatalytic hydrophilic coating is formed. Therefore, the hydrophilicity of the surface is affected by the influence of the silicon stain on the existing substrate. Can be prevented from being damaged.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The step of cleaning the surface of a substrate is performed, for example, in the following procedure. First, in order to prevent the cleaning liquid and the photocatalytic hydrophilic coating liquid to be applied thereafter from scattering around the applied part, the peripheral part of the applied part is masked.
Next, the substrate is wiped with a cloth impregnated with a cleaning agent, a waste cloth, absorbent cotton, or the like to remove dirt attached to the surface of the base material. Here, a surfactant, an acid, an alkali, and the like can be appropriately used as the cleaning agent. Moreover, you may mix | blend an abrasive with the said cleaning agent. Next, the cleaning agent remaining on the surface of the base material is removed by wiping with a cloth impregnated with water, a rag, absorbent cotton, or the like. Next, the water is wiped off with a wiper, a dry cloth, a rag, absorbent cotton, or the like.

As the cleaning agent, an acidic cleaning agent, a basic cleaning agent, a cleaning agent containing a surfactant or an abrasive, an organic solvent, and the like can be appropriately used depending on the type and stain of the base material. Two or more cleaning agents may be used in combination. In order to remove stains caused by the hardly soluble calcium salt and permanent stains on window glass mainly containing silica gel, an acidic cleaning agent can be suitably used. Acids that can be used for the acidic cleaning agent include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, hydrogen fluoride, ammonium fluoride and potassium fluoride, formic acid, acetic acid, oxalic acid, citric acid, and apple. Organic acids such as acid, succinic acid, sulfamic acid, glycolic acid, gluconic acid and the like can be mentioned. For removing oily stains, a detergent containing a basic detergent or a surfactant can be suitably used. Examples of the base used for the basic detergent include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium phosphate, aqueous ammonia, monoethanolamine, diethanolamine, triethanolamine, and alkaline electrolyzed water. Can be Examples of the surfactant include polyoxyethylene alkyl phenyl ether ammonium sulphonate, sodium polyoxyethylene alkyl phenyl ether sulphonate, fatty acid soap, fatty acid sodium soap, sodium dioctyl sulfosuccinate, alkyl sulfate, Alkyl ether sulfate, alkyl sulfate soda salt, alkyl ether sulfate soda salt, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether sulfate soda salt, alkyl sulfate -T
EA salt, polyoxyethylene alkyl ether tersulfate TEA salt, 2-ethylhexyl alkyl sulfate sodium salt, sodium acylmethyltaurate,
Sodium lauroylmethyltaurate, sodium dodecylbenzenesulfonate, sodium alkylbenzenesulfonate, disodium lauryl sulfosuccinate,
Disodium lauryl polyoxyethylene sulfosuccinate, polycarboxylic acid, oleoyl sarcosine, amido ether sulphate, lauroyl sarcosine, sodium sulfo FA ester, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate Anionic surfactants such as perfluoroalkyl phosphate, sodium perfluoroalkenyloxybenzenesulfonate, sodium perfluoroalkenyloxybenzenesulfonylsarcosine, perfluoroalkenyloxyaralkylphosphonic acid, and the like; polyoxyethylene lauryl ether; Polyoxyethylene tridecyl ether, polyoxyethylene acetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, poly Carboxymethyl ethylene alkyl ET - ethers,
Polyoxyethylene alkyl ester, polyoxyethylene alkyl phenol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene laurate, polyoxyethylene stearate, poly Oxyethylene alkylphenyl ether, polyoxyethylene oleate
Sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, polyether modified silicone, polyester modified silicone, sorbitan laurate, sorbitan stearate, sorbitan palmitate
, Sorbitan sesquioleate, sorbitan oleate
Polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan oleate, glycerol stearate, polyglycerin fatty acid ester, alkyl alcohol Kiloamide, lauric acid diethanolamide, oleic acid diethanolamide, oxyethylene dodecylamine, polyoxyethylene dodecylamine, polyoxyethylene alkylamine, polyoxyethylene octadecylamine,
Polyoxyethylene alkyl propylene diamine, polyoxyethylene oxypropylene block polymer, polyoxyethylene stearate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl ethylene oxide / propylene oxide adduct, perfluoroalkyl propylene oxide adduct, Nonionic surfactants such as fluoroalkyl oligomers, perfluoroalkenyl polyoxyethylene ether, perfluoroalkenyloxyoxyethylene ether, and diglycerin tetrakis (perfluoroalkenyloxyoxyethylene ether); dimethylalkyl betaine, alkyl glycine, amido betaine; Imidazoline, perfluoroalkylaminosulfonate, perfluoroalkylbetaine, Amphoteric surfactants such as fluoroalkenyloxyaralkylbetaine; octadecyldimethylbenzylammonium chloride, alkyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium chloride, dioleyldimethylammonium chloride, 1-hydroxy-2-alkylimidazoline quaternary salt, alkyl Isoquinolinium bromide, polymeric amine, octadecyltrimethylammonium chloride, alkyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride,
Behenyltrimethylammonium chloride, alkylimidazoline quaternary salt, dialkyldimethylammonium chloride, octadecylamine acetate, tetradecylamine acetate, alkylpropylenediamine acetate, didecyldimethylammonium chloride, perfluoroalkyltrimethylammonium salt, perfluoroalkyl Quaternary ammonium salts, perfluoroalkenyloxybenzenesulfonalkylammonium iodides,
Cationic surfactants such as perfluoroalkenyloxybenzamide alkylammonium iodide and the like can be used. An abrasive may be added to the cleaning agent in order to enhance the cleaning performance. As abrasives, cerium oxide, silica powder, tripoli, dolomite, diatomaceous earth, aluminum oxide, alumina, silica, talc, kaolin, bentonite, calcium hydrogen phosphate, calcium carbonate, hydrous silicate, aluminum silicate, silica, silicon carbide, Aluminum hydroxide, sodium metaphosphate, calcium phosphate, calcium pyrophosphate, zeolite, zircon sand, zircon oxide, zirconia silicate, glass powder, perlite,
Magnesium oxide, activated clay, acid clay, titanium oxide,
Iron oxide, chromium oxide, zinc oxide, diamond powder, boron nitride, boron carbide, and the like can be used. The average particle size of these abrasives is 0.01 to 100 μm, and preferably 0.01 to 10 μm. As components of the detergent, in addition to the above components, builders, stabilizers, solvents,
And solubilizers. Builders include sodium carbonate, sodium phosphate, potassium phosphate, sodium metasilicate, sodium silicate, zeolite, sodium tripolyphosphate, potassium pyrophosphate, sodium sulfate, sodium citrate, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, -Sodium oxapentanoate, sodium polyacrylate, sodium salt of acrylic acid / methacrylic acid copolymer, acrylic acid /
Maleic acid copolymer sodium salt, carboxymethyl cellulose sodium salt and the like can be used. As a stabilizer, carboxymethylcellulose sodium salt, methylcellulose, ethylcellulose, hydroxyethylcellulose, polyethylene glycol, carboxyvinyl polymer, polyacrylate, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate saponified, xanthan gum, guar gum, sodium alginate, Gum arabic, agar, gelatin, pectin, dextrin, starch, lignin sulfonate, vinyl acetate, isobutylmaleic acid copolymer, carboxylate, aluminum magnesium silicate, magnesium silicate, bentonite, montmorillonite, attapulgite, sepiolite, etc. can be used. . Examples of the solvent include water, alcohols such as methanol, ethanol, isopropanol, normal propanol, isobutanol, ethylene glycol, and propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, and dipropyl ketone; Ethyl acetate, propyl acetate, isopropyl acetate,
Esters such as butyl acetate, amyl acetate, ethyl butyrate,
Hydrocarbons such as n-hexane, cyclohexane, heptane, etc., petroleum such as kerosene, white spirit, mineral spirit, naphtha, diethylene glycol, ethylene glycol alkyl ether, diethylene glycol alkyl ether, oligoethylene glycol alkyl ether, dipropylene glycol, propylene glycol Glycol solvents such as alkyl ethers, dipropylene glycol alkyl ethers, oligopropylene glycol alkyl ethers, and glycerin can be used. As the solubilizing agent, paratoluenesulfonic acid, sodium sulfosuccinate and the like can be used.

As the primer used in the step of coating the residual silicon with the primer, an acrylic silicon-based primer, a modified silicone-based primer, a polyester-based primer and the like can be suitably used.

As the ultraviolet light source used in the step of irradiating the surface of the residual silicone with ultraviolet light, for example, a mercury lamp, a xenon lamp, a germicidal lamp, or the like can be used.

The photocatalytic hydrophilic coating liquid contains photocatalyst particles as an essential component. In addition, from room temperature to 150
熱 Thermosetting resin for fixing to base material at low temperature,
Precursors of ultraviolet curable resin and moisture curable resin can also be added. Here, it is preferable to use a silicon resin as the resin from the viewpoint of light-catalytic oxidation resistance and light resistance. In addition, a solvent, a surfactant, a polymerization curing catalyst, a hydrolysis catalyst, a leveling agent, an antibacterial metal, a pH adjuster, a storage stabilizer, and the like may be added to the coating liquid.

In the present invention, a photocatalyst is a catalyst that emits light (excitation light) having a larger energy (ie, shorter wavelength) than the energy gap between the conduction band and the valence band of the crystal. A substance capable of generating conduction electrons and holes by excitation of electrons (photoexcitation) in the electron band. Photocatalytic oxides include, for example, anatase-type titanium oxide, rutile-type titanium oxide, and zinc oxide Oxides such as tin oxide, ferric oxide, bismuth trioxide, tungsten trioxide and strontium titanate can be suitably used.

A silicate according to claim 19 (a).
Is represented by an average composition formula SiX _q O _{(4-q) / 2} (where X is an alkoxy group or a halogen atom, and q is a number satisfying 0 <q <4). This is a coating film forming element made of silicate. This resin can be obtained by partially hydrolyzing, dehydrating and polycondensing a precursor of amorphous silica described below.

Here, the precursor of the amorphous silica includes an average composition formula SiX _q O _{(4-q) / 2} (where X is an alkoxy group,
Or a halogen atom, q is 0 <q <silicate represented by 4 is a number satisfying) - film former consisting of bets, or the general formula SiX ₄ (wherein, X is an alkoxy group, or , A halogen atom) can be suitably used.

Here, the coating film forming element comprising the above-mentioned tetrafunctional hydrolyzable silane derivative includes tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane,
Tetrabutoxysilane, diethoxydimethoxysilane and the like can be suitably used.

Further, the coating film forming element comprising the above silicate can be prepared by partial hydrolysis, dehydration condensation polymerization and the like of the above tetrafunctional hydrolyzable silane derivative.

The silicone described in claim 20 (a)
Is an average compositional formula R _p SiO _{(4-p) / 2} (wherein R is a functional group comprising one or more monovalent organic groups, or
X is a functional group composed of two or more selected from a monovalent organic group and a hydrogen group, X is an alkoxy group or a halogen atom, and p is a number satisfying 0 <p <2). It is a resin that is used. This resin can be obtained by partially hydrolyzing and dehydrating polycondensation of a silicone precursor described later.

Here, the precursor of the silicone is an average compositional formula R _p SiX _q O _{(4-pq) / 2} (where R is a functional group comprising one or more monovalent organic groups) X or a functional group composed of two or more selected from a monovalent organic group and a hydrogen group, X is an alkoxy group or a halogen atom, and p and q are 0 <p <2, 0 < a film-forming element composed of a siloxane represented by the following formula: q <4, or a general formula R _p SiX _4-p (wherein R represents one or more monovalent organic groups) Or a functional group consisting of two or more selected from a monovalent organic group and a hydrogen group,
X is an alkoxy group or a halogen atom, and p is 1
Or 2), which is preferably composed of a hydrolyzable silane derivative.

Here, as the coating film forming element comprising the hydrolyzable silane derivative, methyltrimethoxysilane,
Methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, Phenyltributoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenyl Methyldipropoxysilane, phenylmethyldibutoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, γ-glycoxydoxypropyltrimethoxysilane, γ -Acryloxypropyltrimethoxysilane and the like can be suitably used.

The film-forming element composed of the siloxane includes partial hydrolysis and dehydration-condensation polymerization of the hydrolyzable silane derivative or partial hydrolysis of the hydrolyzable silane derivative, tetramethoxysilane and tetramethoxysilane. It can be produced by dehydration polycondensation with a partial hydrolyzate such as ethoxysilane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane and the like.

The solvent used in the present invention may be water, alcohol
Can be used. Particularly, a liquid alcohol having a molecular weight of 60 to 300 is preferable. As a result, the evaporation of the liquid alcohol having a molecular weight of 60 or more (boiling point of 80 ° C. or more) in the solvent during formation of the coating film is moderately slow, so that when the coating composition is applied, Since fluctuations due to dispersible solvent evaporation can be suppressed, a transparent and uniform coating film can be formed. Molecular weight 60-3
Examples of the liquid alcohol of No. 00 include n-propanol, isopropanol, t-butanol, isobutanol, n-butanol, 2-methylpropanol, pentanole and ethylene glycol. , Monoacetone alcohol
Alcohol, diacetone alcohol, ethylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, dipropylene glycol, propylene glycol
, Tripropylene glycol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-propoxy-2-propanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether -Ter, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether and the like can be suitably used.

As the polymerization catalyst, aluminum chelate is used.
Aluminum compounds such as aluminum acetylacetonate, aluminum perchlorate, aluminum chloride, aluminum isobutoxide and aluminum isopropoxide; titanium compounds such as tetraisopropyl titanate and tetrabutoxy titanate; Basic compounds such as sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, sodium formate, potassium acetate, potassium formate, potassium propionate, and tetramethylammonium hydroxide; n-hexyl Amine, tributylamine, diazabicycloundecene, ethylenediamine, hexanediamine, diethylenetriamine, tetraethylenebentamine, triethylenetetramine, ethanolamines, γ
-Aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ- (2-aminomethyl) -aminopropyltrimethoxysilane, γ- (2-
Amine compounds such as aminomethyl) -aminopropylmethyldimethoxysilane; tin compounds such as tin acetylacetonate and dibutyltin octylate; cobalt octylate, cobalt acetylacetonate, and iron acetylacetonate Metal compounds such as phosphoric acid, nitric acid, phthalic acid, p-toluenesulfonic acid, and acidic compounds such as trichloroacetic acid.

Examples of the hydrolysis catalyst include nitric acid, hydrochloric acid, acetic acid, sulfuric acid, sulfonic acid, maleic acid, propionic acid, adipic acid, fumaric acid, phthalic acid, valeric acid having a pH of 2 to 5.
Lactic acid, butyric acid, citric acid, malic acid, picric acid, formic acid,
Carbonic acid, phenol and the like can be suitably used.

Examples of the leveling agent include diacetone alcohol, ethylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, dipropylene glycol, tripropylene glycol and 1-ethoxy-2. -Propanol, 1-butoxy-2-propano-
Propylene glycol monomethyl ether, 1-propoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether.
Tels and the like can be suitably used.

As the antibacterial metal, metals such as Ag, Cu and Zn can be added. When the metal is added, the surface layer formed by the coating film can kill bacteria and fungi attached to the surface even in a dark place.

The coating composition includes Pt, Pd, R
A platinum group metal such as u, Rh, Ir, Os can be added. When the metal is added, the surface layer formed by the coating film can enhance the oxidation-reduction activity of the photocatalyst, and can improve the decomposability of organic stains and the decomposability of harmful gases and odors.

The above-mentioned surfactants can be added to the coating composition. The wettability to the substrate surface can be improved by adding the surfactant.

The method of using the coating composition of the present invention is basically based on applying the coating composition to the surface of a substrate and curing the coating composition to form a coating film.

The coating method of the above coating composition includes spray coating, dip coating, flow coating, spin coating, roll coating, brush coating, and sponge. A method such as coating can be suitably used. As a curing method, it is possible to carry out polymerization by heat treatment, standing at room temperature, irradiation of ultraviolet rays, or the like.

When a coating film is formed on the member surface by the above method,
The surface of the member becomes hydrophilic in response to the photoexcitation of the photocatalyst. Here, in order for the substrate surface to be highly hydrophilized by photoexcitation of the photocatalyst, the illuminance of the excitation light must be 0.001.
mW suffices / cm ² or more, but preferably that it 0.01 mW / cm ² or more, and more preferably it 0.1 mW / cm ² or more. When the photocatalytic oxide is an anatase type titanium oxide, a rutile type titanium oxide, a zinc oxide, or a strontium titanate, the light source used for photoexcitation of the photocatalyst is sunlight, indoor lighting, fluorescent lamp, mercury lamp, incandescent lamp. Electric lamps, xenon lamps, high-pressure sodium lamps, metal halide lamps, BLB lamps and the like can be suitably used. When the photocatalytic oxide is tin oxide, a germicidal lamp, a BLB lamp, or the like can be suitably used.

The thickness of the surface layer formed by the 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. Furthermore, the thickness of the surface layer is
It is more preferable that the thickness be 0.2 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.
Further, when the film thickness is reduced, the wear resistance of the surface layer is improved.

As shown in PCT / WO96 / 29375, if the surface of the base material is not more than 10 ° in terms of the contact angle with water, even if moisture or steam in the air is dewed, The tendency of condensed water to form a uniform water film without forming individual water droplets becomes remarkable. Therefore, the tendency that light scattering fogging does not occur on the surface becomes remarkable. Similarly, when a window glass, a vehicle back mirror, a vehicle windshield, an eyeglass lens, or a shield of a helmet is subjected to rainfall or splashing, discrete unsightly water droplets are not formed, and high visibility and visibility are achieved. As a result, the effects of ensuring safety, ensuring the safety of vehicles and traffic, and improving the efficiency of various tasks and activities are greatly improved. Similarly, as shown in PCT / WO96 / 29375, when the surface of the base material is in a state of not more than 20 ° in terms of a contact angle with water, it is contained in exhaust gas from city dust, automobiles, and the like. Car
Both combustion products such as bon black, hydrophobic contaminants such as oils and fats, sealant eluting components, and inorganic clay contaminants do not easily adhere, and even if they adhere, they can be easily dropped by rainfall or washing with water.

If the surface of the base material exhibits the above-mentioned high hydrophilicity and keeps its state, the anti-fogging effect, the surface cleaning effect, the antistatic effect (the effect of preventing adhesion of dust), and the heat insulating effect. Thus, an effect of preventing air bubbles from adhering in water, an effect of improving efficiency in a heat exchanger, an effect of improving biocompatibility, and the like are exhibited.

The substrate to which the present invention can be applied is a transparent substrate when an anti-fogging effect is expected, and glass, plastic, or the like can be suitably used as the material. Speaking of applicable base materials, mirrors such as rearview mirrors for vehicles, bathroom mirrors, toilet mirrors, dental mirrors, road mirrors; spectacle lenses, optical lenses, illumination lenses, semiconductor lenses Lenses for copiers, copier lenses, rear view camera lenses for vehicles; prisms; windows of buildings and towers; automobiles, railway vehicles, aircraft, ships, submersibles, snowmobiles, lowway gondola, amusement parks Gondolas, vehicle windows such as spaceships; cars, motorbikes, railway vehicles, aircraft, ships, submersibles, snowmobiles, snowmobiles, lowway gondola, amusement park gondola, space Windshield for vehicles such as ships; protective goggles, sports goggles, protective mask shield, sports mask shield, helmet shield, frozen food display Case glass, Chinese bun, etc. Glass for display case of warm food; Cover of measuring instrument, Cover of camera lens for confirming the rear of vehicle, Focusing lens of laser dental treatment device, etc., Laser light detection of inter-vehicle distance sensor, etc. Cover for an infrared sensor; cover for an infrared sensor; a filter for a camera; and a film, sheet, seal, or the like to be attached to the surface of the article.

When a surface cleaning effect is expected as a substrate to which the present invention can be applied, the material may be, for example, metal, ceramic, glass, plastic, wood, stone, cement, concrete, fiber, Fabrics, combinations thereof, and laminates thereof can be suitably used. Speaking of applicable base materials, building materials, building exteriors, building interiors, window frames, windowpanes, structural members, vehicle exteriors and coatings, machinery and articles exteriors, dustproof covers and coatings, traffic signs, Various display devices,
Advertising towers, noise barriers for roads, noise barriers for railways, bridges, exterior and coating of garages, tunnel interiors and coatings, insulators, solar battery covers, solar water heater collector covers, vinyl houses, vehicle lighting Light covers, housing equipment, toilets, bathtubs, wash basins, lighting fixtures, lighting covers, kitchen utensils, dishes, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods
And a film, a sheet, a seal, and the like for attaching to the surface of the article.

As a substrate to which the present invention can be applied, when a drying acceleration effect is expected, its material is, for example, metal,
Ceramic, glass, plastic, wood, stone, cement, concrete, fiber, fabric, combinations thereof, and laminates thereof can be suitably used. Examples of applicable substrates include automobile bodies, windows, pavements, and films, sheets, and seals to be adhered to the surface of the article.

As a substrate to which the present invention can be applied, when an antistatic effect is expected, its material is, for example, metal,
Ceramic, glass, plastic, wood, stone, cement, concrete, fiber, fabric, combinations thereof, and laminates thereof can be suitably used. Speaking of applicable substrates, cathode ray tubes, magnetic recording media, optical recording media, magneto-optical recording media, audio tapes, video tapes, analog records, housings and parts for household electrical appliances, Exterior and coating, OA equipment product housing and parts and exterior and painting, building materials, building exterior, building interior, window frames, window glass, structural members, vehicle exterior and painting, machinery and articles exterior, dustproof cover and Includes films, sheets, seals, etc. for painting and sticking to the surface of the article.

[0040]

【Example】

Examples 1 to 9; application to window glass. After masking the periphery of the application surface of the window facing the north side to prevent the paint from scattering around the periphery, a water-based detergent (pH 9.5) to which sodium alkylbenzenesulfonate and fatty acid alkanolamide are added as surfactants. The window was wiped with a cloth impregnated with 5) to remove adhered dirt. Next, the window was wiped with a water-impregnated rag to remove the cleaning agent, and furthermore, water adhering to the window was removed with a wiper and a dry rag. Next, a photocatalyst coating solution ST-K01 (Titanium oxide particles 8
Parts by weight, 2 parts by weight of alkyl silicate and aqueous solution of nitric acid 5
A composition consisting of 4.8 parts by weight, 28 parts by weight of methanol and 7.2 parts by weight of propanol) and a photocatalyst coating liquid ST-K03 manufactured by Ishihara Sangyo (5 parts by weight of titanium oxide particles and alkyl silicate) 5 parts by weight, 54.8 parts by weight of a nitric acid aqueous solution, 28 parts by weight of methanol and 7.2 parts by weight of propanol) are mixed in a one-to-one ratio, and the solution obtained is mixed with 2-propanol. Photocatalyst coating liquid A obtained by diluting 25-fold
On the surface of the window glass that has been subjected to the above-mentioned cleaning treatment, φ0.8 mm
Co - - of 105 g / m ² spray with air gun after coating by plating method, by drying 20 minutes at 20 ° C., to cure the coating film to obtain # 1 specimen. On the other hand, for comparison, the above-mentioned photocatalyst coating liquid A was also applied to the window facing the north side not subjected to the above-mentioned cleaning treatment by the spray coating method, and then dried at 20 ° C. for 20 minutes. The coating was cured to give a # 2 sample. Next, # 1
The sample and the # 2 sample were examined for contact angle with water and appearance. The contact angle with water was determined by exposing the window glass sample to ultraviolet light by leaving it for 2 days after forming the coating film and exposing it to sunlight. Contact angle measuring device (Kyowa Interface Science, CA-X15
Using 0), water droplets were dropped on the sample surface from the micro syringe and measured 30 seconds after the drop. as a result,#
In the two samples, the contact angle with water was about 30 °, whereas in the # 1 sample, the contact angle with water was superhydrophilized to 0 °. The # 2 sample surface was slightly turbid, while the # 1 sample was transparent.

Embodiment 2 FIG. After masking the area around the application surface of the window facing the north side to prevent the paint from scattering around the area, a water-based detergent (pH 11.9) containing a nonionic surfactant and an alkali-inorganic builder is added. The window was wiped with an impregnated rag to remove adhered dirt. Next, the window was wiped with a water-impregnated rag to remove the cleaning agent, and furthermore, water adhering to the window was removed with a wiper and a dry rag. Next, a photocatalyst coating solution ST manufactured by Ishihara Sangyo
-K01 (8 parts by weight of titanium oxide particles and alkyl silicate)
2 parts by weight, 54.8 parts by weight of an aqueous nitric acid solution and methanol 2
Composition comprising 8 parts by weight and 7.2 parts by weight of propanol)
And a photocatalyst coating liquid ST-K03 manufactured by Ishihara Sangyo (5 parts by weight of titanium oxide particles, 5 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) Of a photocatalyst coating liquid A obtained by diluting a liquid obtained by mixing the composition consisting of 1: 1) and 2-propanol 25-fold, onto the surface of the window glass having been subjected to the above-mentioned washing treatment. 105g / using a 0.8mm air gun
After coating by m ² spray coating method,
The coating film was cured by drying for 0 minutes to obtain a # 3 sample. Next, the contact angle with water and the appearance of the # 3 sample were examined. The contact angle with water was determined by exposing the window glass sample to ultraviolet light by leaving it for 2 days after forming the coating film and exposing it to sunlight. It was measured. As a result, the contact angle with water was superhydrophilized to 0 °. Also, the sample was transparent.

Embodiment 3 FIG. After masking the area around the application surface of the window facing the north side in order to prevent the paint from scattering around the area, a cleaning agent (pH 6) containing petroleum and water to which a nonionic surfactant and a leveling agent are added is used. The window was wiped with a rag impregnated with .9) to remove adhered dirt. Next, the window was wiped with a water-impregnated rag to remove the cleaning agent, and furthermore, water adhering to the window was removed with a wiper and a dry rag. Then, a photocatalyst coating solution ST-K01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) A photocatalyst coating liquid ST-K manufactured by Ishihara Sangyo Co., Ltd.)
03 (5 parts by weight of titanium oxide particles and alkyl silicate 5
1 part by weight of a nitric acid aqueous solution, 54.8 parts by weight of a nitric acid aqueous solution, 28 parts by weight of methanol and 7.2 parts by weight of propanol.
The photocatalyst coating liquid A obtained by diluting the liquid obtained by mixing one to one with 2-propanol was applied to the surface of the window glass having been subjected to the above-mentioned washing treatment by using an air gun of φ0.8 mm.
After coating by a spray coating method of 05 g / m ² , 2
The coating was cured by drying at 0 ° C. for 20 minutes to obtain a # 4 sample. Next, the contact angle with water and the appearance of the # 4 sample were examined. The contact angle with water was determined by exposing the window glass sample to ultraviolet light by leaving it for 2 days after forming the coating film and exposing it to sunlight. It was measured. As a result, the contact angle with water was superhydrophilized to 0 °. Also, the sample was transparent.

Embodiment 4 FIG. A water-based detergent (pH 7.9) to which a nonionic surfactant and an anionic surfactant are added after masking the area around the application surface of the window facing the north side to prevent the paint from scattering around the area. The window was wiped with a rag impregnated with to remove adhering dirt. Next, the window was wiped with a water-impregnated rag to remove the cleaning agent, and furthermore, water adhering to the window was removed with a wiper and a dry rag. Next, photocatalyst coating solution ST-
K01 (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of aqueous nitric acid solution, and methanol 28
(A composition comprising parts by weight and 7.2 parts by weight of propanol)
And a photocatalyst coating liquid ST-K03 manufactured by Ishihara Sangyo (5 parts by weight of titanium oxide particles, 5 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) Of a photocatalyst coating liquid A obtained by diluting a liquid obtained by mixing the composition consisting of 1: 1) and 2-propanol 25-fold, onto the surface of the window glass having been subjected to the above-mentioned washing treatment. 105g / using a 0.8mm air gun
After coating by m ² spray coating method,
The coating film was cured by drying for 0 minutes to obtain a # 5 sample. Next, the contact angle with water and the appearance of the # 5 sample were examined. The contact angle with water was determined by exposing the window glass sample to ultraviolet light by leaving it for 2 days after forming the coating film and exposing it to sunlight. It was measured. As a result, the contact angle with water was superhydrophilized to 0 °. Also, the sample was transparent.

Embodiment 5 FIG. The area around the application surface of the window facing the west was masked to prevent the paint from scattering around, and then impregnated with an aqueous detergent (pH 11.8) containing a nonionic surfactant and an amine. The window was wiped with a rag to remove the adhered dirt. Next, the window was wiped with a water-impregnated rag to remove the cleaning agent, and furthermore, water adhering to the window was removed with a wiper and a dry rag. Then, a photocatalyst coating solution ST-K01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) Parts) and a photocatalyst coating liquid ST-K03 manufactured by Ishihara Sangyo (5 parts by weight of titanium oxide particles, 5 parts by weight of alkyl silicate and 5 parts by weight of nitric acid aqueous solution).
A liquid obtained by mixing 4.8 parts by weight, 28 parts by weight of methanol and 7.2 parts by weight of propanol) in a one-to-one ratio is diluted 25-fold with 2-propanol to obtain a liquid. Photocatalyst core
The coating liquid A was applied to the surface of the window glass subjected to the above-mentioned cleaning treatment by a spray coating method of 105 g / m ² using an air gun of φ0.8 mm, and then dried at 20 ° C. for 20 minutes to form a coating film. After curing, a # 6 sample was obtained.
Next, the contact angle with water and the appearance of the # 6 sample were examined. The contact angle with water was determined by exposing the window glass sample to ultraviolet light by leaving it for 2 days after forming the coating film and exposing it to sunlight. It was measured. As a result, the contact angle with water was superhydrophilized to 0 °. Also, the sample was transparent.

Embodiment 6 FIG. After masking the area around the application surface of the window facing the west to prevent the paint from scattering around the window, use a cloth impregnated with a cleaning agent containing electrolytic alkaline water (Hungry Water, manufactured by Painthouse). Was wiped off to remove adhered dirt. Next, the window is wiped with a rag impregnated with water to remove the cleaning agent, and further wiped.
Then, water adhering to the window was removed with a dry waste cloth. Next, a photocatalyst coating solution ST-K01 manufactured by Ishihara Sangyo Co., Ltd.
(A composition comprising 8 parts by weight of titanium oxide particles, 2 parts by weight of an alkyl silicate, 54.8 parts by weight of a nitric acid aqueous solution, 28 parts by weight of methanol and 7.2 parts by weight of propanol); -Sting liquid ST-K03 (5 parts by weight of titanium oxide particles, 5 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol, and propanol-
Of a photocatalyst coating liquid A obtained by diluting a liquid obtained by mixing 1: 1 of a composition consisting of 7.2 parts by weight of toluene with 2-propanol and subjecting it to the above-mentioned washing treatment. After coating on the surface of the window glass by a spray coating method of 105 g / m ² using an air gun of φ0.8 mm, the coating film was cured by drying at 20 ° C. for 20 minutes to obtain a # 7 sample. Next, the contact angle with water and the appearance of the # 7 sample were examined. The contact angle with water was determined by measuring the window glass sample after coating film formation.
By leaving it for a day and exposing it to sunlight, ultraviolet rays were irradiated. Thereafter, the contact angle with water was measured for the removed window glass. As a result, the contact angle with water was superhydrophilized to 0 °. Also, the sample was transparent.

Embodiment 7 FIG. After masking the area around the application surface of the window facing the west to prevent the paint from scattering around the area, wipe the window with a cloth impregnated with a cleaning agent containing cerium oxide abrasive to remove any adhered dirt. Removed. Next, the window was wiped with a water-impregnated rag to remove the cleaning agent, and furthermore, water adhering to the window was removed with a wiper and a dry rag. Then, a photocatalyst coating solution ST-K01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) A photocatalyst coating liquid ST-K manufactured by Ishihara Sangyo Co., Ltd.)
03 (5 parts by weight of titanium oxide particles and alkyl silicate 5
1 part by weight of a nitric acid aqueous solution, 54.8 parts by weight of a nitric acid aqueous solution, 28 parts by weight of methanol and 7.2 parts by weight of propanol.
The photocatalyst coating liquid A obtained by diluting the liquid obtained by mixing one to one with 2-propanol was applied to the surface of the window glass having been subjected to the above-mentioned washing treatment by using an air gun of φ0.8 mm.
After coating by a spray coating method of 05 g / m ² , 2
The coating was cured by drying at 0 ° C. for 20 minutes to obtain a # 8 sample. Next, the contact angle with water and the appearance of the # 8 sample were examined. The contact angle with water was determined by exposing the window glass sample to ultraviolet light by leaving it for 2 days after forming the coating film and exposing it to sunlight. It was measured. As a result, the contact angle with water was superhydrophilized to 0 °. Also, the sample was transparent.

Embodiment 8 FIG. After masking the area around the application surface of the window facing the west to prevent the paint from scattering around, the window was wiped with a water-impregnated cloth, and then the window was cleaned with n-hexane-impregnated cloth. It was wiped to remove the adhered dirt. Further, the solvent adhering to the window was removed with a dry rag. Next, photocatalyst coating solution ST-
K01 (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of aqueous nitric acid solution, and methanol 28
(A composition comprising parts by weight and 7.2 parts by weight of propanol)
And a photocatalyst coating liquid ST-K03 manufactured by Ishihara Sangyo (5 parts by weight of titanium oxide particles, 5 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) Of a photocatalyst coating liquid A obtained by diluting a liquid obtained by mixing the composition consisting of 1: 1) and 2-propanol 25-fold, onto the surface of the window glass having been subjected to the above-mentioned washing treatment. 105g / using a 0.8mm air gun
After coating by m ² spray coating method,
The coating film was cured by drying for 0 minutes to obtain a # 9 sample. Next, the contact angle with water and the appearance of the # 9 sample were examined. The contact angle with water was determined by exposing the window glass sample to ultraviolet light by leaving it for 2 days after forming the coating film and exposing it to sunlight. It was measured. As a result, the contact angle with water was superhydrophilized to 0 °. Also, the sample was transparent.

Embodiment 9 FIG. After masking the area around the application surface of the window facing the west to prevent the paint from scattering around, it consists of basic silica sol, monoethanolamine, nonionic surfactant, glycol solvent, ethanol, and water The window was wiped with a rag impregnated with a cleaning agent to remove adhered dirt. Then, a photocatalyst coating solution ST-K01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) Of a photocatalyst coating liquid obtained by diluting a 1-propanol and a leveling agent with a mixed solvent (90 parts by weight of 1-propanol and 10 parts by weight of propylene glycol ethyl ether) 50-fold. After coating with a nonwoven fabric made of polypropylene on the surface of the window glass that has been subjected to the above cleaning treatment,
By drying at 20 ° C. for 20 minutes, the coating film was cured to obtain a # 10 sample. Next, the contact angle with water and the appearance of the # 10 sample were examined. The contact angle with water was determined by exposing the window glass sample to ultraviolet light by leaving it for 2 days after forming the coating film and exposing it to sunlight. It was measured. As a result, the contact angle with water was superhydrophilized to 0 °. Also, the sample was transparent.

Examples 10 to 12; Application to window glass with permanent stains A cleaning agent containing ammonium acid fluoride after masking the area around the application surface of the window installed near the outlet of the outdoor unit of the air conditioner facing the north to prevent the paint from scattering around The colored stain and the calcium salt stain were removed with a cloth impregnated with. Next, after washing with tap water, the window was wiped with a rag impregnated with water to remove the cleaning agent, and furthermore, moisture adhering to the window was removed with a wiper and a dry rag. Next, a photocatalyst coating liquid ST-K01 (Ishihara Sangyo Co., Ltd.) (8 parts by weight of titanium oxide particles, 2 parts by weight of ethyl silicate, and 5 parts of nitric acid aqueous solution)
A composition comprising 4.8 parts by weight, 28 parts by weight of methanol and 7.2 parts by weight of propanol) and a photocatalyst core manufactured by Ishihara Sangyo Co., Ltd.
1 part of the liquid ST-K03 (a composition comprising 5 parts by weight of titanium oxide particles, 5 parts by weight of ethyl silicate, 54.8 parts by weight of a nitric acid aqueous solution, 28 parts by weight of methanol and 7.2 parts by weight of propanol). : 1. The liquid mixed at 1: 1 was diluted 25-fold with 2-propanol, and the photocatalytic coating liquid A was applied to the window glass surface having been subjected to the above-mentioned cleaning treatment to 105 g / m 2 using a φ0.8 mm air gun. ⁽²⁾ After coating by a spray coating method, the coating film was cured by drying at 20 ° C. for 20 minutes to obtain a # 11 sample. On the other hand, for comparison, the above-mentioned photocatalytic coating liquid A was also applied to the window facing the north side not subjected to the above-mentioned cleaning treatment by the spray coating method, and then dried at 20 ° C. for 20 minutes. Then, the coating film was cured to obtain a # 12 sample. next,#
Eleven samples and # 12 samples were examined for contact angles with water and appearance. The contact angle with water is measured for the window glass sample after coating film formation.
By leaving it for two days and exposing it to sunlight, ultraviolet rays are radiated.
A contact angle measuring device for measuring the contact angle with water (Kyowa Interface Science, CA-X
150), a water drop was dropped on the sample surface from the microsyringe and measured 30 seconds after the drop. As a result, both the # 11 sample and the # 12 sample were superhydrophilized to 0 °. However, as for the appearance, white stain was recognized in the # 12 sample, while transparency was maintained in the # 11 sample.

Embodiment 11 FIG. A cleaning agent containing a cerium oxide abrasive after masking the area around the application surface of the window installed near the nozzle of the outdoor unit of the air conditioner facing the north to prevent the paint from scattering around The colored stain and the calcium salt stain were removed with a cloth impregnated with. Next, after washing with tap water, the window was wiped with a rag impregnated with water to remove the cleaning agent, and furthermore, moisture adhering to the window was removed with a wiper and a dry rag. Then, a photocatalyst coating liquid ST-K01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of ethyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) Parts) and a photocatalyst coating liquid ST-K03 manufactured by Ishihara Sangyo (5 parts by weight of titanium oxide particles, 5 parts by weight of ethyl silicate, and 54.8 parts of nitric acid aqueous solution).
Photocatalytic coating obtained by diluting a liquid obtained by mixing 1: 1 by weight of a composition consisting of 28 parts by weight of methanol, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) with 2-propanol 25-fold. The solution A was applied to the surface of the window glass having been subjected to the above-mentioned cleaning treatment by φ0.8 m.
After coating by a spray coating method of 105 g / m ² using an air gun of m, the coating film was cured by drying at 20 ° C. for 20 minutes to obtain a # 13 sample. The contact angle with water and the appearance of the # 13 sample were examined. as a result,
It was superhydrophilized to 0 °. In addition, its appearance maintained transparency.

Embodiment 12 FIG. After masking the area around the application surface of the window installed near the outlet of the outdoor unit of the air conditioner facing the north side to prevent the paint from scattering around, an abrasive made of silicate mineral was added. A stain impregnated with a cleaning agent (TOTO KIKI, TOTO powder) was used to remove stains stained with color and calcium salts. Then
After rinsing with tap water, the window was wiped with a rag impregnated with water to remove the cleaning agent, and furthermore, water adhering to the window was removed with a wiper and a dry rag. Next, a photocatalyst coating solution ST-K01 (Titanium oxide particles 8
54 parts by weight, 2 parts by weight of ethyl silicate and an aqueous solution of nitric acid
8 parts by weight, 28 parts by weight of methanol and 7.2 parts of propanol
Parts by weight) and a photocatalyst coating liquid ST-K03 manufactured by Ishihara Sangyo (5 parts by weight of titanium oxide particles, 5 parts by weight of ethyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol, and propanol Of a mixture consisting of 7.2 parts by weight of 2-propanol in 25% by 2-propanol.
The photocatalytic coating solution A obtained by doubling the dilution was applied to the surface of the window glass having been subjected to the above-mentioned cleaning treatment by a spray coating method of 105 g / m ² using an air gun of φ0.8 mm. The coating film was cured by drying for 20 minutes to obtain a # 14 sample. The # 14 sample was examined for contact angle with water and appearance. As a result, it became superhydrophilic to 0 °. In addition, its appearance maintained transparency.

Examples 13 to 16; Application to window glass to which dirt caused by a silicone sealant adhered. After masking the area around the application surface of the window installed under the silicone sealant facing the north side to prevent the paint from scattering around, impregnated with a cleaning agent containing ammonium acid fluoride The stained stain and the stain stained with the sealant were removed from the waste cloth. Then
After rinsing with tap water, the window was wiped with a rag impregnated with water to remove the cleaning agent, and furthermore, water adhering to the window was removed with a wiper and a dry rag. Next, a photocatalyst coating solution ST-K01 (Titanium oxide particles 8
Parts by weight, 2 parts by weight of alkyl silicate and aqueous solution of nitric acid 5
A composition comprising 4.8 parts by weight, 28 parts by weight of methanol and 7.2 parts by weight of propanol) and a photocatalyst core manufactured by Ishihara Sangyo Co., Ltd.
1 part of a liquid ST-K03 (a composition comprising 5 parts by weight of titanium oxide particles, 5 parts by weight of an alkyl silicate, 54.8 parts by weight of a nitric acid aqueous solution, 28 parts by weight of methanol and 7.2 parts by weight of propanol). : 2-propano-
After coating the photocatalyst coating solution A obtained by diluting 25-fold with a 105 g / m ² spray coating method using an air gun having a diameter of 0.8 mm on the surface of the window glass subjected to the above-mentioned cleaning treatment, The coating film was cured by drying at 20 ° C. for 20 minutes to obtain a # 15 sample. On the other hand, for comparison, an attempt was made to apply the photocatalyst coating liquid A to the window facing the north side which had not been subjected to the above cleaning treatment by the spray coating method in the same manner. The material was repelled without being adapted to the material surface, and a uniform coating film could not be formed. Thereafter, the coating was cured by drying at 20 ° C. for 20 minutes to obtain a # 16 sample. next,#
The contact angle with water was examined for 15 samples and # 16 sample.
The contact angle with water was determined by exposing the window glass sample to ultraviolet light by leaving it for two days after forming the coating film and exposing it to sunlight. Contact angle measuring instrument (Kyowa Interface Science, CA-X150)
Drop a water droplet on the sample surface from the micro syringe using
It was determined by measuring after 0 seconds. As a result, # 16
In the sample, the contact angle with water was 80 °, while the contact angle with water was # 1.
In five samples, the contact angle with water was superhydrophilized to 0 °.

Embodiment 14 FIG. Silicone facing north
After masking the area around the application surface of the window installed at the bottom of the runt to prevent the paint from scattering around, wipe with a cloth impregnated with a cleaning agent containing cerium oxide abrasive, and apply color. Dirt and sealant-adhered dirt were removed. Next, after washing with tap water, the window was wiped with a rag impregnated with water to remove the cleaning agent, and furthermore, moisture adhering to the window was removed with a wiper and a dry rag. Then, a photocatalyst coating solution ST-K01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) Part) and a photocatalyst coating liquid ST-K03 (titanium oxide particles 5) manufactured by Ishihara Sangyo Co., Ltd.
Parts by weight, 5 parts by weight of alkyl silicate and 5 parts of nitric acid aqueous solution
A composition comprising 4.8 parts by weight, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) was mixed at a ratio of 1: 1 to obtain a photocatalyst core obtained by diluting 25-fold with 2-propanol. -Plating liquid A is applied to the surface of the window glass which has been subjected to the above-mentioned cleaning treatment by φ.
105 g / m ² spray using a 0.8 mm air gun
After coating by a coating method, the coating film was cured by drying at 20 ° C. for 20 minutes to obtain a # 17 sample.
Next, the contact angle with water was examined for the # 17 sample. As a result, the contact angle with water was superhydrophilized to 0 °.

Embodiment 15 FIG. Silicone facing north
After masking the area around the application surface of the window installed at the bottom of the runt to prevent the paint from scattering around, the window was wiped with a rag impregnated with a cleaning agent containing cerium oxide abrasive. Thereafter, the cleaning agent was removed with a dry rag.
Next, the window was wiped with a rag impregnated with a cleaning agent containing electrolytic alkaline water (Hungry Water, manufactured by Paint House), and the cleaning agent was removed with a rag impregnated with water.
Further, water adhering to the window was removed with a wiper and a dry rag. Then, a photocatalyst coating solution ST-K01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, and methanol
Composition consisting of 28 parts by weight of toluene and 7.2 parts by weight of propanol) and a photocatalyst coating liquid ST-K03 manufactured by Ishihara Sangyo.
(A composition comprising 5 parts by weight of titanium oxide particles, 5 parts by weight of alkyl silicate, 54.8 parts by weight of a nitric acid aqueous solution, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) is 1: 1.
Of the photocatalyst coating liquid A obtained by diluting the liquid mixed with 2-propanol 25-fold on the surface of the window glass having been subjected to the above-mentioned washing treatment using an air gun of φ0.8 mm at a rate of 105 g /
After coating by m ² spray coating method,
By drying for 0 minutes, the coating film is hardened, and # 18
A sample was obtained. Next, the contact angle with water was examined for the # 18 sample. As a result, the contact angle with water was superhydrophilized to 0 °.

Embodiment 16 FIG. Silicone facing north
After masking the area around the application surface of the window installed at the bottom of the runt to prevent the paint from scattering around, a cleaning agent containing an abrasive made of silicate minerals (TOTOKIKI, TOTO Powder) was wiped with a cloth impregnated with the powder) to remove stains adhering to color and sealants. Next, after washing with tap water, the window was wiped with a rag impregnated with water to remove the cleaning agent, and furthermore, moisture adhering to the window was removed with a wiper and a dry rag. Next, a photocatalyst coating solution ST-K01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, and an aqueous solution of nitric acid 54.
8 parts by weight, 28 parts by weight of methanol and 7.2 parts of propanol
Parts by weight) and a photocatalyst coating liquid ST-K03 manufactured by Ishihara Sangyo (5 parts by weight of titanium oxide particles, 5 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol, and propanol) Of a mixture consisting of 7.2 parts by weight of toluene (1: 1) in 2-propanol.
The photocatalyst coating solution A obtained by diluting 5-fold was applied to the surface of the window glass having been subjected to the above-mentioned washing treatment by a spray coating method of 105 g / m ² using an air gun of φ0.8 mm. The coating film was cured by drying for 20 minutes to obtain a # 19 sample. Next, the contact angle with water was examined for the # 19 sample. As a result, the contact angle with water is 0
It was superhydrophilized to ゜.

Examples 17 to 18; Application to mirrors with stains caused by poorly soluble calcium salts. The area around the application surface of the wash mirror, on which the surface is whitened due to the adhesion of the dirt caused by the hardly soluble calcium salt, is masked in order to prevent the paint from scattering around the area, and then the cloth is impregnated with a hydrochloric acid aqueous solution (pH 2). , And calcium salt adhered dirt was removed. Next, after washing with tap water, the window was wiped with a rag impregnated with water to remove the cleaning agent, and furthermore, moisture adhering to the window was removed with a wiper and a dry rag. Next, photocatalyst coating solution ST-
K01 (8 parts by weight of titanium oxide particles and ethyl silicate 2
2 parts by weight of a nitric acid aqueous solution, 28 parts by weight of methanol and 7.2 parts by weight of propanol)
-A photocatalytic coating solution obtained by diluting 25-fold with propanol was applied to the surface of a window glass having been subjected to the above-mentioned washing treatment to a diameter of 0.2 mm.
105 g / m ² spray-coat using an 8 mm air gun
After coating by the coating method, the coating film was cured by drying at 20 ° C. for 20 minutes to obtain a # 20 sample. Next, the water wettability and appearance of the # 20 sample were examined.
The wettability with water was measured by spraying water with a hand spray on a mirror. As a result, the sprayed water formed a uniform water film without forming water droplets on the window. Also, the sample was transparent.

Embodiment 18 FIG. A cleaning agent containing a cerium oxide abrasive after masking the area around the application surface of the wash mirror, which has a whitened surface due to adhesion of dirt due to the hardly soluble calcium salt, to prevent scattering around the paint. The soil impregnated with calcium salt was removed with a waste impregnated with.
Next, after washing with tap water, the window was wiped with a rag impregnated with water to remove the cleaning agent, and furthermore, moisture adhering to the window was removed with a wiper and a dry rag. Then, a photocatalyst coating liquid ST-K01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of ethyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol, and propanol-
(A composition consisting of 7.2 parts by weight of toluene) was diluted 25-fold with 2-propanol, and the photocatalytic coating solution was applied to the surface of the window glass subjected to the above-mentioned washing treatment using an air gun of φ0.8 mm. After coating by 105 g / m ² spray coating method, the coating film was cured by drying at 20 ° C. for 20 minutes to obtain # 21 sample. Next, the water wettability and appearance of the # 21 sample were examined. The wettability with water was measured by spraying water with a hand spray on a mirror. As a result, the sprayed water formed a uniform water film without forming water droplets on the window.
Also, the sample was transparent.

Embodiments 19 and 20; Application to Automotive Window Glass Embodiment 19 After masking the rear window of the automobile to prevent the paint from scattering around, the adhered dirt was removed by wiping with a cloth impregnated with a detergent containing a cerium oxide abrasive. Next, the window was wiped with a rag impregnated with water to remove the cleaning agent, and furthermore, water adhering to the window was removed with a wiper and a dry rag. Next, a photocatalyst coating solution ST manufactured by Ishihara Sangyo
-K01 (8 parts by weight of titanium oxide particles and alkyl silicate)
2 parts by weight, 54.8 parts by weight of an aqueous nitric acid solution and methanol 2
Composition comprising 8 parts by weight and 7.2 parts by weight of propanol)
Was diluted 50-fold with 1-propanol, and a photocatalyst coating solution obtained was applied to the surface of the window subjected to the above-mentioned cleaning treatment by φ.
After coating by a 30 g / m ² spray coating method using a 0.8 mm air gun, the coating film was cured by drying at 20 ° C. for 20 minutes to obtain a # 22 sample. Next, the water wettability and appearance of the # 22 sample were examined.
The wettability with water is determined by exposing the window to ultraviolet light by leaving the window for two days after forming the coating film and exposing it to sunlight. The properties were measured. As a result, the sprayed water formed a uniform water film without forming water droplets on the window. Also, the sample was transparent.

Embodiment 20 FIG. After masking the rear window of the car to prevent paint from splashing around,
The window was wiped with a cloth impregnated with a cleaning agent composed of a basic silica sol, monoethanolamine, a nonionic surfactant, a glycol-based solvent, ethanol, and water to remove adhered dirt. Next, Ishihara Sangyo photocatalyst core
1 part of a liquid ST-K01 (composition comprising 8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol and 7.2 parts by weight of propanol). -A window surface that has been subjected to the above-mentioned washing treatment with a photocatalyst coating liquid obtained by diluting 50-fold with a mixed solvent of propanol and a leveling agent (90 parts by weight of 1-propanol, 10 parts by weight of propylene glycol ethyl ether). After coating with a polypropylene nonwoven fabric, the coating film was cured by drying at 20 ° C. for 20 minutes to obtain a # 23 sample. Next, the water wettability and appearance of the # 23 sample were examined. The wettability of the water is measured by exposing the window to ultraviolet light by leaving the window for two days after forming the coating film and then exposing it to sunlight, and then spraying the water with a hand spray to wet the window. The properties were measured. As a result, the sprayed water formed a uniform water film without forming water droplets on the window. Also, the sample was transparent.

Embodiments 21 to 24; Application to Automobile Body Embodiment 21 The hood of the automobile was cleaned with a car wash sponge while running water, and then the surface of the hood was lightly rubbed with a liquid compound (manufactured by Musashi Holt) using a wax application sponge. Before the compound was dry, it was removed with a waste cloth and the bonnet was dried. Then, a photocatalyst coating solution ST-K01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) Parts) in a solvent (2-
A photocatalytic coating solution B obtained by diluting 100 times with a mixed solution of 9 parts by weight of propanol and 1 part by weight of diacetone alcohol) was obtained by using an air gun with a diameter of 0.8 mm to obtain 30 g / m 2.
² After applying by spray coating method,
The coating film was hardened by minute drying to obtain # 24 sample. On the other hand, for comparison, the car hood
After removing dirt with a car wash sponge while running water,
Without compound treatment, the photocatalyst coating liquid B was
30 g / m ² spray with air gun 0.8 mm in diameter -
The coating film was applied by a coating method and dried at 20 ° C. for 20 minutes to harden the coating film to obtain a # 25 sample. #
Comparison of the appearance immediately after application of the 24 and # 25 samples showed that the # 24 sample was the same as before the application, whereas the # 24 sample was the same as before the application.
In 25 samples, the coating film became cloudy. The # 24 sample was exposed to sunlight for 2 days after the coating film was formed, so that ultraviolet rays were irradiated. Then, water was sprayed using a hand spray. Spreading was observed.

Embodiment 22 FIG. The hood of the automobile was cleaned with a car wash sponge while running water, and then the surface of the hood was lightly rubbed with a liquid compound (manufactured by Musashi Holt) using a wax application sponge. Before the compound was dry, it was removed with a waste cloth and the bonnet was dried. Then, colloidal silica sol (Nissan Chemical,
After diluting organosilica sol, IPA-ST) with isopropanol and applying a liquid material C having a solid content concentration of 0.3% by weight with a sponge wipe, the photocatalyst coating liquid ST-K01 (titanium oxide particles 8%) manufactured by Ishihara Sangyo Co., Ltd. Parts, 2 parts by weight of an alkyl silicate, 54.8 parts by weight of an aqueous nitric acid solution, and methanol
Photocatalyst obtained by diluting 100 parts of a solvent (composition comprising 9 parts by weight of 2-propanol and 1 part by weight of diacetone alcohol) with 28 parts by weight of toluene and 7.2 parts by weight of propanol. The coating liquid B was applied by a 30 g / m ² spray coating method using an air gun having a diameter of 0.8 mm and then dried at 20 ° C. for 20 minutes to cure the coating film. Obtained. On the other hand, for comparison, after the bonnet of the automobile was washed with a car wash sponge while flowing water to remove mud and dirt, the liquid material C was applied by a sponge wipe without compound treatment, and the photocatalyst coating liquid B was applied.
30 g / m ² spray with air gun 0.8 mm in diameter -
By coating by a coating method and drying at 20 ° C. for 20 minutes, the coating film was cured to obtain a # 27 sample. #
The appearance of the # 26 sample and the # 27 sample immediately after application were compared.
In the 27 samples, the coating film became cloudy. For the # 26 sample, after being exposed to sunlight for 3 hours after the coating film was formed, ultraviolet rays were irradiated, and then water was sprayed with a hand spray. Spreading was observed.

Embodiment 23 FIG. The hood of the automobile was washed with water to remove mud stains, and then washed with a water-based detergent to which an inorganic fine particle abrasive and an anionic surfactant had been added using a car wash sponge. After thoroughly washing with water and wiping off the moisture with a dry waste cloth, the bonnet was dried. Next, a colloidal silica sol (manufactured by Nissan Chemical Industries, organosilica sol, IPA-ST) was diluted with isopropanol to apply a liquid having a solid content of 0.3% by weight by a sponge wipe, and then coated with a photocatalyst coating solution ST manufactured by Ishihara Sangyo. -K01 (a composition comprising 8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of an aqueous nitric acid solution, 28 parts by weight of methanol and 7.2 parts by weight of propanol) in a solvent (2- A photocatalyst coating solution B obtained by diluting 100 times with a mixed solution of 9 parts by weight of propanol and 1 part by weight of diacetone alcohol) was sprayed with a spray gun of 30 g / m ² using an air gun of φ0.8 mm. After coating by a coating method, the coating film was cured by drying at 20 ° C. for 20 minutes to obtain a # 28 sample. For the # 28 sample, the appearance immediately after coating was the same as before coating. Also,
After the coating film was formed, the film was exposed to sunlight for 3 hours to be irradiated with ultraviolet rays, and then water was sprayed with a hand spray. As a result, it was observed that water droplets were not formed and the water spread evenly. .

Embodiment 24 FIG. Water is applied to the hood of the automobile to remove mud stains, and then an aqueous detergent (pH:
11.9) was washed by gently rubbing it with a car wash sponge. After thoroughly washing with water and wiping off the moisture with a dry waste cloth, the bonnet was dried. Next, colloidal silica sol (manufactured by Nissan Chemical Industries, organo silica sol,
(IPA-ST) is diluted with isopropanol to obtain a solid concentration of 0.
After applying a liquid material of 3% by weight with a sponge wipe, a photocatalyst coating solution ST-K01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of aqueous nitric acid solution, methanol Photocatalyst obtained by diluting 100 parts by weight of a solvent (a mixture of 9 parts by weight of 2-propanol and 1 part by weight of diacetone alcohol) with 28 parts by weight of toluene and 7.2 parts by weight of propanol. Coating liquid B
Was applied by a 30 g / m ² spray coating method using an air gun having a diameter of 0.8 mm, and then dried at 20 ° C. for 20 minutes to cure the coating film, thereby obtaining a # 29 sample. For the # 29 sample, the appearance immediately after application was the same as before the application. In addition, after the coating film was formed, it was exposed to sunlight for 3 hours so that ultraviolet rays were irradiated, and then water was sprayed with a hand spray. Was done.

Examples 25 to 26: Application to window glass to which dirt caused by a silicone sealing material has adhered. After masking the area around the application surface of the window installed below the silicone sealant facing the north side to prevent the paint from scattering around the area, sodium alkylbenzene sulfonate and fatty acid alkanolamide are used as surfactants. Aqueous detergent (pH 9.
The window was wiped with a cloth impregnated with 5) to remove colored stains. Next, after washing with tap water, the window is wiped with a rag impregnated with water to remove the cleaning agent, and further wiped.
Then, water adhering to the window was removed with a dry waste cloth. Thereafter, a primer was applied to the surface of the base material and cured.
Next, a photocatalyst coating solution STK01 manufactured by Ishihara Sangyo Co., Ltd.
(A composition comprising 8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of nitric acid aqueous solution, 28 parts by weight of methanol and 7.2 parts by weight of propanol) and a photocatalyst core manufactured by Ishihara Sangyo Liquid STK03 (5 parts by weight of titanium oxide particles, 5 parts by weight of alkyl silicate and aqueous solution of nitric acid 5)
A composition comprising 4.8 parts by weight, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) was mixed at a ratio of 1: 1 to obtain a photocatalyst core obtained by diluting 25-fold with 2-propanol. -Plating liquid A is applied to the surface of the window glass which has been subjected to the above-mentioned cleaning treatment by φ.
105 g / m ² spray using a 0.8 mm air gun
After coating by a coating method, the coating film was cured by drying at 20 ° C. for 20 minutes to obtain a # 30 sample.
Next, the contact angle with water was examined for the # 30 sample. As a result, the contact angle with water was superhydrophilized to 0 °.

Embodiment 26 FIG. Silicone facing north
A water-based cleaning agent to which sodium alkylbenzenesulfonate and fatty acid alkanolamide are added as surfactants after masking the area around the application surface of the window installed at the bottom of the runt to prevent the paint from scattering around the area. The window was wiped with a rag impregnated with (pH 9.5) to remove colored stains. Next, after washing with tap water, the window was wiped with a rag impregnated with water to remove the cleaning agent, and furthermore, moisture adhering to the window was removed with a wiper and a dry rag. Thereafter, the surface of the substrate was irradiated with a 500 W mercury lamp. Next, photocatalyst coating liquid STK manufactured by Ishihara Sangyo
01 (8 parts by weight of titanium oxide particles and alkyl silicate 2
Parts by weight, 54.8 parts by weight of a nitric acid aqueous solution, 28 parts by weight of methanol, and 7.2 parts by weight of propanol) and a photocatalyst coating liquid STK03 manufactured by Ishihara Sangyo (5 parts by weight of titanium oxide particles and alkyl silicate). -5 parts by weight, 54.8 parts by weight of a nitric acid aqueous solution, 28 parts by weight of methanol and propanol-
Of a photocatalyst coating liquid A obtained by diluting a liquid obtained by mixing a 1: 1 mixture of the above-mentioned composition with 7.2 parts by weight with 2-propanol and subjecting the same to the above-mentioned cleaning treatment. To φ
105 g / m ² spray using a 0.8 mm air gun
After coating by a coating method, the coating film was cured by drying at 20 ° C. for 20 minutes to obtain a # 31 sample.
Next, the contact angle with water was examined for the # 31 sample. As a result, the contact angle with water was superhydrophilized to 0 °.

[0066]

According to the present invention, the transparency, design and hydrophilicity of the surface of the photocatalytic hydrophilic film formed thereon may be impaired due to the effect of dirt adhering to the substrate surface. No longer occurs.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification code FI B32B 33/00 B32B 33/00 C09D 1/00 C09D 1/00 5/00 5/00 Z // B01J 35/02 B01J 35 / 02 J Examiner Yoshitsune Murayama (56) References JP-A-9-78462 (JP, A) JP-A-9-227832 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B05D 1/00-7/26 B32B 27/00 B32B 33/00 C09D 1/00 C09D 5/00 B01J 35/02

Claims (12)

(57) [Claims] 1. a step of cleaning a surface of a substrate with a cleaning liquid containing at least one selected from the group consisting of a surfactant, an abrasive, an acid, a base, and a solvent; and removing the cleaning liquid. Average composition formula SiX _q O _{(4-q) / 2} (where X is an alkoxy group or a halogen atom, and q is 0 <q <4
A film-forming element comprising a silicate represented by the formula (a), which forms an amorphous silica film when cured: (b) dispersed in the film-forming element, Applying a photocatalytic hydrophilic coating solution containing photocatalytic oxide particles for hydrophilizing the surface of the coating, and curing the coating. 2. a step of cleaning the surface of the base material with a cleaning liquid containing at least one selected from the group consisting of a surfactant, an abrasive, an acid, a base and a solvent; and (a) removing the cleaning liquid. in the average composition formula _{R p SiX q O (4-} q) / 2 ( wherein, R is one or functional groups of two or more of the monovalent organic group, X is an alkoxy group or a halogen atom, Yes,
(p and q are numbers satisfying 0 <p <2, 0 <q <4), which is a film-forming element made of siloxane, which forms a silicone resin film when cured. b) the organic groups dispersed in the film-forming element and bound to the silicon atoms in the silicone molecules on the surface of the coating by photoexcitation are at least partially replaced by hydroxyl groups by photocatalysis, and Coating and curing a photocatalytic hydrophilic coating solution containing photocatalytic oxide particles for hydrophilizing the surface, and a photocatalytic hydrophilic film. 3. A method for forming a photocatalytic hydrophilic film on a surface of a substrate to which dirt caused by a silicone sealing material has adhered, the method comprising: applying a surfactant, an abrasive, an acid, At least one selected from the group consisting of a base and a solvent
A step of removing colored stain components by washing with a washing liquid containing seeds; a step of coating the remaining silicone with a primer; (a) an average composition formula SiX _q O _{(4-q) / 2} (where X is An alkoxy group or a halogen atom, and q is 0 <q <4
A film-forming element comprising a silicate represented by the formula (a), which forms an amorphous silica film when cured: (b) dispersed in the film-forming element, Applying a photocatalytic hydrophilic coating solution containing photocatalytic oxide particles for hydrophilizing the surface of the coating, and curing the coating. 4. A method for forming a photocatalytic hydrophilic film on a surface of a substrate to which dirt caused by a silicone sealing material has adhered, wherein the method comprises the steps of: At least one selected from the group consisting of a base and a solvent
Removing the dirt component colored and washed with a washing solution containing seeds, during the process of coating the primer on the remaining silicones, (a) the average composition formula _{R p SiX q O (4-} q) / 2 ( wherein, R is a functional group composed of one or more monovalent organic groups, X is an alkoxy group or a halogen atom,
(p and q are numbers satisfying 0 <p <2, 0 <q <4), which is a film-forming element made of siloxane, which forms a silicone resin film when cured. b) the organic groups dispersed in the film-forming element and bound to the silicon atoms in the silicone molecules on the surface of the coating by photoexcitation are at least partially replaced by hydroxyl groups by photocatalysis, and Coating and curing a photocatalytic hydrophilic coating solution containing photocatalytic oxide particles for hydrophilizing the surface, and a photocatalytic hydrophilic film. 5. A method for forming a photocatalytic hydrophilic film on a surface of a substrate to which dirt caused by a silicone sealing material has adhered, the method comprising: applying a surfactant, an abrasive, an acid, At least one selected from the group consisting of a base and a solvent
A step of removing colored stain components by washing with a washing liquid containing seeds; a step of irradiating the residual silicone surface with ultraviolet rays; (a) an average composition formula SiX _q O _{(4-q) / 2} (where X is An alkoxy group or a halogen atom, and q is 0 <q <4
A film-forming element comprising a silicate represented by the formula (a), which forms an amorphous silica film when cured: (b) dispersed in the film-forming element, Applying a photocatalytic hydrophilic coating solution containing photocatalytic oxide particles for hydrophilizing the surface of the coating, and curing the coating. 6. A method for forming a photocatalytic hydrophilic film on a surface of a substrate to which dirt caused by a silicone sealing material has adhered, the method comprising: applying a surfactant, an abrasive, an acid, At least one selected from the group consisting of a base and a solvent
A step of removing colored stain components by washing with a washing liquid containing seeds; a step of irradiating the residual silicone surface with ultraviolet rays; (a) an average composition formula R _p SiX _q O _{(4-q) / 2} ( R is a functional group consisting of one or more monovalent organic groups, X is an alkoxy group or a halogen atom,
(p and q are numbers satisfying 0 <p <2, 0 <q <4), which is a film-forming element made of siloxane, which forms a silicone resin film when cured. b) the organic groups dispersed in the film-forming element and bound to the silicon atoms in the silicone molecules on the surface of the coating by photoexcitation are at least partially replaced by hydroxyl groups by photocatalysis, and Coating and curing a photocatalytic hydrophilic coating solution containing photocatalytic oxide particles for hydrophilizing the surface, and a photocatalytic hydrophilic film. 7. The cleaning liquid according to claim 1, wherein the cleaning liquid contains at least an abrasive.
7. The method for forming a photocatalytic hydrophilic film according to any one of claims 1 to 6. 8. The method for forming a photocatalytic hydrophilic film according to claim 7, wherein the abrasive has an average particle diameter of 10 μm or less. 9. The photocatalytic hydrophilic solution according to claim 1, wherein the cleaning solution contains at least one selected from the group consisting of a surfactant, an acid, a base, and a solvent. Method of forming a functional film. 10. The cleaning liquid according to claim 1, wherein the cleaning liquid contains a nonionic surfactant.
9. The method for forming a photocatalytic hydrophilic film according to any one of claims 8 to 8. 11. The method for forming a photocatalytic hydrophilic film according to claim 1, wherein the detergent always contains a base so as to have a pH of at least 10. 12. The cleaning agent according to claim 1, further comprising at least one selected from the group consisting of hydrogen fluoride, ammonium acid fluoride and sodium acid fluoride. The method for forming a photocatalytic hydrophilic coating according to the above.