Untitled record

Description: TECHNICAL FIELD [Detailed description of the invention]

Technical field: The present invention relates to a structure carrying a photocatalyst used for antifouling, water purification, deodorization, sterilization, wastewater treatment, water decomposition, suppression of algae growth, various chemical reactions, and the like. Background technology: Titanium oxide, an n-type semiconductor, is known as a photocatalyst that promotes various chemical reactions such as water decomposition, deodorization, sterilization, water purification, and wastewater treatment by the energy of ultraviolet rays. Although it is generally said that the photocatalyst is used in the form of powder or suspended in a solution, the catalytic activity is generally higher, but practically, it must be used in the form of being supported on some carrier. There are many. In order to effectively utilize the energy of ultraviolet rays, which is light, it is advantageous that the shape of the carrier is a paper shape or a sheet shape that can take a wide irradiation area of light, and a chemical reaction occurs by a photocatalyst. In order to increase the contact area with the reactant to be formed, it is preferable that the surface thereof has a porous structure. Various carrier materials for supporting a photocatalyst have been proposed. For example, (A) light-transmitting substances such as nitrocellulose, glass, polyvinyl chloride, plastic, nylon, methacrylic resin, polypropylene (Japanese Patent Laid-Open No. 62-66861), (Japanese Patent Laid-Open No. 62-66861), B) Polypropylene fiber, ceramic (Japanese Patent Laid-Open No. 2-68190), (C) glass, ceramic, nylon, acrylic, polyester (Japanese Patent Laid-Open No. 5-309267) and the like. However, among these materials, those mainly composed of organic substances have been reported to decompose or deteriorate due to their catalytic action when a photocatalyst is supported, and there is a problem in durability (Otani Bunsho). , Polymer Processing Vol. 42, No. 5, P18 (1993), Manabu Kiyono, "Titanium Oxide" Gihodo, P165). Further, even when the carrier material is an inorganic substance such as glass or ceramic, if an organic polymer resin is used as an adhesive to support the photocatalyst, the surface of the photocatalyst particles is covered with the resin and the catalytic activity is lowered. Not only that, the resin is decomposed and deteriorated by the photocatalytic action, and the photocatalyst is peeled off, which causes a problem in durability. Therefore, when the carrier material is a heat-resistant inorganic substance, the sputtering method (Japanese Patent Laid-Open No. 60-044053) in which no organic substance remains, the coating method of organic titanate-firing method (Japanese Patent Laid-Open No. 60-118236), and the spraying of titania sol- A method such as a firing method (Japanese Patent Laid-Open No. 5-253544) is adopted. However, these methods require firing at a high temperature in order to generate and crystallize photocatalytic particles on the carrier and have adhesiveness to the carrier, and not only are it difficult to support a large area, but also. There was a problem that the manufacturing cost was very high. On the other hand, in order to support the photocatalyst on the glass fiber paper, a method using a metal oxide sol as an adhesive (Japanese Patent Laid-Open No. 5-309267) has been proposed. However, the adhesive strength of metal oxide sol such as silica sol is very weak because it is due to the van der Waals force (Fine Ceramics Vol. 1, p216 ~ 223 1980), and the adhesiveness and durability are insufficient. In addition, it is not applicable to all carriers including general-purpose resins that easily cause thermal decomposition because it requires baking treatment at a high temperature. In addition, in the case where the photocatalyst powder is supported on a metal oxide gel such as silica or clay mineral, there is a report that the photocatalytic decomposition reaction of propionaldehyde gas is promoted by the effect of the carrier as an adsorbent (Symposium "Photocatalyst". Recent Developments of Reactions, Proceedings, 1994, Photofunctional Materials Study Group, 2-11, p.39). However, there have been no reports that a carrier having excellent adhesiveness and durability was obtained while maintaining high catalytic activity of a photocatalyst uniformly dispersed in such a metal oxide gel. Further, a method of immobilizing the photocatalyst with a fluororesin has also been proposed (Japanese Patent Laid-Open No. 6-315614). However, not only is the fluororesin expensive, but in order to firmly bond the photocatalyst particles, it is necessary to cover most of the surface of the catalyst particles with the fluororesin, and as a result, the catalytic activity is lower than that of the powder. There was a problem of doing it. There is an example (EP-0633064) in which a photocatalyst is mixed with a persistent binder such as fluororesin or polyorganosiloxane and supported on a substrate, but there are practical problems such as adhesiveness and long-term durability. It is not enough to solve. As described above, the problems that must be solved in order to support the photocatalyst on the carrier are 1) good adhesion between the photocatalyst and the carrier, and 2) the photocatalytic activity is supported on the carrier. 3) The carrier and adhesive are not deteriorated by the supported photocatalyst, and the strength is maintained for a long period of time, and the durability and catalytic activity are maintained. Further, when it is used in a high temperature and high humidity environment, it is required to have excellent adhesion after being immersed in boiling water, for example. Further, as a characteristic required for a photocatalyst coating agent for supporting a photocatalyst on a carrier, a photocatalyst coating liquid that does not increase viscosity or settle particles even after storage for at least 1 month, preferably 3 months or more is required. It is also necessary to support a practical product without deteriorating the photocatalytic action when the photocatalyst is coated. The present inventors provide a specific adhesive layer between the photocatalyst layer and the carrier, protect the underlying carrier from deterioration due to the photocatalytic action, firmly adhere the photocatalytic layer to the carrier, and the adhesive layer itself. For the first time, it was found that the photocatalyst can be firmly adhered to the carrier by making it less susceptible to deterioration due to the photocatalytic action, and the above-mentioned problems have been solved. Disclosure of invention: The present inventors use an acrylic-silicon resin having a silicon content of 2 to 60% by weight, a silicon-modified resin such as an epoxy-silicon resin, a resin containing 5 to 40% by weight of colloidal silica, or a general formula as the material of the adhesive layer. (1) SiCln₁(OH) n₂R¹n₃(OR²) n₄ (1) [In the formula, R¹Is an alkyl group with 1 to 8 carbon atoms (which may be substituted with an amino group, a carboxyl group, or a chlorine atom), R.²Represents an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms substituted with an alkoxy group, and n₁Represents an integer from 0 to 2, n₂And n₃Represents an integer from 0 to 3, respectively, n₄Represents an integer from 2 to 4, and n₁+ n₂+ n₃+ n₄A resin containing 3 to 60% by weight of polysiloxane, which is a polycondensation reaction product of the compound represented by [= 4], is suitable for firmly adhering the photocatalyst and protecting the carrier from the photocatalyst. We have found and completed the present invention. Furthermore, the present inventors have solved the above-mentioned problems required for the photocatalytic coating agent by using the general formula (2). SiR³n₅(OR⁴)₄-n₅ (2) [However, in the formula, R³Represents an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a chlorine atom, or a carboxyl group), and R⁴Represents an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms substituted with an alkoxy group, and n₅Represents any number of 0,1,2,3. ], 0.001 to 5% by weight of one or more of the alkoxysilanes or their hydrolysis products, and 0.1 to 30% by weight of the metal oxide and / or hydroxide sol as a solid form. The present invention has been completed by finding that a photocatalyst coating solution containing 0.1 to 30% by weight of% and a photocatalyst powder and / or sol as a solid form is stable for a long period of time and does not increase viscosity or settle particles. Further, the present inventors can support the photocatalyst-supporting structure and the photocatalyst coating agent on carrier materials such as glass, plastic, metal, cloth, and wood materials, and can be used on lenses, adhesive films, blinds, non-woven fabrics, wood doors, and the like. Also found that it is possible to apply with the photocatalytic coating agent according to the present invention. Hereinafter, the present invention will be described in detail. In the present invention, the resin used for the adhesive layer of the photocatalyst-supporting structure contains 5 to 40% by weight of an acrylic-silicon resin having a silicon content of 2 to 60% by weight, a silicon-modified resin such as an epoxy-silicon resin, and colloidal silica. It is selected from a resin to be used and a resin containing 3 to 60% by weight of polysiloxane. Silicon-modified resins such as acrylic-silicon resins with a silicon content of less than 2% by weight, resins with a polysiloxane content of less than 2% by weight, and resins with a colloidal silica content of less than 5% by weight have poor adhesion to the photocatalyst layer. In addition, the adhesive layer is deteriorated by the photocatalyst, and the photocatalyst layer is easily peeled off. On the other hand, in a silicon-modified resin such as an acrylic-silicon resin having a silicon content of more than 60% by weight, the adhesion between the adhesive layer and the carrier is poor, and the hardness of the adhesive layer is small, so that the abrasion resistance is poor. Further, in the case of a resin having a polysiloxane content of more than 60% by weight or a resin having a colloidal silica content of more than 40% by weight, the adhesive layer becomes porous, the underlying carrier is deteriorated by the photocatalyst, and the adhesive adheres to the carrier. Adhesion between the layers is poor, and both photocatalysts are easier to peel off than carriers. When the adhesive layer resin is a silicon-modified resin such as acrylic-silicon resin or epoxy-silicon resin, the methods for introducing silicon into the resin are ester exchange reaction, graft reaction using silicon macromer and reactive silicon monomer, and hydrosilylation reaction. , Block copolymerization method and the like, but in the present invention, any method can be used. Acrylic resins and epoxy resins are the most excellent resins into which silicone is introduced in terms of film formation, toughness, and adhesion to carriers, but alkyd resins, urethane resins, polyester resins, and the like are also available. Can be used. These resins can be used in either solvent-soluble or emulsion types. Further, there is no problem even if an additive such as a cross-linking agent is contained. When the adhesive layer resin contains polysiloxane, and the polysiloxane is a hydrolyzate of silicon alkoxide having an alkoxy group having 1 to 5 carbon atoms or a product from the hydrolyzate, the adhesiveness and durability are improved. A more improved carrying structure can be obtained. When the alkoxy group of the silicon alkoxide has 6 or more carbon atoms, it is expensive and the hydrolysis rate is very slow, so that it becomes difficult to cure in the resin, and the adhesiveness and durability deteriorate. It is possible to use a polysiloxane obtained by hydrolyzing a silicon alkoxide that partially contains chlorine, but if a polysiloxane containing a large amount of chlorine is used, the carrier may be corroded by the chlorine ions of impurities, or the adhesiveness may be improved. Make it worse. As a method of introducing polysiloxane into a resin, a method of mixing a silicon alkoxide monomer with a resin solution and hydrolyzing it with water in the air at the time of forming an adhesive layer, or a method of partially hydrolyzing silicon alkoxide in advance with a resin is used. There are various methods such as mixing and further hydrolyzing with water in the air when forming the protective film, but any method can be used as long as it can be uniformly mixed with the resin. Further, in order to change the hydrolysis rate of the silicon alkoxide, a small amount of acid or base catalyst may be added. As the resin into which polysiloxane is introduced, acrylic resin, acrylic-silicon resin, epoxy-silicon resin, silicon-modified resin, urethane resin, epoxy resin, polyester resin, alkyd resin and the like can be used, but acrylic-silicon resin and epoxy can be used. -Silicon modified resins, including silicone resins, are the best in terms of durability. When the adhesive layer is a resin containing colloidal silica, the particle size of the colloidal silica is preferably 10 nm or less. At 10 nm or more, not only the resin in the adhesive layer is easily deteriorated by the photocatalyst, but also the adhesion between the photocatalyst layer and the adhesive layer is deteriorated. The simplest method for introducing this colloidal silica into the resin is to mix the resin solution and the colloidal silica solution, then apply and dry to form an adhesive layer. However, the resin is introduced in a state where the colloidal silica is dispersed. A polymerized and synthesized product may be applied, dried and used. Further, in order to improve the adhesiveness and dispersibility between the colloidal silica and the resin, the colloidal silica can be treated with a silane coupling agent before use. Examples of the resin into which colloidal silica is introduced include acrylic resin, acrylic-silicon resin, epoxy-silicon resin, silicon-modified resin, urethane resin, epoxy resin, polyester resin, and alkyd resin. Silicon-modified resins, including resins and epoxy-silicon resins, are the most durable. The colloidal silica can be any material, whether it is a silica sol made by cation exchange of a sodium silicate solution or a silica sol made by hydrolyzing silicon alkoxide. Further, for the purpose of suppressing deterioration due to photocatalytic action in the adhesive layer resin, light stabilizersAndcan improve the durability by mixing beauty / or UV absorbers. As the light stabilizer that can be used, a hindered amine type is preferable, but other light stabilizers can also be used. As the ultraviolet absorber, a triazole type or the like can be used. The amount added is 0.005 wt% or more and 10 wt% or less, preferably 0.01 wt% or more and 5 wt% or less with respect to the resin. If the surface of the adhesive layer is treated with a silane-based or titanium-based coupling agent, the adhesiveness with the photocatalyst layer may be improved. As a method of supporting the adhesive layer on the carrier, a method of coating the resin solution by a printing method, a sheet molding method, a spray spraying method, a dip coating method, a spin coating method or the like and drying can be used. The drying temperature varies depending on the type of solvent and resin, but is generally preferably 150 ° C. or lower. If the thickness of the adhesive layer is 0.1 μm or more, the photocatalyst layer can be firmly adhered to form a highly durable photocatalyst-supported structure. In the case of a coating method such as a gravure printing method in which the adhesive layer needs to be dried and cured in a short time, a curing agent such as silicon is applied to the solid content of the adhesive layer by 0.1 to 10 depending on the required curing speed. It is also preferably added in% by weight. The metal oxide gel or hydroxide gel in the photocatalyst layer has the effect of adhering the photocatalyst powder and firmly adhering it to the adhesive layer. It has excellent long-term durability and weather resistance. Since this metal oxide gel or hydroxide gel is porous, it has adsorptive properties and also has the effect of increasing photocatalytic activity. The content of the metal oxide gel or the metal hydroxide gel in the photocatalyst layer is preferably 25 to 95% by weight. If it is less than 25% by weight, the adhesion to the adhesive layer is insufficient, and if it exceeds 95% by weight, the photocatalytic activity is insufficient. The specific surface area of the metal oxide gel or metal hydroxide gel is preferably 150 ° C and 50 m after drying.²/ G or more, more preferably 100m²When it is more than / g, the adhesiveness becomes stronger and the catalytic activity also improves. As the metal component, oxide gels or hydroxide gels of metals such as silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten and tin can be preferably exemplified. In addition, by using an oxide or hydroxide gel containing two or more metals selected from silicon, aluminum, titanium, zirconium, and niobium as the metal component, the photocatalyst after immersion in boiling water is used. It is possible to increase the adhesiveness of the layer. Examples of combinations of metal components with excellent boiling water resistance are silicon-aluminum, silicon-titanium, silicon, zirconium, silicon-niobium, aluminum-titanium, aluminum-zirconium, aluminum-niobium, aluminum-tantalam, and titanium-zirconium. , Titanium-Niobium, Titanium-Tantalam, Silicon-Aluminum-Zirconium, Silicon-Aluminum-Titanium, etc., more preferably Silicon-Aluminum, Silicon-Titanium, Silicon-Zirconium, Silicon-Titanium-Aluminum, Silicon-Aluminum- Examples thereof include oxide gels such as zirconium and hydroxide gels. The specific surface area of these oxide gels or hydroxide gels is 50 m.²When it is / g or more, the adhesiveness is high, the catalytic activity is improved, and the adhesiveness is excellent even after being immersed in boiling water. Further, in actual use, a gel obtained by mixing and drying a sol for forming a gel, or a composite oxide gel prepared by a method such as a coprecipitation method may be used. For compounding with the photocatalyst, it is desirable to uniformly mix in the state of the sol before forming a gel, or to mix at the stage of the raw material before preparing the sol. Methods for preparing the gel include a method of hydrolyzing a metal salt, a method of neutralizing and decomposing, a method of ion exchange, a method of hydrolyzing a metal alkoxide, and the like. The photocatalyst powder is uniformly dispersed in the gel. Any method can be used as long as it can be obtained in a state of being. However, the presence of a large amount of impurities in the gel adversely affects the adhesiveness and catalytic activity of the photocatalyst, so a gel having few impurities is preferable. Also, by adding 10 to 50% by weight of a silicon-modified resin or silane coupling agent in the photocatalyst layer, JIS is used after immersing in boiling water for 15 minutes while maintaining high catalytic activity. An excellent adhesiveness with an evaluation score of 6 points or more can be obtained in the adhesiveness test by the grid tape method specified in K5400. The silicon-modified resin or silane coupling agent added to the photocatalyst layer has the effect of enhancing the adhesion of the photocatalyst layer in boiling water. As the silicon-modified resin, commercially available silicon-acrylic or silicon-epoxy type resins can be used, and either those dissolved in a solvent or those dispersed in water as an emulsion can be used. is there. As a silane coupling agent, the general formula: RSi (Y)₃And (R)₂Si (Y)₂(However, R indicates an organic functional group, Y indicates a chlorine atom or an alkoxy group.), Etc. can be used. In the above general formula, R is a methyl group, an ethyl group, a vinyl group, a γ-glycidoxypropyl group, a γ-methacryloxypropyl group, a γ- (2-aminoethyl) aminopropyl group, or a γ-chloropropyl group. , Γ-Mercaptopropyl group, γ-aminopropyl group, γ-acryloxypropyl group, etc. Y is C such as methoxy group, ethoxy group, β-methoxyethoxy group, β-ethoxyethoxy group in addition to chlorine atom.₁~ C₅Any of the alkoxy groups of the above can be used. It is desirable that the amount of the silicon-modified resin or the silane coupling agent added is 10 to 50% by weight in the photocatalyst layer as a solid content. If it is less than 10% by weight, the adhesiveness after the boiling water test is lowered, and if it is added in a larger amount than 50% by weight, the photocatalytic activity is significantly lowered. As a method of adding the silicon-modified resin or the silane coupling agent into the photocatalyst layer, a method of adding the silicon-modified resin or the silane coupling agent into the liquid of the photocatalyst powder or the sol, or a metal oxide for forming a metal oxide gel to be added together with the photocatalyst, or Various methods such as a method of adding the hydroxide into the sol solution are possible. It is particularly desirable to add an emulsion-type silicone-modified resin to the above-mentioned sol solution because the adhesiveness of the photocatalyst layer in boiling water can be significantly enhanced without substantially reducing the photocatalytic activity. In addition, additives such as a cross-linking agent can be included in the silicon modified resin or the silane coupling agent. Any photocatalyst used in the present invention can be used, such as powder, sol, and solution, as long as it adheres to the adhesive layer and exhibits photocatalytic activity when dried at the drying temperature of the photocatalyst layer. When a sol-shaped photocatalyst is used, if a particle size of 20 nm or less, preferably 10 nm or less is used, the transparency of the photocatalyst layer is improved and the linear transmittance is increased, so that a glass substrate requiring transparency is required. It is particularly preferable when it is applied to a plastic molded body or a plastic molded body. Further, when such a transparent photocatalyst layer is applied to a carrier on which a color or pattern is printed, the color or pattern of the base is not impaired. As a photocatalyst in the photocatalyst layer, TiO₂, ZnO, SrTiO₃, CdS, GaP, InP, GaAs, BaTiO₃, KNbO₃, Fe₂O₃, Ta₂O₅, WO₃, SnO₂, Bi₂O₃, NiO, Cu₂O, SiC, SiO₂, MoS₂, InPb, RuO₂, CeO₂And so on, and to these photocatalysts, Pt, Rh, RuO₂, Nb, Cu, Sn, Ni, Fe and other metals and those to which oxides of those metals are added can be used. In addition, Pt, Rh, RhO can be applied to these photocatalysts by utilizing the photocatalytic reducing action.₂, Nb, Cu, Sn, Ni, Fe and other metals added can also be used. As for the content of the photocatalyst in the photocatalyst layer, the larger the amount, the higher the catalytic activity, but from the viewpoint of adhesiveness, it is preferably 75% by weight or less. The photocatalyst coating liquid according to the present invention contains 0.001% to 5% by weight of a silicon compound, 0.1 to 30% by weight of a sol of a metal oxide and / or hydroxide as a solid form, and a powder and / or sol of a photocatalyst. It is characterized by containing 0.1 to 30% by weight as a solid form. The silicon compound added to the coating liquid of the photocatalyst layer of the present invention includes the general formula (2). SiR³n₅(OR⁴)₄-n₅ Equation (2) [However, in the formula, R³Represents an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a chlorine atom, or a carboxyl group), and R⁴Represents an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms substituted with an alkoxy group, and n₅Represents any number of 0,1,2,3. ], One or a mixture of one or more of the alkoxysilanes or their hydrolysis products can be used. In general formula (2), R³Methyl group, ethyl group, vinyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ- (2-aminoethyl) aminopropyl group, γ-chloropropyl group, γ-mercaptopropyl group. , Γ-Aminopropyl group, γ-Acryloxypropyl group, etc., -OR⁴Cs include methoxy group, ethoxy group, n-propoxy group, i-provoxy group, n-ptoxy group, β-memethoxyethoxy group, β-ethoxyethoxy group, 2-ethylhexyloxy group and the like.₁~ C₈Alkoxy group of is desirable. Examples of the silicon compound represented by the general formula (2) are tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and one or a mixture of two or more of their hydrolysis products. Can be preferably mentioned. By adding a small amount of the above silicon compound to the coating liquid of the photocatalyst layer, a stable photocatalyst coating liquid with less increase in viscosity and less particle settling can be obtained even after long-term storage. The amount of the silicon compound added is preferably 0.001 to 5% by weight as a solid content in the coating liquid of the photocatalyst layer. If it is less than 0.001% by weight, the stability of the photocatalyst layer coating liquid during long-term storage is lowered, and if it is added in an amount larger than 5% by weight, the photocatalytic activity is significantly lowered. As a method of adding the silicon compound to the coating liquid of the photocatalyst layer, a method of adding the silicon compound to the liquid of the photocatalyst powder or the sol, or a method of adding the silicon compound to the liquid of the sol of the metal oxide and / or hydroxide added together with the photocatalyst. Various methods such as a method are possible. Further, a partially hydrolyzed silicon compound may be added. Since the silicon compound added to the coating liquid of the photocatalyst layer also has the effect of enhancing the adhesion of the photocatalyst layer in boiling water, the amount of the silicon compound added should be increased when the above-mentioned silane coupling agent or the like is added. It is possible to reduce it. The metal oxide and / or hydroxide sol added to the coating liquid of the photocatalyst layer is 0.1 to 30% by weight with respect to the coating liquid as a solid content, and the photocatalyst powder and / or sol is a solid content. It is desirable to add 0.1 to 30% by weight, respectively, to the coating solution. The metal oxide and / or hydroxide sol has a poor function of adhering the photocatalyst to the substrate when added in an amount of 0.1% by weight or less, and the photocatalyst powder and / or sol added at the same time when added in an amount of 30% by weight or more. The amount is reduced and the photocatalytic activity is reduced. Further, when the amount of the photocatalyst powder and / or sol added is 0.1% by weight or less, the photocatalytic activity is low, and when the amount of the photocatalyst powder and / or sol is 30% by weight or more, the amount of the metal oxide and / or hydroxide sol for adhering to the substrate is small. Therefore, it becomes easy to peel off. Since the photocatalyst coating liquid of the present invention provides an adhesive layer between the photocatalyst layer and the carrier, the coating liquid of the adhesive layer to be applied on the carrier can also be used in combination. As the coating liquid for the adhesive layer, a silicon-modified resin having a silicon content of 2 to 60% by weight, a resin containing 3 to 60% by weight of polysiloxane, or a resin containing 5 to 40% by weight of colloidal silica is used as the resin solid content 1. A solution containing ~ 50% by weight can be used. As the resin used for the coating liquid of the adhesive layer, it is preferable to use the above-mentioned resin that can be used for the adhesive layer alone or in combination, and the resin solid content is 1 to 50% by weight as an organic solvent solution or an aqueous emulsion. It is desirable to use the coating solution of. With a coating liquid having a resin solid content of 1% or less, the adhesive layer becomes too thin and it becomes difficult to bond the photocatalyst layer, and with a coating liquid having a resin solid content of 50% by weight or more, the adhesive layer becomes too thick, which is good. Not only does it not result in a good coating film, but it also becomes too viscous and difficult to handle. In order to form the photocatalyst layer on the adhesive layer, a suspension in which the photocatalyst is dispersed in a metal oxide sol or a metal hydroxide sol solution can be coated by a coating method similar to that for forming the adhesive layer. .. The photocatalyst may be dispersed in the state of a metal oxide sol or a precursor solution of a metal hydroxide sol, and hydrolyzed or neutralized and decomposed at the time of coating to form a sol or gel. When a sol is used, an acid or alkaline gelatinizing agent or the like may be added for stabilization. Further, it is also possible to add 5% by weight or less of a surfactant, a silane coupling agent, or the like to the photocatalyst in the sol suspension to improve the adhesiveness and operability. The drying temperature at the time of forming the photocatalyst layer varies depending on the carrier material and the resin material in the adhesive layer, but is preferably 50 ° C or higher and 200 ° C or lower. The thicker the photocatalyst layer, the higher the activity, but when it is 5 μm or more, there is almost no change. Even if it is 5 μm or less, it exhibits high catalytic activity and also exhibits translucency, and the catalyst layer becomes inconspicuous, which is preferable. However, if the thickness is less than 0.1 μm, the translucency is improved, but the ultraviolet rays used by the photocatalyst are also transmitted, so that high activity cannot be expected. The thickness of the photocatalyst layer is 0.1 μm or more and 5 μm or less, and the photocatalyst particles with a crystal particle size of 40 nm or less and the specific surface area of 100 m.²When a metal oxide gel or metal hydroxide gel of / g or more is used, the total light transmittance of the photocatalyst layer and the adhesive layer at a wavelength of 550 nm becomes 70% or more. The structure supported so that the total light transmittance at a wavelength of 550 nm is 70% or more can use the transmitted visible light as illumination when the carrier is transparent, and even when the carrier is opaque, it is on the carrier. Since the pattern is not damaged, it is also useful in terms of decorativeness. A structure provided with the adhesive layer and a photocatalyst layer can be obtained regardless of the shape of the carrier, such as a film shape, a plate shape, a tubular shape, a fibrous shape, or a net shape. Further, if the size is 10 μm or more, it can be firmly supported. As a carrier material, a structure provided with this adhesive layer and a photocatalyst layer can be obtained even for an organic polymer that cannot be heated when supported or a metal that is easily oxidatively corroded by heat or water. Shows durability. In order to improve the adhesion between the carrier and the adhesive layer, a carrier whose surface has been subjected to discharge treatment, primer treatment, or the like may be used. As shown in Examples, the structure supporting the photocatalyst shown in the present invention includes architectural paints, wallpaper, windowpanes, blinds, curtains, carpets, lighting fixtures, lighting lamps, black lights, ship bottom / fishing net antifouling paints, etc. It can be used as a filler for water treatment, agricultural bifilm, weed control sheet, packaging material, etc. It is also possible to use a photocatalyst carrier that can be used even in a high temperature and high humidity environment. In the structure according to the present invention provided with the adhesive layer and the photocatalyst layer, the ultraviolet intensity is 3 mW / cm.²Even after irradiating with the black light of No. 4 for 500 hours at a temperature of 40 ° C and a relative humidity of 90%, the adhesiveness of JIL K5400 by the grid tape method maintains a high durability of 6 points or more. You can also make things that show sex. In addition, in the accelerated weather resistance test using the sunshine weather meter, even after 500 hours of the test time, there are some products that show excellent weather resistance such that the adhesion by the grid tape method of JIL K5400 maintains an evaluation score of 6 points or more. Has been obtained. Furthermore, after immersing in boiling water with a conductivity of 200 μS / cm at 20 ° C for 15 minutes, the adhesiveness by the grid tape method specified in JIL K5400 shows high boiling water resistance with an evaluation score of 6 points or more. Since a product can be obtained and the photocatalytic activity is high in any of the samples, the characteristics can be sufficient for the above-mentioned various uses. As the shape of the glass that can be used as a carrier, any complicated shape such as a plate shape, a tubular shape, a spherical shape, and a fibrous shape can be obtained, and the glass provided with the adhesive layer and the photocatalyst layer can be obtained. Moreover, if the size is 10 μm or more, it can be firmly supported. Further, depending on the application such as a window glass, a showcase, and eyeglasses that have already been constructed, the processed glass can be treated to obtain the photocatalyst-supporting glass of the present invention. The glass carrying the photocatalyst shown in the present invention includes window glass, instrument cover glass, lighting equipment, lighting lamps, black lights, water treatment fillers, cameras, spectacle lenses, etc., antibacterial, deodorant, antifouling, etc. It can be used in all situations that require the effect of. The plastic molded body carrying the photocatalyst shown in the present invention requires antibacterial, deodorizing, antifouling and other effects such as wallpaper, interior boards, furniture, electrical equipment, vehicle parts, cameras, eyeglass lenses, etc. It can be used in many situations. The shape of the plastic molded body may be any complicated shape such as a film shape, a plate shape, a tubular shape, a spherical shape, a fibrous shape, or the like, and a plastic molded body provided with the adhesive layer and a photocatalyst layer can be obtained. Moreover, if the size is 10 μm or more, it can be firmly supported. In addition, depending on the application such as construction materials, household appliances, and eyeglasses that have already been constructed, it is possible to obtain the photocatalyst-supported plastic molded product of the present invention by processing it into a processed plastic molded product, so its application range is extremely wide. It can be said that it is wide. The fabric used in the present invention includes natural fibers such as hair, silk, cotton and linen, recycled fibers such as rayon and acetate, synthetic fibers such as nylon, acrylic, polyamide, polyester, polyacrylonitrile and polyvinyl chloride, and aramid. As a carrier, a woven fabric, a knitted fabric, a non-woven fabric, etc. made of the heat-resistant fiber of In addition, fabrics treated with water repellents such as silicon-based water repellents, fluorine water repellents such as perfluoroalkyl acrylate, zirconium salt water repellents, and ethylene urea water repellents, and durability as required. Water-repellent fabrics that use ethyleneimine-based, epoxy-based, melamine-based cross-linking agents in combination to improve, pseudo-leather made of polyamide and polyester fibrillated composite fibers, woven fabrics, non-woven fabrics, knitting It is also possible to use synthetic leather or the like in which a polyurethane resin layer is formed on a base material such as cloth via a polyurethane adhesive. Further, the photocatalyst-supporting fabric of the present invention can be obtained by treating a processed fabric such as an umbrella, a tent, or a bag. The fabric carrying the photocatalyst shown in the present invention has many uses that require antibacterial, deodorant, antifouling and other effects, such as interior products such as curtains and wallpaper, daily necessities such as tents, umbrellas and tablecloths, and food packaging. It can also be used as a material and in the agricultural field such as seedling raising sheets. As the metal bearing the photocatalytic activity shown in the present invention, in addition to a single metal such as aluminum, iron and copper, various alloys such as stainless steel, brass, brass, aluminum alloy and titanium alloy can also be used as a carrier. Further, depending on the shape and material of the metal used, a photocatalyst carrier is provided with an adhesive layer and a photocatalyst layer according to the present invention on a metal sheet or plate painted with ordinary paint, a colored steel plate, a color aluminum sash, or the like. In this case, if the adhesive layer and the photocatalyst layer have high light transmittance and are transparent, the color tone of the underlying paint is not impaired, which is preferable. The metal having the adhesive layer and the photocatalyst layer can be obtained in any complicated shape such as a plate shape, a tubular shape, a spherical shape, a fibrous shape, and a sheet shape. Moreover, if the size is 10 microns or more, it can be firmly supported. Further, depending on the application such as a window frame, furniture, showcase, and eyeglass frame that has already been constructed, the processed metal can be treated to obtain the photocatalyst-supporting metal of the present invention. The metal carrying the photocatalyst shown in the present invention requires effects such as antibacterial, deodorizing, and antifouling on window frames, furniture, decorations, interior panels, exterior panels, water treatment fillers, strainers, filters, etc. Can be used in many situations. The shape of the wood and the wood-based material provided with the adhesive layer and the photocatalyst layer according to the present invention can be any complicated shape such as a plate shape, a plate shape, a spherical shape, or a sheet shape. In addition, if the size is 10 μm or more, it can be firmly supported, and by processing it on the already constructed walls, ceiling boards, pillars, as well as processed wood and wood materials such as furniture and woodwork, this book It can also be the photocatalyst-supported wood and wood-based material of the invention. The wood and wood-based materials bearing the photocatalyst shown in the present invention can be used in many situations where antibacterial, deodorizing, antifouling and other effects are required, such as building materials, furniture, woodwork products, interior materials and interior materials. The plastic film provided with the photocatalyst-supporting structure according to the present invention makes use of its antifouling, antibacterial, and deodorizing functions to form a film in which an adhesive is applied to a surface that does not support a photocatalyst. It is possible to attach it to the inside of window glass, window glass of buildings, freezing / refrigerating showcases, greenhouses, etc., decomposing trace harmful substances in the internal space, preventing contamination of the glass surface and preventing scattering when damaged. It is possible to obtain a highly transparent film that is effective for this purpose. Further, a thin plastic film on which the photocatalyst-supporting structure according to the present invention is formed can also be used as a wrap film for food packaging. Resins that can be used for this plastic film include polyethylene terephthalate resin, polycarbonate resin, polyacrylic acid ester resin, polymethylmethacrylate resin, polyethylene resin, polypropylene resin, polyamide resin, polyimide resin, polystyrene resin, polyvinyl chloride resin, and polyfluoride. Highly transparent synthetic resin with a linear transmittance of 50% or more for light with a wavelength of 550 nm when molded into a film such as vinylidene resin, ethylene fluoride-propylene copolymer resin, ethylene fluoride-ethylene copolymer resin, etc. Either film or sheet can be used. Further, even on the surface of an opaque material in which an adhesive layer and a release film are provided on the back surface of a wallpaper or a decorative sheet and a pattern is printed on the front surface, the photocatalyst-supporting structure according to the present invention is transparent, so that the underlying wallpaper or decorative sheet It can be preferably adopted because it does not damage the pattern or pattern printed on the paper. The surface of these synthetic resin films or sheets can be surface-treated to further improve the adhesiveness of the adhesive layer of the photocatalyst-supporting structure, and the surface to which the adhesive layer is applied is treated with corona discharge treatment or UV-ozone treatment. It is also preferable to physically oxidize the surface to a very small amount by such means, or to apply a thin layer of a surface treatment agent such as silicon to improve the compatibility with the adhesive layer. Further, as shown in the examples, it is possible to form a thin film on the front surface or the back surface of these base materials to have a heat ray reflection / shielding function and an ultraviolet ray reflection / shielding function, and it is possible to form an antifouling / antibacterial film. -In addition to being able to be a heat ray reflecting film or an ultraviolet ray blocking film that also has a deodorizing function, the photocatalyst-supporting structure according to the present invention has extremely high durability and photocatalyst activity as shown in the examples. Therefore, it can be a product with extremely high added value. As a method for providing the above-mentioned heat ray reflection function, conductive metals such as Al, Ag, Cu, Cr, Ni, Ti, stainless steel, and aluminum alloys, indium oxide, tin oxide, and tin oxide-indium oxide compounds are used. A method of forming a conductive metal oxide on the film surface by a physical method such as sputtering or vacuum deposition, a solution of a conductive metal oxide or a sol solution is applied and dried, or a plating method or a CVD method is used. Various methods can be adopted, such as a method of forming a film on the film surface and a method of mixing a material having heat ray reflecting characteristics and heat ray shielding characteristics in the resin of the base material. In addition, as a method of providing an ultraviolet shielding function, an ultraviolet absorber such as hindered amine or titanium oxide or a reflecting agent is applied to the surface of the film to form a film, or an ultraviolet absorber is added and mixed in advance on the film substrate. Various methods such as a method of keeping the film can be adopted, and the method can be appropriately selected according to the purpose of use and the structure. When titanium oxide is used as an ultraviolet shielding agent or a reflecting agent, as described in detail in the present invention, the surrounding organic substances are decomposed by the photocatalytic action of titanium oxide alone, so the surface of titanium oxide is thinned with water glass or the like. It is desirable to use one that has been coated to eliminate photocatalytic activity. Further, these materials having a heat ray reflecting function and a material having an ultraviolet ray shielding function can be added and mixed with an adhesive layer formed on the back surface of the film to exert the effect. For example, "Convertec" 1996 3 Materials such as the UV-shielding clear coating agent described in the monthly issue pp95 are solvent-dispersible and can be used. Acrylic-based or silicon-based adhesives are usually used as the adhesive, but various ultraviolet shielding agents and heat ray shielding agents can be added to the adhesive. It is desirable to avoid the use of a pressure-sensitive adhesive having strong adhesiveness in consideration of stains due to residual adhesion of the pressure-sensitive adhesive at the time of reattachment. As a method of providing the pressure-sensitive adhesive and the release film on the photocatalyst-supporting film, for example, a solution-type pressure-sensitive adhesive is coated on the back surface of the film by gravure printing, and then the polypropylene film for peeling is laminated and wound when it is dried and wound. Such a method is simple and can be preferably adopted. A brief description of the drawing: FIG. 1 is a schematic cross-sectional view of the photocatalyst-supported structure of the present invention. The best form for carrying out the invention: Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. <Evaluation test method> 1) Evaluation of photocatalytic activity A sample carrying a photocatalyst having a size of 70 mm × 70 mm was placed in a Pyrex glass container having a volume of 4 L. A mixed gas of air and aldehyde was added to this container so that the aldehyde concentration was 500 ppm. UV intensity 2 mW / cm on supported sample²After irradiating with the light of Black Light (FL 15BL-B manufactured by Matsushita Electric Co., Ltd.) for 2 hours, the aldehyde gas concentration inside the container was measured by a gas chromatograph, and the photocatalytic activity was evaluated from the amount of decrease. The evaluation criteria were as follows. Evaluation of aldehyde gas concentration after irradiation for 2 hours 50ppm or less A 50 ~ 200ppm B 200 ~ 300ppm C 300 ~ 450ppm D 450ppm or more E 2) Adhesiveness evaluation Adhesion was evaluated by the grid tape method test specified in JIS K 5400. The cut spacing was set to 2 mm, and the number of stitches was set to 25. The evaluation points were based on the criteria described in JIS K 5400. 3) Immersion test in boiling water Put tap water with a conductivity in the range of 170 to 230 μS / cm into a 1000 ml Pyrex glass beaker with a small amount of zeolite, and hang it with a commercially available clip so that the entire sample cut into 70 mm × 70 mm after boiling is submerged in water. Lower. After soaking in boiling water for 15 minutes, allowing it to cool for 4 hours at room temperature and drying, the adhesion test described in 2) was performed, and the evaluation score was determined according to the criteria described in JIS K 5400. 4) Total light transmittance Using the carrier before supporting the adhesive layer and the photocatalyst layer as a reference, the total light transmittance of the supported sample at a wavelength of 550 nm was measured with a self-recording spectrophotometer (U-4000 type manufactured by Hitachi, Ltd.). 5) Durability evaluation UV intensity 3 mW / cm with black light on the supported sample²After irradiating the light in a constant temperature and humidity chamber with a temperature of 40 ° C and a relative humidity of 90% for 500 hours, the adhesion test described in 2) was performed, and the evaluation score was obtained according to the criteria described in JIS K 5400. 6) Accelerated weathering test with sunshine carbon arc weather meter Accelerated weather resistance test using sunshine carbon arc weather meter specified in JIS K5400 using WEL-SUN-HCH type manufactured by Suga Test Instruments Co., Ltd., test time 500 hours, black panel temperature 63 ° C, 120 minutes The cycle was carried out under the condition of rainfall for 18 minutes. After the three samples were subjected to the accelerated weathering test, the presence or absence of swelling, cracking, peeling, whitening and surface changes were visually compared with the original test piece not subjected to the accelerated weathering test, and the state of expression was expressed according to the following evaluation criteria. evaluated. Evaluation criteria A: No change was observed in any of the three samples. B: Slight changes are observed in 1 or 2 samples C: Slight changes are observed in all 3 samples, or large changes are clearly observed in 1 or 2 samples. In addition, after the test, the adhesiveness test described in 2) was performed, and the evaluation score was calculated according to the criteria described in JIS K 5400. 7) Antibacterial evaluation test method A sample cut into 5 cm squares is disinfected with 80% ethanol, dried at 150 ° C, sterilized, and then pre-cultured and diluted to a bacterial concentration of 10.⁵Drop 0.2 ml of Escherichia coli solution adjusted to / ml in front of the sample and set it in the incubator. Those irradiated with black light (15W x 2, distance to the light source 10 cm), those irradiated with fluorescent light (15W x 2, distance 10 cm from the light source), those that were not irradiated at all Set 4 samples each under the 3 types of light irradiation conditions. After a predetermined time (1, 2, 3, 4 hours), take out the sample and wipe off the bacterial solution on the sample with sterile gauze soaked in sterile saline. Place the wiped sterile gauze in 10 ml of sterile saline and stir well. This supernatant bacterial solution is planted in an autoclave-sterilized 95 mmφ Petri dish agar medium, and the number of Escherichia coli colonies is counted after culturing at 36 ° C for 24 hours. The procedure from dropping the E. coli bacterial solution to putting it in the incubator is exactly the same. The sample is processed by the same method, the number of E. coli colonies is counted, and the number is used as a reference when dark or when irradiating with black light. , Calculate the survival rate of each sample after a predetermined time when irradiated with a fluorescent lamp. The evaluation criteria were based on the following criteria Evaluation of residual rate of E. coli after 4 hours 20% or less A 20% -40% B 40% ~ 60% C 60% -80% D 80% or more E 8) Evaluation of antifouling property (fat decomposition activity) As an index for evaluating the antifouling function, the amount of decomposition on the photocatalytic structure is quantified using commercially available salad oil containing linoleic acid as the main component in order to measure how quickly the oil and fat adhering to the surface can be decomposed. It was decided to. 1 cm of thin salad oil with paper on the surface of the photocatalyst-supported structure cut into 5 cm squares²It was applied so as to be 0.1 to 0.15 mg per hit. The coating amount was determined by measuring the weight before and after coating with a precision balance. UV intensity on the sample surface of the sample is 3 mW / cm²Adjust the distance between the sample and the black light so that, after turning on the black light, determine the relationship between the elapsed time and the amount of weight loss, measure the amount of decomposition of salad oil after a predetermined time, and use it as an index of antifouling property. did. Evaluation of residual rate of salad oil after 24-hour light irradiation 10% or less A 30 ~ 10% B 50 ~ 30% C 80 ~ 50% D 80% or more E <Example> The following materials were used as the material of the carrier. (TA) Primed polyester film (TB) PVC film (TC) Soda lime glass plate (TD) Metal aluminum plate (TE) High density polyethylene net (Thickness of thread 0.2mm, mesh opening 0.6mm) (TF) Polypropylene tube (Inner diameter 30 mm, outer diameter 36 mm) The following polysiloxane was used as the polysiloxane contained in the adhesive layer. (PS-1) Silicon tetramethoxydomonomer (manufactured by Shin-Etsu Chemical) (PS-2) Polymethoxysiloxane (trade name: Methylsilicate 51 manufactured by Corcote) (PS-3) Polyethoxysiloxane (trade name: Ethylsilicate 40 manufactured by Corcote) The following colloidal silica was used as the colloidal silica contained in the adhesive layer. (KS-1) JGC Catalysts and Chemicals, trade name Cataloid SI-350, particle size 7-9nm (KS-2) Nissan Chemical Industries, Ltd. Brand name Snowtex ST-XS, particle size 4 ~ 6nm The following resin solutions were used to introduce polysiloxane or colloidal silica. (J-1) Acrylic-silicon resin xylene solution with a silicon content of 3% by weight (J-2) Acrylic-silicon resin xylene solution with a silicon content of 10% by weight (J-3) Acrylic-silicon resin emulsion aqueous solution with a silicon content of 20% by weight (J-4) Acrylic-silicon resin emulsion aqueous solution with a silicon content of 50% by weight (J-5) Polyester-silicon resin xylene solution with 10% silicone content (J-6) Acrylic resin xylene solution (J-7) Polyester resin xylene solution (J-8) Epoxy-silicon resin methyl ethyl ketone solution with a silicon content of 3% by weight Polysiloxane or colloidal silica was mixed with a resin solution to adjust the concentration to obtain a solution for forming an adhesive layer. The adhesive layer was formed by a dipping method when the thickness was 2 μm or less and when the shape was other than a flat plate, and by a baker applicator when the film thickness was 2 μm or more and the shape was a flat plate. In particular, when the carrier shape was tubular or reticulated, the dipping method was used. The adhesive layer was dried at 80 ° C when the carrier material was (TE) and (TF), 60 ° C when it was (TB), and 120 ° C otherwise. The following photocatalysts were used. (C-1) Titanium oxide fine particles (trade name P-25 manufactured by Aerosil Japan, crystal particle size 27 nm) (C-2) Titanium oxide sol (acidic nitrate sol, crystal particle size 10 nm) (C-3) Titanium oxide sol (weak alkaline sol with pH 9, crystal particle size 20 nm) The metal oxide gel or metal hydroxide gel to be carried together with the photocatalyst was obtained by drying the following sol solution. (Z-1) Silica sol: JGC Catalysts and Chemicals Trade name Cataloid SI-30, Specific surface area 180m after drying at 150 ° C²/ g (Z-2) Alumina sol: Nissan Chemical Alumina sol-200, specific surface area 400m after drying at 150 ° C²/ g (Z-3) Zirconia sol: Zirconium tetrabutoxide (TBZR) manufactured by Nippon Soda is hydrolyzed in ethanol, dried at 150 ° C, heat-treated at 300 to 500 ° C, and then gelatinized with a dilute aqueous nitric acid solution. , The specific surface area of the deglued product dried at 150 ° C is 50-80m2 / g. (Z-4) Niobium oxide sol: An aqueous solution of niobium acid manufactured by CBMM was neutralized with 10% aqueous ammonia, dried at 150 ° C and then defibrated with a dilute nitric acid aqueous solution, and the deflated product was dried at 150 ° C. Specific surface area is 60m2 / g (Z-5) Acrylic silicone resin emulsion aqueous solution with a silicone content of 20% by weight (Z-6) Silane Coupling Agent Tri (β-methoxyethoxy) vinylsilane manufactured by Nippon Unicar Co., Ltd. (trade name: A-172) A titanium oxide photocatalyst was dispersed in the above solution, and a predetermined amount of a surfactant was added to prepare a photocatalyst layer forming solution. The photocatalyst layer was formed by a dipping method when the thickness was 2 μm or less or when the carrier shape was other than a flat plate, and by a bar coater when the carrier was a flat plate and the thickness was 2 μm or more. The photocatalyst layer was dried at the same temperature as the adhesive layer was dried. Hereinafter, the compositions of Examples and Comparative Examples in which the type, amount, thickness, film forming method, etc. of the above materials are changed and the performance of the obtained photocatalyst-supported structure are summarized in Tables 1 to 4. In Examples 1 to 18 and Comparative Examples 1 to 4, titanium oxide (P-25) manufactured by Nippon Aerosil Co., Ltd. shown in (C-1) was used as a photocatalyst. The results are shown in Table 1. In Comparative Example-1, when the photocatalyst layer was supported without providing the adhesive layer, the photocatalyst layer had no adhesiveness at all and was easily peeled off, and the surface of the polyester film after the durability test was a photocatalyst. It deteriorated due to the action, and holes and cracks were observed. In Examples-1 to -2, when acrylic-silicone resin or polyester-silicone resin was used for the adhesive layer, the adhesiveness of the photocatalyst layer was good and the durability was also good. In Examples -3 to -12, when a resin containing polysiloxane was used for the adhesive layer, the catalytic activity was good, and the adhesiveness and durability were also good. Durability was good even when the resin into which the polysiloxane was introduced was an acrylic-silicon resin (Examples-3, 4, 5) or a polyester-silicon resin (Example-9). As the resin into which polysiloxane was introduced, a good one was obtained even if it was an acrylic resin (Example-7) or a polyester resin (Example-12). On the other hand, as shown in Comparative Example-2, even if an acrylic-silicon resin containing polysiloxane is used for the adhesive layer, the photocatalyst layer does not adhere when the polysiloxane content is 70% by weight. , Has peeled off. In Examples -13 to -18, when a resin containing colloidal silica was used for the adhesive layer, the catalytic activity, adhesiveness and durability were good. In particular, when a fine particle size (KS-2) is used for colloidal silica and the resin into which colloidal silica is introduced is an acrylic-silicon resin (Examples-15 and 16), it is very good. I got the thing. On the other hand, when the content of colloidal silica in the adhesive layer was as high as 50% by weight (Comparative Example-3), the adhesiveness and durability deteriorated sharply. In Examples-1 to -18, titanium oxide (P-25) of Nippon Aerodil Co., Ltd. shown in (C-1) is used as a photocatalyst, and a metal oxide sol or a metal hydroxide sol composited with the photocatalyst layer is used. Most of them use silica sol, but all of them are good. The results of supporting the product on a polyethylene net or a polypropylene tube were shown in Examples 8 and -9, and products having good photocatalytic activity, adhesiveness and durability were obtained. Even if the content of the silica sol in the photocatalyst layer was reduced to 30% by weight (Example-6), a good product was obtained, but when it was reduced to 20% by weight (Comparative Example-4), the adhesiveness and durability were obtained. Suddenly got worse. In Example-11, when alumina sol was used instead of silica sol, a good product was obtained as in the case of silica sol. The case where the thickness of the adhesive layer and the photocatalyst layer was 0.5 μm and 0.1 μm, respectively, was shown in Example-17, but the adhesiveness and durability were good, and the photocatalytic activity was high even though the film thickness was extremely thin. The value is shown. The data for Examples-19-23 are shown in Table 2.Example-19 Use of titania sol Nitric acid acidic titania sol (titanium oxide content 12% by weight) is adjusted to PH1.5 of JGC Catalysts and Chemicals silica sol (trade name: Cataloid SI-30) instead of fine particle titanium oxide (P-25) manufactured by Nippon Aerosil. And dispersed, and a surfactant was added to prepare a coating solution for a photocatalyst layer. Polymethoxysiloxane (PS-2) was added to the resin solution used in Example-10 to dry the SiO in the adhesive layer.₂A solution added so as to have a content of 35% by weight was prepared and used as a solution for an adhesive layer. The adhesive layer was applied with a baker applicator and the photocatalyst layer was applied with a bar coater on a soda lime glass substrate having a thickness of 1 mm cut out to 7 cm × 7 cm. The drying temperature was the same as in the above-mentioned Examples. The obtained photocatalyst carrier had a very high total light transmittance. Example-20 Use of Silica-Alumina Sol Photocatalyst using exactly the same raw materials and methods as in Example-19, except that a 50:50 mixed sol solution of alumina sol and silica sol manufactured by Nissan Chemical Industries, Ltd. was used instead of the silica sol used in Example-19. A carrier was created. The obtained photocatalyst carrier had high adhesiveness and catalytic activity. Example-21 Coating by gravure printing method Using the adhesive layer solution and photocatalyst solution used in Example-9, a polyester film (Cosmo Shine A4100) manufactured by Toyobo Co., Ltd. was dried at a speed of 10 m / min so that each dry film thickness was 3 μm. Gravure printing was performed at a zone temperature of 130 ° C. A microgravure coater (70 cm width) manufactured by Yasui Seiki Co., Ltd. was used for printing. The total light transmittance of the obtained photocatalyst carrier was as high as 95%. Example-22 Application by spray method Using the adhesive layer solution and the photocatalyst layer solution used in Example-9, a spray was applied onto a soda lime glass substrate using a spray gun WIDER88 manufactured by Iwata Coating Machine Industry Co., Ltd. Both the adhesive layer and the photocatalyst layer were dried at 120 ° C. for 30 minutes. The obtained photocatalyst carrier had good adhesiveness and photocatalytic activity. Example-23 Use of Epoxy-Silicone Resin In Example-12, a photocatalyst carrier was prepared by the same method as the same raw material except that a methyl ethyl ketone solution of an epoxy resin having a silicon content of 3% by weight was used instead of the polyester resin xylene solution. The obtained photocatalyst carrier had good adhesiveness and photocatalytic activity. The composition and performance test results of Examples 24 to 35 below are shown in Table 3. In Examples -24 to -25, acrylic-silicon resin is used for the adhesive layer, and 50% by weight of fine particle titanium oxide P-25 (C-1) manufactured by Nippon Aerosil Co., Ltd. is shown in (Z-1) as the photocatalyst layer. In an example using a composite obtained by preparing raw material powder and sol solution so as to have a composition containing 25% by weight of silica sol and 25% by weight of alumina sol shown in (Z-2), the adhesiveness after the boiling water test is It was good, and the durability and accelerated weather resistance were also good. In Examples-26 to -31, a resin containing a polysiloxane in the adhesive layer was used, and in Examples -26 to -28, fine particle titanium oxide of (C-1) was used as the photocatalyst layer. For -31, the titania sol of (C-2) was used, and the type and amount of the sol solution for forming the complex gel were changed. The catalytic activity was good, and the adhesiveness after the boiling water test was changed. Both durability and accelerated weather resistance were good. Adhesion after boiling water test in either acrylic-silicone resin (Examples-26, -27, -28) or epoxy-silicone resin (Examples-29, -30) in which the polysiloxane-introduced resin is introduced. , Durability and accelerated weather resistance were good. As for the resin into which polysiloxane was introduced, a good acrylic resin (Example-31) was also obtained. In Examples-32 and -33, the results of supporting on a polyethylene net or a polypropylene tube were shown, and those having good photocatalytic activity, adhesiveness and durability were obtained. In Examples-32 to -35, a resin containing colloidal silica was used for the adhesive layer, and the catalytic activity, the adhesiveness after the boiling water test, the durability, and the accelerated weather resistance were good. In particular, when a fine particle size (KS-2) is used for colloidal silica and the resin into which colloidal silica is introduced is an emulsion of acrylic-silicon resin (Examples-34, 35), it is very difficult. A good product was obtained. In Example-29, a nitrate acidic titania sol (titanium oxide content 12% by weight), a catalytic chemical silica sol (trade name: Cataloid SI-30), and a Nissan Chemical alumina sol-200 were dispersed in the photocatalytic layer by adjusting the pH to 1.5. Then, a predetermined amount of surfactant was added to prepare a coating solution for the photocatalyst layer, and the thicknesses of the adhesive layer and the photocatalyst layer were set to 0.5 μm and 0.3 μm, respectively, by the dip method. The photocatalytic activity was also high for the thin film. Even if the total content of silica sol and alumina sol in the photocatalyst layer was reduced to 30% by weight (Example-30), good results were obtained. The samples obtained in Examples-24 to -35, which were subjected to the durability test by black light under high temperature and high humidity, the boiling water immersion test, and the accelerated weather resistance test by the sunshine carbon arc weather meter, were subjected to the photocatalytic activity again. Was examined by the amount of photocatalytic activity of acetaldehyde by the same method as in the initial stage, and it was found that all the samples showed exactly the same decomposition activity as the initial amount of acetaldehyde decomposition, and the initial photocatalytic activity was completely maintained. It was. The composition and performance test results of Examples 36 to 53 below are shown in Tables 4 and 5. In Comparative Example-5, when the photocatalyst layer was supported without providing the adhesive layer, the photocatalyst layer had no adhesiveness at all and was easily peeled off, and the surface of the polyester film after the durability test was a photocatalyst. It deteriorated due to the action, and holes and cracks were observed by a stereomicroscope. In Examples-36 to -37, acrylic-silicon resin is used for the adhesive layer, 40 to 50% by weight of fine particle titanium oxide P-25 manufactured by Nippon Aerosil Co., Ltd. is used as the photocatalyst layer, and 40 silica sol shown in (Z-1) is used. This is an example of using a composite obtained by preparing raw material powder and sol solution so that the composition of the acrylic silicone resin emulsion is 10 to 20% by weight. The adhesiveness after the boiling water test is good and the durability is high. The sex and accelerated weather resistance were also good. In Examples-38 to -42, an acrylic-silicon resin containing polysiloxane is used for the adhesive layer, and the same photocatalyst powder as in Example-36 is used for the photocatalyst layer to form a composite gel. It was used by changing the type and amount of the sol solution, and the catalytic activity was good, and the adhesion, durability, and accelerated weather resistance after the boiling water test were all good. The resin into which the polysiloxane is introduced is either an acrylic-silicone resin having a silicon content of 3% (Examples-38, 39) or an acrylic-silicone resin having a silicon content of 10% (Examples-40, 41, 42). However, the adhesion, durability, and accelerated weather resistance after the boiling water test were good. In Examples-44 and -45, the results of carrier on a polyethylene net or a polypropylene tube were shown, and those having good photocatalytic activity, adhesiveness and durability were obtained. Epoxy-silicone resins (Examples-43 and 46), polyester resins (Examples-44), and acrylic resins (Examples-47) were also good as the resins into which polysiloxane was introduced. On the other hand, as shown in Comparative Example-6, even if an acrylic-silicon resin containing polysiloxane is used for the adhesive layer, the photocatalyst layer does not adhere when the polysiloxane content is 70% by weight. It has peeled off. In Examples-48 to -53, a resin containing colloidal silica was used for the adhesive layer, and the catalytic activity, the adhesiveness after the boiling water test, the durability, and the accelerated weather resistance were good. In particular, when a fine particle size (KS-2) is used for colloidal silica and the resin into which colloidal silica is introduced is an acrylic-silicon emulsion resin (Examples-50, ~ 53), it is very difficult. A good product was obtained. On the other hand, when the content of colloidal silica in the adhesive layer was as high as 50% by weight (Comparative Example-7), the adhesiveness and durability deteriorated sharply. In Examples-44 to -47, instead of fine particle titanium oxide (P-25) manufactured by JGC Catalysts and Chemicals, a nitrate acid titania sol (titanium oxide content 12% by weight) and a catalytic chemical silica sol (trade name: Cataroid SI) were used in the photocatalytic layer. -30) and Nissan Chemical's alumina sol-200 or Nippon Soda's zirconia sol were adjusted to PH1.5 and dispersed, and a predetermined amount of surfactant was added to prepare a coating solution for the photocatalyst layer. The case where the photocatalyst layer was provided was shown, but the adhesiveness and durability were good, and the photocatalyst activity was also high for the thin film. Even if the total content of the acrylic-silicone resin emulsion and the silane coupling agent in the photocatalyst layer was reduced to 20% by weight (Example-47), good results were obtained, but when it was reduced to 5% by weight (comparison). Example-8), Adhesion and durability decreased sharply even when acrylic-silicone emulsion resin was added. The samples obtained in Examples-36 to -53, which were subjected to the durability test by black light under high temperature and high humidity, the boiling water immersion test, and the accelerated weather resistance test by the sunshine carbon arc weather meter, were subjected to the photocatalytic activity again. Was examined by the amount of photocatalytic decomposition of acetaldehyde by the same method as in the initial stage, and it was found that all the samples showed exactly the same value as the initial amount of acetaldehyde decomposition, and the initial photocatalytic activity was completely maintained. .. Example-54 A sample of the titanium oxide photocatalyst structure was prepared by the same method as that used in Example 42, and the antibacterial property was evaluated using the sample. As a result, the survival rate of E. coli in the dark place without light irradiation was 92% after 1 hour, 91% after 2 hours, and 91% after 3 hours, whereas the light of black light The survival rate after 1 hour was 52%, after 2 hours was 29%, and after 3 hours was 11%. In addition, the survival rate of Escherichia coli even when irradiated with fluorescent light was 76% after 1 hour, 54% after 2 hours, and 22% after 3 hours. It showed higher antibacterial properties. The following silicon compounds were used as the coating liquid for the photocatalyst. (S-1) 5 wt% ethanol solution of tetraethoxysilane (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) (S-2) 5 wt% ethanol solution of tetramethoxysilane (manufactured by Shin-Etsu Chemical) (S-3) 5 wt% ethanol solution of methyltriethoxysilane (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) (S-4) Tri (β-methoxyethoxy) vinylsilane (manufactured by Nippon Unicar Co., Ltd .: trade name: A-172) in a 5 wt% ethanol solution Titanium oxide photocatalyst powder or sol solution in the sol solution shown in (Z-1) to (Z-3) and the silicon compound solution is suitable at pH 1.5 to 9 depending on the raw materials used and the types of additives. The range was adjusted, dispersed with water or a mixed solvent of water-ethanol as a solvent, and a predetermined amount of surfactant was added to prepare a coating solution for forming a photocatalyst layer. Table 6 summarizes the content of the components contained in the coating liquid of the obtained photocatalyst layer, the viscosity immediately after the preparation of the coating liquid and 90 days after the sealing, and the sedimentation state of the particles. Examples -55 to -57 are examples in which titanium oxide powder (P-25) was used as the photocatalyst, and the stability of the photocatalyst coating liquid after 90 days was very improved by adding a small amount of silicon compound. In Examples-58 to -60, nitrate acidic titania sol is used as a photocatalyst, and in Examples -59 and -60, silica sol and alumina sol are used in combination as a composite metal oxide sol, and methyltriethoxysilane is used as a silicon compound. It was used. This makes it possible to significantly improve the boiling water resistance of the coated product formed by using this coating liquid, particularly the boiling water resistance in tap water. In Examples-61 and -62, tetramethoxysilane was used as the silicon compound, and it was possible to obtain the effect of maintaining the stability of the liquid even if the amount added was small. In Example-63, powdered titanium oxide (P-25) and nitric acid acidic titania sol were used in combination as a photocatalyst, and silica sol and zirconia sol were used in combination as a metal oxide sol to be composited, and tetramethoxysilane was added. By doing so, the stability of the coating liquid and the sedimentation property of the particles could be improved. In Examples-64 to -66, coating liquids were prepared by changing the type of silicon compound, and all of them were stable coating liquids with a predetermined addition amount. On the other hand, in Comparative Examples -9 to -13, since no silicon compound was added, the viscosity of the coating liquid increased extremely after 90 days had passed, and the particles were always settled for coating. When used as a liquid, it was difficult to control the film forming conditions, and it was not possible to obtain a photocatalyst-coated product of constant quality. <Examples 67 to 71> Using the photocatalyst coating liquid prepared in Examples -55 to -59, a photocatalyst coated product was prepared using the following carrier. The following materials were used as the carrier material. (SA) Primer treated polyester film (SB) Soda lime glass plate (SC) Metal aluminum plate (SD) High density polyethylene net (Thickness of thread 0.2mm, mesh opening 0.6mm) (SE) Polypropylene tube (inner diameter 30 mm, outer diameter 36 mm) The adhesive layer was formed by a dipping method when the thickness was 2 microns or less or when the carrier shape was other than a flat plate, and by a baker applicator when the carrier was a flat plate and the thickness was 2 microns or more. The adhesive layer was dried at 80 ° C when the carrier material was (SD) or (SE), and at 120 ° C otherwise. The photocatalyst layer was formed by a dipping method when the thickness was 2 microns or less or when the carrier shape was other than a flat plate, and by a bar coater when the carrier was a flat plate and the thickness was 2 microns or more. The photocatalyst layer was dried at the same temperature as the adhesive layer was dried. Hereinafter, the performances of the photocatalyst-supported structures of Examples and Comparative Examples in which the types and amounts of the above materials, the thickness of the coating film, the film forming method, etc. are changed are summarized in Tables 7 and 8. The samples obtained in Examples -67 to -71, which were subjected to the durability test by black light under high temperature and high humidity, the boiling water immersion test, and the accelerated weather resistance test by the sunshine carbon arc weather meter, were subjected to the photocatalytic activity again. Was examined by the amount of photocatalytic decomposition of acetaldehyde by the same method as in the initial stage, and it was found that all the samples showed exactly the same value as the initial amount of acetaldehyde decomposition, and the initial photocatalytic activity was completely maintained. .. Example-72 A sample of the titanium oxide photocatalyst structure was prepared by the same method as that used in Example 67, and the antibacterial property was evaluated by the above method using the sample. As a result, the survival rate of E. coli in the dark place without light irradiation was 92% after 1 hour, 91% after 2 hours, and 91% after 3 hours, whereas the light of black light The survival rate after 1 hour was 52%, after 2 hours was 29%, and after 3 hours was 11%. In addition, the survival rate of Escherichia coli even when irradiated with fluorescent light was 76% after 1 hour, 54% after 2 hours, and 22% after 3 hours. It showed higher antibacterial properties. <Example 73> Adhesive film In a xylene-isopropanol (50/50) solution containing 25% by weight of acrylic-silicon resin with a silicon content of 3% by weight, polysiloxane [Methylsilicate 51 manufactured by Corcote Co., Ltd.] is added at 30% by weight with respect to the acrylic-silicon resin. The adhesive layer solution obtained by mixing 5% by weight of the curing agent (silane coupling agent) with the acrylic-silicon resin was diluted with a methyl ethyl ketone solvent so as to have a solid content of 10% by weight. This diluted solution was applied to a polyester film (Cosmo Shine 50 μm) A4100 manufactured by Toyobo Co., Ltd. using a micro gravure coater (70 cm width) manufactured by Yasui Seiki Co., Ltd. at a speed of 15 m / min so that the drying film thickness became 1 μ. Dry zone temperature 13 Next, on the polyester film on which this adhesive layer was formed, a nitrate acidic titania sol having a titanium oxide content of 20% by weight was dispersed as a photocatalytic layer in a nitrate acidic silica sol having a silicon oxide content of 20% in the presence of a surfactant. After that, gravure printing was performed in the same manner as the adhesive layer using a solution diluted with ion-exchanged water-ethanol (50/50) and used as a coating solution for the photocatalyst layer having a solid content of 10% by weight, and the dry film thickness was obtained. A polyester film on which a 1μ photocatalyst layer was formed was obtained. Next, on the surface of the polyester film having the photocatalyst-supporting structure on which the photocatalyst was not applied, a commercially available acrylic adhesive was similarly applied by the gravure printing method, and the heat ray shielding coating agent STS-500 manufactured by Sumitomo Osaka Cement Co., Ltd. Was added and mixed so that the solid content was 5%. When this adhesive coating film is dried and wound in the drying zone of a gravure printing machine, it is laminated with a polypropylene film (Pyrene film-OT 20 μm) P-2161 manufactured by Toyobo Co., Ltd. It was made into a film. This film can be used as a film with adhesive to be attached to automobile window glass, window glass of general households, window glass of medical facilities, etc., and its antibacterial, antifouling, and deodorant effects can be utilized, and it is a shatterproof film when the glass is broken. It was also possible to use it as. Example 74 Flat glass Polysiloxane (manufactured by Corcoat Co., Ltd.) in a xylene-isopropanol (50/50) solution containing 25% by weight of acrylic-silicon resin with a silicon content of 3% by weight in a 1mm-thick soda lime glass cut into 5cm x 5cm. A solution prepared by mixing 30% by weight of methyl silicate 51) with acrylic-silicon resin was applied with a No. 7 bar coater and dried at 100 ° C for 60 minutes to form an adhesive layer. After allowing to cool at room temperature, a nitrate acidic titania sol having a titanium oxide content of 20% by weight was dispersed as a photocatalyst layer in a nitrate acidic silica sol having a silicon oxide content of 20% in the presence of a surfactant to prepare a coating solution for the photocatalyst layer. Using this solution, it was also applied to the surface of the adhesive layer with a No. 7 bar coater, and dried at 100 ° C. for 60 minutes to obtain a photocatalyst-supported glass. (Sample.1) Example 75 Glass fiber paper The adhesive layer solution used in Example 74 was diluted with a xylene-isopropanol (50/50) solution to a solid content of 5% by weight. E-Glass fiberglass paper SAS-030 (grain weight 30 g / m2) manufactured by Olivest Co., Ltd. is immersed in this diluted solution, pulled up and allowed to stand, and then dried at 100 ° C for 120 minutes on the surface of the glass fiber paper. An adhesive layer was formed. Next, the glass fiber paper on which this adhesive layer was formed was immersed in a solution obtained by diluting the coating solution of the photocatalyst layer used in Example 74 with ion-exchanged water to 10% by weight, pulled up, and similarly at 100 ° C. for 120 minutes. It was dried to obtain a photocatalyst-supported glass fiber paper. (Sample.2) Example 76 Eyeglass lens Nikon Eyeglass Lens PC Pointer Coat TC (+) 1.00S0.00 Polysiloxane (Methylsilicate 51 manufactured by Colcoat Co., Ltd.) is added to a xylene-isopropanol (50/50) solution containing 10% by weight of acrylic-silicone resin having a silicon content of 3% by weight in 65 mmΦ 20% of acrylic-silicone resin. Using the solution prepared by mixing by weight, an adhesive layer was formed by the same dipping method as in Example 75, and dried at 100 ° C. for 20 minutes. After allowing to cool at room temperature, nitrate acidic titania sol having a titanium oxide content of 5% was dispersed as a photocatalyst layer in nitrate acidic silica sol having a silicon oxide content of 5% in the presence of a surfactant to prepare a coating solution for the photocatalyst layer. Using this solution, a photocatalyst layer was applied to the surface of the adhesive layer by the same dipping method, and dried at 100 ° C. for 20 minutes to obtain a photocatalyst-coated spectacle lens. (Sample.3) Example 77 Polychlorinated wallpaper SG5328 polyvinyl chloride wallpaper made by Sangetsu Co., Ltd. with a thickness of 1 mm cut into 5 cm x 5 cm, and poly in a xylene-isopropanol (50/50) solution containing 25% by weight of acrylic-silicon resin with a silicon content of 3% by weight. A solution prepared by mixing 30% by weight of siloxane (methyl silicate 51 manufactured by Colcoat Co., Ltd.) with acrylic-silicon resin was applied with a No. 7 bar coater and dried at 100 ° C. for 20 minutes to form an adhesive layer. After allowing to cool at room temperature, a nitrate acidic titania sol having a titanium oxide content of 20% by weight was dispersed as a photocatalyst layer in a nitrate acidic silica sol having a silicon oxide content of 20% in the presence of a surfactant to prepare a coating solution for the photocatalyst layer. Using this solution, it was also applied to the surface of the adhesive layer with a No. 7 bar coater and dried at 100 ° C. for 20 minutes to obtain a photocatalyst-supported wallpaper. (Sample.4) Example 78 Polyester film The adhesive layer solution used in Example 77 was diluted with a xylene-isopropanol (50/50) solution to a solid content of 25% by weight. This diluted solution was applied to a polyester film (Cosmo Shine) A4100 manufactured by Toyobo Co., Ltd. using a microgravure coater (70 cm width) manufactured by Yasui Seiki Co., Ltd., and a speed drying zone of 10 m / min so that the drying film thickness was 3 μm. Gravure printing was performed at a temperature of 130 ° C. Next, the polyester film on which this adhesive layer was formed was subjected to gravure printing in the same manner using the coating solution of the photocatalyst layer used in Example 77 to obtain a polyester film on which a photocatalyst layer having a dry film thickness of 3μ was formed. It was. (Sample.5) Example 79 PC display protection filter Polysiloxane (methyl silicate 51 manufactured by Corcote Co., Ltd.) is mixed with 30% by weight of acrylic-silicone resin in a xylene solution containing 20% by weight of acrylic-silicone resin with a silicon content of 20% by weight, and solidified with an isopropanol solution. A VDT filter E-filter III manufactured by Toray Co., Ltd. was immersed in a solution diluted to 20% by weight per minute, pulled up, and dried at 100 ° C. for 20 minutes to form an adhesive layer. Next, the VDT protective filter on which this adhesive layer was formed was immersed in a solution obtained by diluting the coating solution of the photocatalyst layer used in Example 77 with ion-exchanged water so as to have a solid content of 10% by weight, and pulled up in the same manner. It was dried at 100 ° C. for 20 minutes to obtain a photocatalyst-coated VDT filter. (Sample.6) Example 80 Phone Case The adhesive layer solution used in Example 77 was diluted with a xylene-isopropanol (50/50) solution to a solid content of 20% by weight. This diluted solution was spray-painted on the case of a HIT-1 type telephone manufactured by Hitachi, Ltd. with a spray gun WIDER 88 type manufactured by Iwata Coating Machine Industry Co., Ltd. After drying at 100 ° C. for 20 minutes, the solution of the photocatalyst layer used in Example 1 was spray-painted in the same manner using a solution diluted with ion-exchanged water so as to have a solid content of 8% by weight. Drying at 100 ° C. for 2 minutes gave a phone case carrying a photocatalyst. (Sample.7) Example 81 Eyeglass lens Polysiloxane (50/50) solution containing 10% by weight of acrylic-silicon resin with 3% by weight of silicon content in NL70HCCTc (+) 1.00S0.00 (70mmΦ), a lens for eyeglasses manufactured by Nikon Co., Ltd. Using a solution prepared by mixing 20% by weight of methyl silicate 51) manufactured by Corcote Co., Ltd. with acrylic-silicon resin, an adhesive layer was formed by the same dipping method as in Example 79, and 20 at 100 ° C. It was dried for a minute. After allowing to cool at room temperature, nitrate-acidic titania sol having a titanium oxide content of 15% was dispersed as a photocatalyst layer in nitrate-acid silica sol having a silicon oxide content of 15% in the presence of a surfactant to prepare a coating solution for the photocatalyst layer. Using this solution, a photocatalyst layer was applied to the surface of the adhesive layer by the same dipping method, and dried at 100 ° C. for 20 minutes to obtain a photocatalyst-coated spectacle lens. (Sample.8) Example 82 Curtain Cut out Hospia (for schools and hospitals), a curtain fabric manufactured by Kawashima Textile Co., Ltd., and add epoxy-silicon resin with a silicon content of 3% by weight to a 15% by weight xylene / isopropanol (50/50) solution with polysiloxane ( Methyl silicate 51) manufactured by Corcote Co., Ltd. was impregnated into a solution mixed with 20% by weight of acrylic-silicon resin, pulled up, and dried at 80 ° C. for 120 minutes. After allowing to cool at room temperature, the ammonia alkali titania sol having a titanium oxide content of 10% by weight was dispersed as a photocatalyst layer in a silica sol having a silicon oxide content of 10% by weight in the photocatalyst layer in the presence of a surfactant. The layered curtain fabric was impregnated, pulled up and dried at 80 ° C for 120 minutes to obtain a photocatalyst-supported curtain fabric. (Sample.9) Example 83 Non-woven fabric Unbleached product of Nisshinbo Co., Ltd. cotton non-woven fabric (trade name Orcos) (weight 50 g / m)²) Is cut into 7 cm x 7 cm, acrylic-silicon resin with a silicon content of 3% by weight is mixed with 25% by weight xylene / isopropanol (50/50) solution, and polysiloxane (methyl silicate 51 manufactured by Corcote Co., Ltd.) is added to the acrylic-silicon resin. A solution mixed with 30% by weight was spray-applied using a spray gun WIDER88 manufactured by Iwata Coating Machine Industry Co., Ltd. After drying at 100 ° C for 30 minutes, apply in the same manner using the solution of the photocatalyst layer used in Example 82, and dry at 100 ° C for 30 minutes for surgical gown, tablecloth, toilet seat cover, shoji paper, and seedling raising. A photocatalyst-supported cotton non-woven fabric suitable for sheets, food packaging materials, etc. was obtained. (Sample.10) Example 84 Printed polyester fabric for umbrellas The adhesive layer and the photocatalyst layer were applied by the same method as in Example 83 using the printed polyester fabric used for a commercially available umbrella. The printed polyester fabric supporting the photocatalyst layer had almost no change in the pattern and texture of the fabric. (Sample.11) Example 85 Wallpaper (woven cloth) The adhesive layer and the photocatalyst layer were applied by the same method as in Example 83 using the plain woven wallpaper SG6758 manufactured by Sangetsu Co., Ltd. The woven wallpaper supporting the photocatalyst layer was a good carrier that hardly impaired the texture of the fabric. (Sample.12) Example 86 Aluminum sash An aluminum sash plate cut into 7 cm x 7 cm is mixed with a xylene-isopropanol (50/50) solution containing 25% by weight of acrylic-silicon resin with a silicon content of 3% by weight, and polysiloxane (Methylsilicate 51 manufactured by Colcoat Co., Ltd.). ) Was mixed with 30% by weight of acrylic-silicon resin, applied with a No. 7 bar coater, and dried at 100 ° C for 60 minutes to form an adhesive layer. After allowing to cool at room temperature, a nitrate acidic titania sol having a titanium oxide content of 20% by weight was dispersed as a photocatalyst layer in a nitrate acidic silica sol having a silicon oxide content of 20% in the presence of a surfactant to prepare a coating solution for the photocatalyst layer. Using this solution, it was also applied to the surface of the adhesive layer with a No. 7 bar coater, and dried at 130 ° C. for 10 minutes to obtain a photocatalyst-supported aluminum plate. (Sample.13) Example 87 Stainless steel plate The adhesive layer solution used in Example 86 was diluted with a xylene-isopropanol (50/50) solution to a solid content of 5% by weight. A sample of a SUS316 stainless steel plate (thickness 0.2 mm) cut into 7 cm x 7 cm is dipped in this diluted solution, pulled up and allowed to stand, and then dried at 120 ° C for 20 minutes to form an adhesive layer on the surface of the stainless steel plate. I let you. Next, the stainless steel plate on which this adhesive layer was formed was immersed in a solution obtained by diluting the coating solution of the photocatalyst layer used in Example 86 with ion-exchanged water to 10% by weight, pulled up, and similarly dried at 120 ° C. for 20 minutes. To obtain a photocatalyst-supported stainless steel plate. (Sample.14) Example 88 Tin plate Polysiloxane (methyl silicate 51 manufactured by Corcote Co., Ltd.) is mixed with 30% by weight of acrylic-silicone resin in a xylene solution containing 20% by weight of acrylic-silicone resin with a silicon content of 20% by weight, and solidified with an isopropanol solution. A 0.1 mm thick tin plate cut into 7 cm × 7 cm was dipped in a solution diluted to 20% by weight, pulled up and dried at 100 ° C for 60 minutes to form an adhesive layer. Next, the tin plate on which this adhesive layer was formed was immersed in a solution obtained by diluting the coating solution of the photocatalyst layer used in Example 86 with ion-exchanged water to 10% by weight, pulled up, and similarly dried at 100 ° C. for 60 minutes. Then, it was made into a photocatalyst-supported tin plate. (Sample.15) Example 89 Blinds Tachikawa Blind Industry Co., Ltd.'s blind "Silky Curtain" (slat width 15 mm type) T-12 (white) 800 mm wide and 700 mm high Slats are removed, and 25% by weight of acrylic-silicon resin with a silicon content of 3% by weight is removed. Iwata Coating Machine Industry Co., Ltd. spray gar was prepared by mixing 30% by weight of polysiloxane (methyl silicate 51 manufactured by Corcote Co., Ltd.) with acrylic-silicon resin in the containing xylene-isopropanol (50/50) solution. Spray coated with WIDER 88 type. After drying at 120 ° C. for 20 minutes, the solution of the photocatalyst layer used in Example 86 was spray-painted in the same manner using a solution diluted with ion-exchanged water so as to have a solid content of 8% by weight. It was dried at 120 ° C. for 20 minutes to obtain a blind carrying a photocatalyst. (Sample.16) Example 90 Printed plywood Neowood (2.5 mm thick) printed plywood cut into 7 cm x 7 cm from Eidai Sangyo Co., Ltd. in a xylene-isopropanol (50/50) solution containing 25% by weight of acrylic-silicon resin with a silicon content of 3% by weight. A solution prepared by mixing 30% by weight of horisiloxane (methyl silicate 51 manufactured by Colcoat Co., Ltd.) with acrylic-silicon resin was applied with a No. 7 bar coater and dried at 100 ° C. for 30 minutes to form an adhesive layer. After allowing to cool at room temperature, a nitrate acidic titania sol having a titanium oxide content of 20% by weight was dispersed as a photocatalyst layer in a nitrate acidic silica sol having a silicon oxide content of 20% in the presence of a surfactant to prepare a coating solution for the photocatalyst layer. Using this solution, it was also applied to the surface of the adhesive layer with a No. 7 bar coater and dried at 100 ° C. for 30 minutes to obtain a catalyst-supported printed plywood. (Sample.17) Example 91 Synthetic wood The adhesive layer solution used in Example 90 was diluted with a xylene-isopropanol (50/50) solution to a solid content of 5% by weight. Sekisui Chemical Co., Ltd. Eslon Neo Lumber FFU-50 is dipped in this diluted solution to a size of 7 cm x 7 cm x 7 cm, pulled up and allowed to stand, and then dried at 100 ° C for 120 minutes on the surface of synthetic wood. An adhesive layer was formed. Next, the synthetic wood on which this adhesive layer was formed was immersed in a solution obtained by diluting the coating solution of the photocatalyst layer used in Example 90 with ion-exchanged water to 10% by weight, pulled up, and similarly at 100 ° C. for 120 minutes. It was dried to obtain a photocatalyst-supported synthetic wood. (Sample.18) Example 92 Wooden door Daiken Kogyo Co., Ltd. Indoor wooden door Engraved door 38 type RC0202-IR6 (oak pattern) cut into a size of 7 cm x 7 cm, acrylic with a silicon content of 3% by weight-Xylene containing 10% by weight of silicone resin Using a solution prepared by mixing 20% by weight of polysiloxane (methyl silicate 51 manufactured by Corcote Co., Ltd.) with an isopropanol (50/50) solution with acrylic-silicon resin, by the same dipping method as in Example 91. An adhesive layer was formed and dried at 100 ° C for 20 minutes. After allowing to cool at room temperature, nitrate acidic titania sol having a titanium oxide content of 5% was dispersed as a photocatalyst layer in nitrate acidic silica sol having a silicon oxide content of 5% in the presence of a surfactant to prepare a coating solution for the photocatalyst layer. Using this solution, a photocatalyst layer was applied to the surface of the adhesive layer by the same dipping method, and dried at 100 ° C. for 20 minutes to obtain a photocatalyst-coated wooden door material. (Sample.19) <Evaluation of photocatalytic activity> The photocatalytic activity was evaluated using the samples of Samples 1 to 19, and the results shown in Table 9 were obtained.Industrial applicability: As described above, the photocatalyst-supporting structure of the present invention is antibacterial for glass, plastic, metal materials, cloths, wood and wood materials carrying a highly durable photocatalyst that has high photocatalytic activity and is not easily deteriorated. For the purpose of deodorization, antifouling, etc., it can be applied to products in a wide range of application fields such as various building materials such as lenses, various window glasses, adhesive films, decorative sheets, wallpaper, curtains, blinds, and interior products.