TW201210695A - Photocatalytic paint - Google Patents

Abstract

Disclosed is a photocatalyst that has excellent elasticity. In particular, the disclosed photocatalytic paint ensures the adhesiveness of a base and a photocatalytic layer, even when cracks form in the photocatalyst coating due to seasonal variations in the temperature of the coating surface, and considerably suppress the propagation and development of these cracks in both the surface and the base. The disclosed photocatalytic paint is provided with a base, a photocatalytic layer that includes the photocatalyst, and an intermediate layer that is provided so as to be interposed between the base and the photocatalytic layer and in contact with the underside of the photocatalytic layer. The intermediate layer includes a resin component, which has a silicone component and a flexible non-silicone component. The loss tangent of the intermediate layer at 25 DEG C, measured by a solid-matter viscoelasticity measuring device, is between 0.2 and 1.5. At least one spectral peak of the temperature change curve of the loss elasticity ratio, which is measured by a solid-matter viscoelasticity measuring device that is based on JIS K7244-4 for the intermediate layer, is greater than -80 DEG C and up to 30 DEG C.

Description

201210695 VI. Description of the invention: [Related application] This application is an application for the application of the International Patent Application No. 2010-070197 filed on March 25, 2010 and PCT/ filed on October 18, 2010. The priority of JP 20 10/068790 is hereby incorporated by reference in its entirety in its entirety in its entirety in its entirety in its entirety in its entirety in its entirety. [Technical Field of the Invention] The present invention relates to a photocatalyst-coated body, and more particularly relates to a photocatalyst-coated body which is excellent in self-cleaning function and harmful gas decomposition function due to rainfall, and has good weather resistance for a long period of time. [Prior Art] In recent years, photocatalysts such as titanium oxide have been used for many purposes such as building materials. The photocatalyst is excited by the light energy to decompose various harmful substances or to hydrophilize the surface of the substrate coated with the photocatalyst, and the dirt adhering to the surface can be easily washed away with water. A technique of obtaining a photocatalyst coated body coated with such a photocatalyst, for example, a photocatalyst film formed on a composite material having excellent photocatalyst hydrophilic function, for example, International Publication No. 98/03607 (Patent Document) 1) a photocatalyst particle composed of a metal oxide; and a precursor selected from the group consisting of cerium oxide microparticles, a cerium oxide resin film precursor capable of forming a cerium oxide resin film, and a cerium oxide film precursor capable of forming a cerium oxide film At least one type of capsule consisting of 201210695. In view of the hydrophilicity at the initial stage of the formation of the coating film, the cerium oxide fine particles or the hardened cerium oxide film precursor which can form the cerium oxide film are excellent as a component of the photocatalyst film. Further, when a photocatalyst hydrophilic film is formed on an organic substrate, as described in the specification of International Publication No. 97/00134 (Patent Document 2), in order to solve the problem that the organic material is decomposed or deteriorated due to the photocatalytic activity of the photocatalyst. In this case, a technique in which an intermediate layer having photocatalytic corrosion resistance such as xenon is interposed between the substrate and the photocatalyst hydrophilic film is used. Further, there has been proposed a technique for preventing cracking of a photocatalyst layer having an anticorrosive property against a photocatalyst in an intermediate layer between a substrate and photocatalyst particles. For example, JP-A-2007- 1 68 1 3 5 (Patent Document 3) discloses that the surface of the substrate 1 of the kiln system is formed in the order of the organic coating film 2, the inorganic coating film 3, and the inorganic coating film 4 containing the photocatalyst. A coated body of a coating film in which the elongation at break of the inorganic coating film 3 is set to 0.8 to 3.0%. In the inorganic coating film 4 containing a photocatalyst, the inorganic coating agent uses a photocatalyst to form a cerium oxide resin film precursor which can form a cerium oxide resin film. For an inorganic coating film containing a photocatalyst, it is possible to select no cerium oxide microparticles. Or a more brittle material of the cerium oxide film precursor of the cerium oxide film. Further, a technique of fixing a photocatalyst particle to a surface of an elastic material is disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei No. 10-202794 (Patent Document 4), and a sheet-like material coated with a silicone elastomer is disclosed. A silicone elastomer coated sheet characterized by photocatalytic titanium oxide powder is adhered to the surface layer portion of the elastomer. The method is relatively unique in that a composition of the cerium oxide elastomer is applied to the sheet, and then the titanium oxide powder having photocatalytic energy is carried on the surface thereof to -6 - 201210695 to cure the cerium oxide elastomer composition. [Prior Art Document] [Patent Document 1] [Patent Document 1] International Publication No. 98/03 607 [Patent Document 2] International Publication No. 9 7/0 0134 [Patent Document 3] Special Opening 2007- 1 68 1 [Patent Document 5] JP-A-2008-272718 (Patent Document 5) JP-A-2008-272718 (Summary of the Invention) [Problem to Solve the Invention] The present inventors have now The layer contact of a specific physical property is disposed under the photocatalyst, and the insight that the photocatalyst coating body having good elasticity can be realized is obtained. In addition, it has been found that the photocatalyst coating body can simultaneously satisfy the basic properties required for the photocatalyst coating body. The present invention has been completed based on this finding. Accordingly, it is an object of the present invention to provide a photocatalyst-coated body which has the required basic properties and which has excellent weather resistance and good elasticity. [Means for Solving the Problem] The photocatalyst coated body of the present invention includes: a substrate; a photocatalyst layer containing a photocatalyst; and a substrate and the photocatalyst layer interposed between the photocatalyst layer and the photocatalyst layer The light contacted by the intermediate layer in contact with the 201210695 dielectric coated body is characterized in that the intermediate layer is made of a resin component, and the resin component is made of a non-oxygen component and a soft non-oxygen component. The loss tangent measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 at 25 ° C exceeds the above-mentioned intermediate layer of 〇 2 'under 1.5 ' by the solid viscoelasticity measuring apparatus according to JIS Κ 7244-4. At least one of the spectral peaks in the measured temperature change curve of the loss elastic modulus exceeds _80 degrees and is 30 degrees or less. [Effect of the Invention] The photocatalyst coating system of the present invention has excellent weather resistance and has good elasticity. Specifically, the photocatalyst-coated body of the present invention can ensure the denseness of the substrate and the photocatalyst layer even if it is applied outdoors, for example, when the temperature of the surface of the coating film changes due to seasonal changes or the like, and cracks occur in the photocatalyst film. The property can suppress the propagation or development of cracks generated on the surface side or the substrate side. Further, according to a preferred aspect, the photocatalyst coating system of the present invention exhibits hydrophilicity at the initial stage of formation of the coating film, and as a result, it can exhibit excellent self-cleaning function with rainfall from the coating film, and can maintain its hydrophilicity for a long period of time. The advantage of sex. [Mode for Carrying Out the Invention] Photocatalyst-coated body The photocatalyst-coated body of the present invention basically includes a substrate, and a photocatalyst layer containing a photocatalyst: interposed between the substrate and the photocatalyst layer, and is set to The intermediate layer contacting under the photocatalyst layer; the formed -8-201210695 structure. The intermediate layer is composed of a resin component, and the resin component is a non-oxygen component containing a cerium oxide component and a soft non-oxygen component, and the intermediate layer is subjected to a loss measured by a solid viscoelasticity measuring apparatus according to JIS K7244-4 at 25 ° C. The tangent is over 0.2 and is less than 1.5. The photocatalyst coating system of the present invention has excellent weather resistance and good elasticity. Specifically, even if cracks are formed in the photocatalyst film, the adhesion between the substrate and the photocatalyst layer can be ensured, and the generated cracks can be prevented from propagating or developing toward the substrate side, and the photocatalytic function for the gas decomposition function or the like can be suppressed. It also has excellent performance. Therefore, the coated body of the present invention is not limited to the following, and for example, the members (1) to (6) can be formed as a substrate. In other words, (1) a structure that imparts vibration to a bridge or the like (2) a porous material such as an unglazed ceramic, concrete, cement board, wood, or stone, and a member having an atmosphere having a temperature of 0 ° C or lower, ( 3) A material made of a flexible material such as a metal material, a rubber or a flexible film resin, which is subjected to a bending process after forming a photocatalyst layer, and (4) a temperature change of 20 ° C or more per day. A member made of a material used in a large place, (5) a metal, a resin, a rubber, a silicone sealant, a seal coat, or the like, which has a linear expansion ratio of 1 Ο^Κ·1 or more, and a member having a large thermal expansion coefficient. (6) The temperature difference is the component used in the environment above 30%. The surface of these members is illuminated by light such as sunlight that illuminates the light source of the photocatalyst. According to a preferred aspect of the present invention, the photocatalyst layer contains photocatalyst particles and inorganic oxide particles, and the particle component is 70% by mass or more, preferably 90% by mass or more, based on the photocatalyst layer. When the photocatalyst layer is configured as described above, it is easy to exhibit hydrophilicity at the initial stage of formation of the coating film, and substantially, the coating film can then exhibit excellent self-cleaning performance due to rainfall. In this aspect, especially when the photocatalyst layer is brittle, the propagation or development of cracks can be further suppressed. In general, a photocatalyst layer, particularly a photocatalyst layer composed of an inorganic component, is brittle, and therefore cracks may occur depending on seasonal changes and temperature changes. However, in the case of the photocatalyst-coated body of the present invention, the crack is caused by the multiplication effect of the two reasons shown below, so that the influence of the crack does not propagate to the surface side and the substrate side. However, the following reasons are assumed, but the present invention is not limited to those having such effects. The loss tangent of 2 5 ° C of the intermediate layer in contact with the underside of the photocatalyst layer exceeds 0.2, whereby the intermediate layer absorbs the energy. Further, according to one aspect of the present invention, when 70% or more of the photocatalyst layer is composed of a particulate substance such as photocatalyst particles or inorganic oxide particles, a particle gap exists in the photocatalyst layer, and the development of cracks is suppressed by the gap. Therefore, the crack generated in the photocatalyst layer is less likely to propagate or develop toward the surface or the cross-section, and the surface does not have an appearance defect such as white turbidity accompanying the crack, and the intermediate layer and the substrate are not easily broken, and under the photocatalyst layer. When the loss of tantalum at 25 ° C of the intermediate layer in contact is less than 1.5, the surface of the photocatalyst layer can maintain hydrophilicity of less than 20 ° for a long period of time. Further, by disposing the oxygen-containing component as a resin component of the intermediate layer, deterioration of the substrate due to the photocatalyst can be suppressed. The surface of the photocatalyst layer in the photocatalyst-coated body of the present invention is excited by light of the photocatalyst, and is converted into a contact angle with water to exhibit hydrophilicity of less than 20°. This provides excellent self-cleaning performance with rainfall. The ratio of the photocatalyst -10- 201210695 in the photocatalyst layer in the photocatalyst coating body of the present invention is preferably 1% by mass or more, less than 20% by mass, and more preferably 5% by mass or more and 15% by mass or less. In one aspect of the invention, when the proportion of the photocatalyst in the photocatalyst layer is much smaller than the above range of the inorganic oxide particles, the photocatalyst particles can be directly contacted with the substrate, thereby suppressing the base. Erosion of materials (especially organic substrates). At the same time, it is possible to prevent the photocatalyst from being attacked on the substrate (especially the organic substrate), and at the same time, it is possible to obtain a photocatalyst-coated body excellent in decomposing harmful gases and various desired film properties (transparency, film strength, etc.). . In the present invention, when the photocatalyst is a particle, the average particle diameter of the photocatalyst particles in the photocatalyst coating body is preferably l〇nm or more, less than 100 nm, more preferably l〇nm or more, less than 100 nm, and most preferably 10 nm or more and 60 nm or less. In the present specification, the average particle diameter of the photocatalyst particles is measured by a scanning electron microscope to determine the length of any of the 100 particles in the field of view of 20,000 to 200,000 times, and is calculated by the number average 値. The shape of the particles is preferably a true sphere, or a slightly circular or elliptical shape. In this case, the length of the particles is calculated by ((long diameter + short diameter)/2). When the average particle diameter of the photocatalyst particles is within the above range, the amount of aeration and gas decomposition activity in the photocatalyst layer can be sufficiently exhibited, and sufficient photocatalytic decomposition activity can be exhibited, and various film properties such as weather resistance can be balanced. Further, when the average particle diameter of the photocatalyst particles is in the above range, the photocatalyst layer exhibits good transparency. The average particle diameter of the inorganic oxide particles in the photocatalyst-coated body of the present invention is preferably 5 nm or more, less than 10 nm, more preferably 10 nm, and even more preferably 40 nm in the present specification. The average particle diameter of the inorganic oxide particles is the same as the average particle diameter of the photocatalyst particles, and -11 - 201210695 is used to measure the length of any 100 particles entering a field of view of 200,000 times by a scanning electron microscope. When the average particle diameter of the inorganic oxide particles is in the above range, the gas permeability in the photocatalyst layer can be improved, the gas decomposition reactivity can be improved, and the abrasion resistance and crack resistance can be improved. The film thickness of the photocatalyst layer in the photocatalyst-coated body of the present invention is preferably 3 μm or less. When the film thickness of the photocatalyst layer is 3 μm or less, the transparency and the film strength are excellent, and the effect that the crack does not progress to the surface side and the appearance is poor can be remarkably suppressed. According to a preferred embodiment of the present invention, the film thickness of the photocatalyst layer is preferably 〇.2 μmη or more, more preferably 〇·5 μηι or more. The film thickness of the photocatalyst layer is 〇·2 μm or more, and it exhibits good hydrophilicity. Further, since the ultraviolet rays reaching the interface between the photocatalyst layer and the substrate are sufficiently attenuated, the effect of improving the weather resistance can be obtained. In one aspect of the invention, there is a particle gap in the photocatalyst layer of the photocatalyst-coated body. Thereby, the decomposition function of the harmful gas by the photocatalyst can be improved, and the progress of the crack on the surface side and the profile side can be suppressed. The particle gap in the photocatalyst-coated body of the present invention is preferably from 20% by volume to 5% by volume. When the void ratio is in the above range, the harmful gas and the photocatalyst particles are in contact with each other at a high probability. Therefore, the decomposition activity of the harmful gas is further enhanced. When the gap is mixed, the progress of the crack to the surface side and the cross section side can be sufficiently suppressed. In the present specification, it is preferable to use a reflection spectroscopic film thickness meter: FE-3 000 manufactured by Otsuka Electronics Co., Ltd., and to measure 5 or more points per sample, preferably 10 points or more, and obtain an average of 値. Counting. The order is as follows -12- 201210695. Sequence i. Refractive index of the glass plate 1-1. Measure the reflectance of the glass plate at a wavelength of 23 〇 to 800 nm according to the following conditions 〇 Determination method Absolute reflectance lens Refresh . 2 5 X Standard reflector A1-S-13 filter Picking the slit 〇.2mm><2mm sampling time 1 0 0 0 sec cumulative times 9 times gain normal 1-2. By the medium = air, glass plate, light incident angle ¢ = 0, the air side is incident When the light is reflected by the glass plate, the Fresnel amplitude reflection coefficient of the air/glass plate interface and the dispersion of n-Cauchy are calculated, and the reflectance of the glass plate at a wavelength of 203 to 800 nm is calculated. In the above-mentioned n-Cauchy dispersion, the initial enthalpies of the constants (Cmi, Cm2, Cw) are Cml = l.5, Cm2 = 〇, Cm3 = 0, the refractive index of air is 1, and the extinction coefficient of air (extinction coefficient) ) is 0 (Otaruyama Shinshin, "The Basic Theory of Optical Films" p20~65, (2003, optronics)). 1 - 3 . The measured reflectance (1 -1 ) is compared with the calculated reflectance (1 - 2 ), and Cml, Cm2, and Cm3 whose sum of squared residuals is the smallest are obtained. At this time, the upper limit of the sum of the squares of the residuals is 0.02 -13 - 201210695 1- 4. Substituting Cm|, Cm2, and Cm3 obtained by 1-3 into the dispersion of n-Cauchy' determines the refractive index of the glass plate nm ^ Sequence 2. Determination of the void ratio of the photocatalyst layer 2- 1. The reflectance of the photocatalyst layer at a wavelength of 230 to 800 nm is measured according to the following conditions. Measurement method Absolute reflectance lensRefrec.25X Standard reflector A1-S-13 Filter without slit 0.2mm><2mn Sampling time 1 0 0 0msec Cumulative number 9 times Gain normal 2-2. Composition medium = air, photocatalyst Layer = single-layer film, glass plate, incident angle of light Φ =0 °, light reflected by the air side from the single layer film and light transmitted inside the single layer film above the single layer film (air / Single-layer film interface, single-layer film/glass plate interface) The Fresnel amplitude reflection coefficient of the air/single-film interface of multiple photoreactions with multiple repetitive reflections is approximated by Bruggeman, thereby calculating the wavelength of the photocatalyst layer 23 0~ Reflectivity of 8 0 Onm (Kojiyama Koshinshin, "Basic Theory of Optical Films" p20~65, (2003, optronics), DE A spnes, Thin Solid Films, 89, 249 (1 982)). The initial enthalpy of C] (volume of Si02 -14 - 201210695 fraction), c2 (volume fraction of Ti〇2), and c3 (volume fraction of air) are 0.70, 0.05, and 0.25, respectively. In addition, the refractive index of air is 1, and the extinction coefficient of air is 〇. The refractive index (, n2 ) of Si02 and Ti02, and the extinction coefficient (h, k2) are quoted by E. D. Palik, “Handbook of Optical Constants of Solids”, (1 9 9 8

Academic Press » San Diego ) o 2-3. Change the film thickness d, SiO 2 , TiO 2 , air volume fraction Cr C2, C3 値, measured reflectance (2-1) and calculated reflectance (2-2) Compare and find C!, C2, and C3 when the sum of squared residuals becomes minimum. The residual square is less than 0.02 and becomes the minimum when C3 is used as the void ratio. Other conditions are as follows. Film thickness search method optimization method search range (wavelength) 400 to 800 nm search range (film thickness) 0 to 2000 nm film thickness stage l 〇 nm C3 obtained here as void ratio in the photocatalyst layer of the present invention (% by volume ). The proportion of the soft non-oxygenated resin in the resin component of the photocatalyst-coated body of the present invention is preferably more than 1%, less than 99.5%, more preferably more than 10%, less than 99.5%, and most preferably more than 50%. %, less than 99.5%. When the ratio of the soft non-sandwich resin is in the above range, the deterioration of the photocatalyst in the intermediate layer can be suppressed, and the adhesion between the intermediate layer and the photocatalyst layer can be improved. The ratio of the oxygen component in the resin component of the photocatalyst-coated body of the present invention is preferably 0.5% or more and 30% or less in terms of SiO 2 . Resin -15 - 201210695 When the ratio of the oxygen component in the composition is within this range, deterioration of the photocatalyst in the intermediate layer can be more suppressed. Photocatalyst layer In the present invention, when a photocatalyst is present on the surface of the substrate, preferably, the photocatalyst particles include, in addition to a completely film form, a state in which a portion is formed into a film. Further, it may exist in an island-like discrete state on the surface of the substrate. In accordance with a preferred aspect of the invention, the photocatalyst layer is obtained using a coating liquid. According to a preferred embodiment of the present invention, the photocatalyst layer of the photocatalyst-coated body contains photocatalyst particles and inorganic oxide particles as a particle component, and the particle component is 70% by mass based on the photocatalyst layer, preferably 75 mass%, more preferably 80 mass%, more preferably 90 mass% or more. In the present invention, the particle component means a component accompanying the shape. The particle component contains photocatalyst particles and inorganic oxide particles as essential components, and may contain other particles as an optional component. The shape of the particle component is not particularly limited, and may be a spherical shape, a rod shape, a fibrous shape, a whisker shape, a flat shape, or an amorphous shape. In the present invention, for example, crystalline titanium oxide such as anatase titanium oxide, rutile titanium oxide, or brookite-type titanium oxide, ZnO, Sn〇2, SrTiO3, W03, Bi2〇3, and Fe203 can be used as the photocatalyst. At least one of the metal oxides. It is possible to use only one type or a combination of a plurality of types. A preferred combination of a plurality of types includes crystalline titanium oxide and Sn02, crystalline titanium oxides -16-201210695 and W03. Any of the metal oxides exemplified herein is also suitable for each of the constituent combinations described later. The photocatalyst particles are preferably crystalline titanium oxide particles. Crystalline titanium oxide has better water resistance than ZnO. In addition, in the case of Sn02&, it is possible to exhibit a photocatalytic function such as gas decomposition in a large amount of light having a wavelength of 380 nm to 420 nm in sunlight. Further, compared with SrTi03, it is easier to obtain nanometer-sized fine particles, and therefore has a large specific surface area, and it is easy to obtain practically sufficient photocatalytic activity. In addition, compared with W03, Bi203, and Fe203, the band gap is large, so that it has sufficient oxidizing power, and at the same time, after photoexcitation, recombination of conduction electrons and holes is less likely to occur, and gas decomposition has sufficient activation energy. The crystalline titanium oxide is harmless and chemically stable, and can be obtained at low cost. Further, since the crystalline titanium oxide has a high band gap energy, ultraviolet rays are required for photoexcitation, and visible light is not absorbed by the photoexcitation process, so that color development is not caused by the complementary color component. The photocatalyst particles are preferably anatase type titanium oxide, for example, among the crystalline titanium oxide particles. The anatase type titanium oxide has a stronger oxidizing power than the rutile type titanium oxide, and thus exhibits a stronger photocatalytic function such as gas decomposition. The anatase-type titanium oxide particles as the photocatalyst particles can be appropriately combined with the above respective structures, and the above-described effects can be exhibited without impeding the effects. As the inorganic oxide particles, cerium oxide particles, alumina particles, cerium oxide particles, cerium oxide particles or the like can be used. Preferred is cerium oxide particles. In addition to the photocatalyst particles and the inorganic oxide particles (cerium oxide particles), the photocatalyst layer is added to the inorganic binder or the metal in an amount of preferably 30% by mass or less, more preferably 10% by mass or less, without affecting the amount of the photocatalyst hydrophilic function. Or metallization -17- 201210695 substances, surfactants, etc. The photocatalyst layer contains other particles which can be used as an optional component, for example, resin particles such as fluororesin particles, latex and acrylic beads, color pigment particles, body pigment particles such as whiskers, fibers, and enamel, and mica, talc, and glass balls. Such as creative materials particles. According to a preferred aspect of the present invention, the photocatalyst layer may contain an inorganic binder such as amorphous titanium oxide or amorphous cerium oxide; alkali silicate, alkyl silicate or the like which hardens the precursor before formation of the cerium oxide film. Amorphous zirconia; a hardened material such as ammonium zirconium carbonate, zirconium acetate or cesium formate which can form a precursor of a chrome oxide film. According to a preferred aspect of the present invention, the photocatalyst layer may contain a metal or a metal compound such as a Cu compound such as Cu or Cu2, CuO, or the like, an Ag compound such as Ag or Ag2, a Pt or Pt compound, or a Fe compound. , Pd or Pd compounds, etc. The photocatalyst layer of the photocatalyst-coated body of the present invention is formed by drying or baking a coating liquid obtained by dispersing the above components in a solvent. According to a preferred aspect of the present invention, the coating liquid in forming the photocatalyst layer may contain a surfactant from the viewpoint of dispersion stability of the photocatalyst or inorganic oxide particles and wettability when applied to the intermediate layer. . The surfactant can be appropriately selected from the group consisting of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and a zwitterionic surfactant. Preferably, it is a nonionic surfactant, more preferably an ether type nonionic surfactant, an ester type nonionic surfactant, a polyalkylene glycol nonionic surfactant, a fluorine-based nonionic surfactant. Polyfluorinated non-ionic surfactant -18- 201210695 The photocatalyst used in the present invention receives a photo-excited hydrophilization system and can change the contact angle with water in the hydrophobic direction by one night without light irradiation. It can be recovered by the Twilight carbon arc lamp type weathering test in 24 hours. The Twilight carbon arc lamp type weathering test system is made by SUGA Test Machine Co., Ltd. (Condition: light irradiation 30W/m2, atmosphere temperature 60 °C, 120 minutes light irradiation, water spray for 18 minutes, water temperature 16±5 °C ). The contact angle with water was measured by the method described in JIS R 1 703-1. Intermediate Layer The photocatalyst coating of the present invention has an intermediate layer interposed between the substrate and the photocatalyst layer and is placed in contact with the underside of the photocatalyst layer. The intermediate layer contains a resin component containing a ruthenium oxygen component and a soft non-oxygenated resin, and the loss tangent at 25 °C exceeds 0.2 to less than 1.5, preferably more than 0.2 to less than 1.0. The state of "between the substrate and the photocatalyst layer and being placed under the photocatalyst layer" may be a state in which the interface is substantially straight or may be one as long as it is above the contact photocatalyst layer and above the intermediate layer. Any of a number of interlaced states. In the present specification, the loss of the intermediate layer of the photocatalyst coating material is such that the intermediate layer is provided in accordance with JIS K7244-4 ("Testing Method for Dynamic Mechanical Properties of Plastics - Part 4: Tensile Vibration and Non-Resonance Method") On the solid viscoelasticity measuring device, the obtained enthalpy was measured at a frequency of 1 Hz in a tensile mode. -19- 201210695 In the present invention, the intermediate layer contains a resin component. This resin component contains a neon component and a soft non-oxygen component. Here, the oxygen-enhancing component may use a silicone resin or a helium oxygen moiety, and the soft non-oxygen component may use a soft non-oxygen resin or a soft non-oxygen moiety. Further, the resin component may be composed of only the above two components, or may contain a resin or a fragment other than the above two components. The resin component is obtained by polymerizing and mixing the above two components or the above two components and other resins or fragments. Cross-linked. In the present invention, the amount of the resin component in the intermediate layer is preferably 10% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, still more preferably 55% by mass or more and 100% by mass or less. It is preferably 60% by mass or more and 100% by mass or less. In the present invention, the soft non-oxygenated component means a soft non-oxygenated resin or a soft non-oxygenated component, preferably a temperature change curve of loss elastic modulus measured by a solid viscoelasticity measuring apparatus according to JIS K7244-4. The spectral peak in the middle is a component exceeding -80 degrees and below 30 degrees. The soft non-oxygen component contained in the intermediate layer is found to have a spectral peak in the temperature profile of the intermediate layer by the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4. At least one of them exceeds _80 degrees and is below 30 degrees. Further, the amount of the soft non-oxygen component is preferably 20% by mass or more and 100% by mass or less, more preferably 100% by mass or more and 2,0,0% by mass or less based on the amount of Si in the cerium oxide component. More preferably, it is 200% by mass or more and 16,000% by mass or less. The soft non-oxygenated resin can utilize, for example, urethane polyether, amine methyl-20-201210695 acid ester polyester, urethane polycarbonate, polyether, polyester, polyacrylate, polymethyl Acrylates, polyacrylic acids, polymethacrylic acid, polyethylene, composites of these such 'make the oxime modified or halogen modified. Soft non-oxygenated fragments can be used, for example, urethane polyether fragments, urethane polyester fragments, urethane polycarbonate fragments, polyether fragments, polyester fragments, polyacrylate fragments, poly a methacrylate fragment, a polyacrylic acid fragment, a polymethacrylic acid fragment, a polyethylene fragment, a fragment which is modified by oxime or halogen. Further, the oxime resin is preferably a sand oxide represented by the following average composition formula (1): R pSi ( OR ) q 〇 (4-pq) /2 ( 1 ) (wherein R 1 is unsubstituted Or substituting a monovalent hydrocarbon group, R2 is selected from a hydrogen atom, an unsubstituted one-valent hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and P and q are satisfied. <p <4,0 <q <4,0 <(p + q) <4 number). In the above formula, the unsubstituted or substituted one-valent hydrocarbon group of 'R1 is more preferably a carbon number of 1 to 18, and the unsubstituted valence hydrocarbon group is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group. An alkyl group such as a tributyl group, a hexyl group, a cyclohexyl group, an octyl group or a decyl group; an aryl group such as a vinyl group, an allyl group, a 5-hexenyl group or a 9-nonenyl group; An aralkyl group such as phenylethyl group. Further, a substituted one or a part of a hydrogen atom which is substituted with a monovalent hydrocarbon group is substituted with a substituent, and a substituent may be used. 1) A halogen atom such as fluorine or chlorine may be used, and 2) An epoxy functional group such as a glycidoxy group or an epoxycyclohexyl group; 3) a (meth)acrylic acid functional group such as a methacrylic acid group or an acrylic group; 4) an amine group, an aminoethylamino group, and a phenyl group. An amine functional group such as an amine group or a dibutylamino group; a sulfur-containing functional group such as a fluorenyl group or a tetrathioether group; an alkyl ether group such as 6) (polyoxyalkylene alkyl) alkyl ether group; An anionic group such as a sulfonyl group; 8) a group having a quaternary ammonium salt structure, and the like, and 2) and 3) are preferable as the reactive group, and particularly preferably an epoxy functional group. Specific examples of the substituted one-valent hydrocarbon group are trifluoropropyl, perfluorobutylethyl, perfluorooctylethyl, 3-chloropropyl, 2-(chloromethylphenyl)ethyl, 3-shrinkable Glyceryloxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(meth)acryloxypropyl, (meth)acryloxymethyl, 3-aminopropyl , N-(2-Aminoethyl)aminopropyl, 3-(indolylphenylamino)propyl, 3-dibutylaminopropyl, 3-mercaptopropyl, polyoxyethylene An oxypropyl group, a 3-hydroxycarbonylpropyl group, a 3-tributyl ammonium propyl group or the like. Among these, a methyl group, a propyl group, a hexyl group or a phenyl group is preferred. Examples of the unsubstituted or substituted one-valent hydrocarbon group having 1 to 6 carbon atoms of R2 include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, and a third butyl group. An alkenyl group such as an isopropenyl group; an unsubstituted monovalent hydrocarbon group of an aryl group such as a phenyl group; or an alkoxyalkyl group such as a methoxymethyl group, an ethoxyethyl group, an ethoxymethyl group or a methoxyethyl group; The alkoxy group is substituted with a monovalent hydrocarbon group. According to the same aspect of the present invention, in order to impart flexibility to the oxime resin, a difunctional decane derivative monomer may be contained (having two hydrolyzable groups X per molecule, and two oxygen atoms bonded to each ruthenium atom form two Functional siloxane-bonded monomer). Preferred hydrolyzable difunctional decane derivative monomer, Example-22-201210695, such as diphenyldichlorodecane, diphenyldibromodecane, decane, diphenyldiethoxydecane, phenylmethyl Dibromodecane, phenylmethyldimethoxydecane, benzocane, γ-glycidoxypropylmethyldimethoxyoxypropylmethyldiethoxydecane, γ-(methyl Methylmethoxysilane, (methyl)propanyloxydecane, γ-aminopropylmethyldimethoxydecane, diethoxydecane, heptadecafluorooctylmethyldimethoxy Further, the oxime moiety is also the same as above, and the average composition of the formula (1) is 矽 oxygen: R^Si(OR2) qO(4-pq) /2 ...(1 (wherein R1 is an unsubstituted or substituted one-valent hydrocarbon group atom, an unsubstituted valence hydrocarbon group having a carbon number of 1 to 6 or a carbon number 1 one-valent hydrocarbon group 'P and q is 0 <p <4,0 <q <4, number). In the above formula, the unsubstituted or substituted -1 to 18 of R1 is specifically an alkyl group such as an isopropyl group, a butyl group, a butyl group, a hexyl group or a cycloalkyl group. 'A vinyl group such as a vinyl group, an allyl group, a 5-hexenyl group, an 'aryl group such as a phenyl group, an aryl group such as a benzyl group or a phenylethyl group; the hydrogen atom of the unsubstituted one-valent hydrocarbon group; Methoxychlorodecane, phenylmethylmethyldiethoxydecane, γ-glycidyl) propyleneoxypropylpropylmethyldiethoxy γ-aminopropylmethyl decane, heptafluorooctyl For use as described below, R2 is selected from the group consisting of alkoxy groups of hydrogen ~ 6 < ( p+q) The hydrocarbon group of <4 is preferably an alkenyl group such as a carbon methyl group, an ethyl group, a propyl group, an octyl group or a fluorenyl 9-decenyl group. Further, a part or all of -23-201210695 may be substituted with a substituent, and a substituent such as a halogen atom such as η fluorine or chlorine, or 2) an epoxy functional group such as a glycidoxy group or an epoxycyclohexyl group may be used. a (meth)acrylic acid functional group such as a methacrylic acid group or an acrylic group; 4) an amine functional group such as an amine group, an aminoethylamino group, a phenylamino group or a dibutylamino group; 5) a fluorenyl group, a sulfur-containing functional group such as a tetrasulfide group; an alkyl ether group such as 6) (polyoxyalkylene) alkyl ether group; 7) an anionic group such as a carboxyl group or a sulfonyl group; and 8) a tetra-ammonium salt structure. A group or the like is preferable, and as the reactive group, 2) and 3) are preferred, and those having an epoxy functional group are particularly preferred. Specific examples of the substituted monovalent hydrocarbon group are trifluoropropyl, perfluorobutylethyl, perfluorooctylethyl, 3-chloropropyl, 2-(chloromethylphenyl)ethyl, 3-glycidol. Oxypropyl' 2 (3,4-epoxycyclohexyl)ethyl, 3-(meth)acryloxypropyl, (meth)acryloxymethyl, 3-aminopropyl, Ν-(2-Aminoethyl)aminopropyl, 3-(anthracene-phenylamino)propyl, 3-dibutylaminopropyl, 3-mercaptopropyl, polyoxyethyloxy A propyl group, a 3-hydroxycarbonylpropyl group, a 3-tributyl ammonium propyl group or the like. Among them, a methyl group, a propyl group, a hexyl group or a phenyl group is preferred. Examples of the unsubstituted or substituted one-valent hydrocarbon group having 1 to 6 carbon atoms of R2 include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, and a third butyl group. An alkenyl group such as an isopropenyl group; an unsubstituted monovalent hydrocarbon group of an aryl group such as a phenyl group; or an alkoxyalkyl group such as a methoxymethyl group, an ethoxyethyl group, an ethoxymethyl group or a methoxyethyl group; The one-valent hydrocarbon group is substituted with an alkoxy group. According to the same state of the present invention, in order to impart flexibility to the oxygen-containing fragment, it is also possible to contain a functional sand compound derivative monomer (having two hydrolyzable groups X per molecule, and two oxygen atoms bonded to each of the germanium atoms) The atom forms a difunctional 矽-24- 201210695 oxyalkylene bond monomer). Preferred hydrolyzable difunctional decane derivative monomers, for example, diphenyldichlorodecane, diphenyldibromodecane, diphenyldimethoxydecane, diphenyldiethoxydecane, phenylmethyl Dichlorodecane, phenylmethyldibromodecane, phenylmethyldimethoxydecane, phenylmethyldiethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, γ - glycidoxypropylmethyldiethoxydecane, γ-(meth)acryloxypropylmethyldimethoxydecane, γ-(meth)acryloxypropylmethyldiethoxy Baseline, γ-aminopropylmethyldimethoxydecane, γ-aminopropylmethyldiethoxydecane, heptafluorooctylmethyldimethoxydecane, heptadecafluorooctyl Diethoxy decane. In the present invention, the intermediate layer may contain resins other than the above two, such as polyester, polyacrylate, polymethyl propyl ester, polyacrylic acid, polymethacrylic acid, polystyrene, polyethylene, epoxy. Resin, polycarbonate, polypropylene decylamine, polyamine, polyamine, polyol, polyurethane, polyether, polythioether, polyphenol, composites of these, etc. A resin modified with a halogen or a halogen. Further, in the present invention, the intermediate layer may contain a fragment other than the above two, such as a polyester segment, a polyacrylate fragment, a polymethyl acrylate fragment, a polyacrylic acid fragment, and a polymethacrylic acid fragment. , polystyrene fragments, polyethylene fragments, polycarbonate fragments, polyacrylamide fragments, polyamine fragments, polyamine fragments, polyol fragments, polyurethane fragments, polyether fragments, polythioether fragments , polyphenol fragments, such oxime-modified or halogen-modified fragments, and the like. In the present invention, the intermediate layer may contain, in addition to the above resin component, a coloring -25 - 201210695 material, an extender pigment, a light adjusting agent, a UV absorber, a light stabilizer, a film forming aid, a hardener, a surfactant, Viscosity modifier, defoamer, pH adjuster, etc. As the coloring material, an inorganic pigment, an organic pigment, a dye, or the like can be used. As the inorganic pigment, a metal oxide such as titanium oxide, zinc white, red iron oxide, chromium oxide, cobalt blue or iron black, a metal hydroxide such as alumina white or yellow iron oxide, or a ferrocyanide compound such as Prussian blue can be used. Lead, such as lead, zinc sulfide, vermilion, cadmium yellow, cadmium red, sulphate, barite, barite Carbonate such as calcium hydride or sedimentary calcium carbonate, hydrated acid salt, limestone, ultramarine, etc., carbonaceous such as carbon black, aluminum powder, bronze powder, zinc powder, and other metal powders, mica • Pearl pigments such as titanium oxide, etc. For the organic pigment, a nitroso pigment such as naphthol green B, a nitro pigment system such as naphthol S, Lithhol Red, or Lake Red C can be used. Azo pigments such as FAST YELLOW and naphthol red, Alkali blue red, Rhodamine red, Quinacridone red, Dioxazine violet a condensed polycyclic pigment system such as isoindolinone yellow. Disperse dyes, basic dyes, direct dyes, and acid dyes can be used as the dye. As the extender pigment, for example, titanium oxide whiskers, calcium carbonate whiskers, potassium titanate whiskers, aluminum borate whiskers, mica, talc, barium sulfate, potassium carbonate, barium sand, diatomaceous earth, kaolin, limestone, clay, Barium carbonate and the like. -26- 201210695 For example, an inorganic light brightening agent, an organic light brightening agent, or the like can be used as the light adjusting agent. As the inorganic light brightening agent, for example, dry cerium oxide, wet cerium oxide, calcium carbonate, mica, boron nitride, or titanium oxide can be used. As the bright light adjusting agent of the organic system, a resin ball such as an acrylic resin ball, a urethane resin ball, a silicone resin powder, or a fluorine resin powder can be used. As the ultraviolet absorber, a benzophenone type, a benzotriazole type, or a triazine type ultraviolet absorber can be used. The above benzophenone-based ultraviolet absorber, specifically, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methyl can be suitably used. Oxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4- Benzyloxybenzophenone, bis(5-benzylidene-4-hydroxy-2-methoxyphenyl)methane, 2,2·-dihydroxy-4·methoxybenzophenone, 2 , 2'-dihydroxy-4,4.-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxyl Benzene, 2-hydroxy-4.methoxy-2,-carboxybenzophenone, 2-hydroxy-4-stearyloxybenzophenone, octyl benzophenone (〇ctabenz〇ne), and 2 -hydroxy-4-propoxy benzophenone, 2-hydroxy-4-methylpropoxy benzophenone, 2-hydroxy-5-propyleneoxybenzophenone, 2-hydroxy-5-methyl Propylene benzophenone, 2-hydroxy-4-((propyleneoxy-ethoxy)benzophenone, 2-hydroxy-4-(acryloxy-ethoxy)benzophenone, 2_ Hydroxy 4- 4-(methacryloxy-diethoxy)benzophenone, 2_ Group _4- (too propoxy group - triethoxy) benzophenone benzophenone polymerizable ultraviolet absorber or their (co) polymer. The above benzotriazine ultraviolet absorber is specifically, for example, 2_( -27- 201210695 2·-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'- Tert-butylphenyl)benzotriazole, 2-(2·-hydroxy-3',5·-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-5-third Octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-t-th-octylphenyl)benzotriazole, 2-[2'-hydroxy-3,,5,_bis ( α,α'·dimethylbenzyl)phenyl]benzotriazole, methyl-3-[3-tert-butyl-5-(2Η-benzotriazol-2-yl)-4-hydroxyl Condensate of phenyl]propionate with polyethylene glycol (molecular weight 300), isooctyl-3-[3-(2Η-benzotris-2-yl)-5-t-butyl-4-hydroxyl Phenyl]propionate, 2-(3-dodecyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5 , methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy·3\5·-di-p-pentylphenyl)benzotriazole, 2-(2'-hydroxy-4 '-Octyloxyphenyl)benzotriazole, 2-[2'-hydroxy-3,-(3",4",5,,,6"-tetrahydrobenzidine imine methyl)-5 '-A Phenyl]benzotriazole, 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2Η-benzotriazol-2-yl)phenol , 2-(2Η-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, and 2-(2,-radio-5'-- Methacryloxyethylphenyl)-2Η-benzotriazine, 2-( 2,-trans--5--methacryloxyethyl-3-tert-butylphenyl)-2Η- Benzotrin, 2-(2·-hydroxy-5'-methacryloxypropyl-3-t-butylphenyl)_ 5-chloro-2-indole-benzotriazole, 3-methylpropene Polymeric benzotriazole system such as mercapto-2-hydroxypropyl-3-[3·-( 2"-benzotriazolyl)-4-hydroxy-5-t-butyl]phenylpropionate Ultraviolet absorber or such (co)polymer. As the triazine-based ultraviolet absorber, a hydroxyphenyltriazine compound can be suitably used. Further, when a light stabilizer such as a hindered amine-based or/or hindered phenol-based compound is contained, -28-201210695 can further improve weather resistance by the synergistic effect with the above-mentioned ultraviolet absorbent, and thus it is preferable to be a hindered amine-based light stabilizer. Specific examples are bis(2,2,6,6·tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethylpiperidyl)sebacate, Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate , 1-[2-[3-(3,5-Di-t-butyl-4-hydroxyphenyl)propenyloxy]ethyl]-4-[3-(3,5-di-t-butyl) 4-hydroxyphenyl)propenyloxy]-2,2,6,6·tetramethylpiperidine, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)indole Mixture of diester with methyl-1,2,2,6,6-pentamethyl-4-piperidinyl-sebacate, bis(octyloxy-2,2,6,6-tetra Methyl-4-piperidinyl) sebacate, and 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-five Methyl-4-piperidinyl acrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidinyl Acrylate, 1,2,2,6,6-pentamethyl-4-arylene Aminopiperidinyl methacrylate, 2,2,6,6-tetramethyl-4-iminopiperidinyl methacrylate, 4-cyano-2,2,6,6-tetramethyl Polymeric hindered amine-based ultraviolet absorber such as 4-piperidinyl methacrylate or 4-cyano-1,2,2,6,6-pentamethyl-4-piperidyl methacrylate Or such (co)polymers. Further, as a specific example of the hindered phenol-based light stabilizer, bis(3,5-di-t-butyl)-4-hydroxytoluene can be suitably used. In accordance with a preferred embodiment of the present invention, the intermediate layer fluid may also contain a film forming aid in order to improve its formability. The film-forming aids are, for example, isoamyl acetate, oxoacetate acetate, methyl methoxybutyl acetate, ethyl ethoxy propionate, ethylene glycol monobutyl ether acetate, diethylene glycol single Ethyl acetate, diethylene glycol-29- 201210695 monobutyl ether acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-tri Methyl-1,3-pentanediol diisobutyrate, 2,2,4-trimethyl-1,3-pentanediol mono-2-ethylhexanoate, 2,2,4-trimethyl Ester-based organic solvent such as 1,3-pentanediol di-2-ethylhexanoate; benzyl alcohol, 2,2,4-trimethyl-1,3-pentanediol isobutyrate (TEXANOL) Alcoholic organic solvents such as diethylene glycol, isotridecyl alcohol, 1,3-octanediol, glycerin; ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol Ethers such as diethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol mono 2-ethylhexyl ether, propylene glycol monophenyl ether, and tripropylene glycol methyl ether Organic solvents and the like can be used singly or in combination. According to a preferred embodiment of the present invention, the intermediate layer may optionally be a hardener which reacts with a functional group contained in the non-oxygen component. The specific example of the hardener has a stanol group and/or hydrolysis. A compound of a mercaptoalkyl group, a polyepoxy compound, a polyoxazoline compound, a polyisocyanate or the like. In particular, when the functional group contained in the above-mentioned oxygen-containing component and non-oxygenated component is a carboxyl group or a carboxylate group, it is preferred to use an epoxy group and a stanol group and/or a hydrolyzable alkyl group. A combination of a compound, a polyepoxide, and a polyoxazoline compound. As the compound having a stanol group and/or a hydrolyzable alkylene group, for example, methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-butoxydecane, ethyltrimethoxydecane, or the like can be used. Propyltrimethoxydecane, isobutyltrimethoxydecane, cyclohexyltrimethoxydecane,phenyltrimethoxydecane,phenyltriethoxydecane,vinyltrimethoxydecane or 3-(methyl) Organic trialkoxyfluorene-30-201210695 alkane such as acryloxypropyltrimethoxydecane; dimethyldimethoxydecane, dimethyldiethoxyphosphonium di-n-butoxydecane, diethyl Dimethoxydecane, diphenyl decane, methylcyclohexyl dimethoxy decane or methylphenyl di-di-di- dialkoxy decane; methyl trichloro decane, ethyl phenyl trichloro decane, ethylene a variety of chlorodecanes such as trichloromethane, 3-(methylpropyltrichlorodecane, dimethyldichlorodecane, diethyldiphenyldichlorodecane, or the like, and preferably, etc. The use of an organic trialkoxy decane or a decane may be used singly or as a hydrazine. For example, he has 3: glycidoxypropyltrimethoxydecane, oxypropylmethyldimethoxydecane, 3-glycidoxypropane, 3-glycidoxypropylmethyldiethoxy An alkoxycyclohexyl)ethyltrimethoxydecane, and the like. The polyepoxy compound is, for example, polycondensed bisphenol A or bisphenol having an aliphatic or alicyclic polyol structure derived from ethylene glycol neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol A or the like. Polycondensation of aromatic diols such as S and bisphenol F: polyether polyglycerol ethers such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; and poly(ethylene-hydroxy) isocyanurate a polyepethylene glycol of adipic acid, butane tetracarboxylic acid, phthalic acid, a p-phenylene aliphatic or aromatic polycarboxylic acid; a diepoxide of a hydrocarbon-based diene such as cyclooctylcyclohexene Bis(cyclohexylmethyl)adipate, 3,4-epoxycyclohexylmethane, dimethyldimethoxymethoxydecyltrichlorodecane)propene oxirane or dihydrolysis The condensate machine is a dialoxy group or more. 3-glycidyl triethoxy c 'β- (3,4-hydrolyzed condensation, hexanediol, alcohol, hydrogenated diglycidyl ether; polyglycidyl ether formic acid) An alicyclic polyepoxide such as a diene or an ethylene 3,4-epoxy group-3,4-epoxy-31 - 201210695-cyclohexylcarboxylate, etc. The above-mentioned oxazoline compound can be used, for example, 2, 2 '-p-phenylene bis(1,3-oxazoline), 2,2^butylbutyl-bis(1,3-oxazoline), 2,2^exetyl-bis(2- Oxazoline), 2-isopropenyl-1,3-oxazoline, or such polymers, etc. As the polyisocyanate, for example, toluene diisocyanate, diphenylmethane-4,4·-diisocyanate, or the like can be used. Aromatic diisocyanates; aralkyl diisocyanates such as m-xylene diisocyanate, α,α,οΤ,α'-tetramethyl-m-xylylene diisocyanate; hexamethylene diisocyanate, lysine Diisocyanate, 1,3-bisisocyanate methylcyclohexane, 2-methyl-1,3-diisocyanate cyclohexane, 2-methyl-1,5-diisocyanate cyclohexane, isophorone II Isocyanate, etc. In addition, As the polyisocyanate, various prepolymers having an isohydrocarbonate group, a prepolymer having an isocyanurate ring, a polyisocyanate having a biuret structure, and a vinyl monomer having an isocyanate group can be used. The isocyanate group of the polyisocyanate may be blocked by a conventionally known blocking agent such as methanol. The intermediate layer of the photocatalyst coating of the present invention may be used to disperse the above components in a solvent. The coating liquid in the coating liquid is formed by drying or baking. The coating liquid may also contain a surfactant to improve the coating property. The surfactant may be a polysulfonic acid polyethylene phenyl ether ether salt. , sulfonic acid polyoxyethylene ethyl phenyl ether, sodium fatty acid sodium soap, fatty acid potassium soap, sodium dioctyl sulfosuccinate, alkyl sulfate, alkyl ether sulfate, sodium alkyl sulfate - 32- 201210695 Salt, sodium alkyl ether sulfate, polyoxyethylene ethyl ether sulfate, polyoxyethylene ethyl ether sulfate, alkyl sulfate TEA salt, polyoxyethylene ethyl ether Sulfate TEA salt, 2-ethylhexylalkyl Sodium sulphate, sodium decylmethyltaurate, sodium lauryl methyl taurate, sodium dodecyl benzene sulfonate, sodium lauryl sulfosuccinate, polyoxyethyl sulfonate Anionic surfactant such as sodium dilaurate, polycarboxylic acid, oleic acid creatinine, guanamine ether sulfate, lauryl salicylate, sulfo-FA ester sodium salt; polyoxygen Lauryl ether, polyoxyethylene ethyltridecyl ether, polyoxyethylidene ethyl ketone ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethyl ether Alkyl ether, polyoxyethylene ethyl ester, polyoxyethylene ethyl phenol ether, polyoxyethyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene Laurate, polyoxyethylidene stearate, polyoxyethylene ethyl phenyl ether, polyoxyethyl oleate, sorbitan alkyl ester, polyoxyethylene sorbitan Alkyl ester, polyether modified oxime, polyester modified oxime, sorbitan laurate, sorbitan stearate, sorbitan palmitate, sorbitan oleic acid Ester, sorbitan sesquioleate Polyoxyethylene ethyl sorbitan laurate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan oil Acid esters, glyceryl stearate, polyglycerol fatty acid esters, alkyl alkanolamines, lauric acid diethanolamine, oleic acid diethanolamine, oxy-ethylidene amine, polyoxygen Dodecylamine, polyoxyethylene ethylamine, polyoxyethylidene octadecylamine, polyoxyethylidene propylene diamine, polyoxyethylene ethyl propyl propyl block polymerization Nonionic surfactants such as polyoxyethylidene stearate: dimethylalkylbetaine, alkylglycine, guanamine-33-201210695 amphoteric surfactants such as betaine and imidazoline. Octadecyldimethylbenzylammonium chloride, alkyldimethylbenzylammonium chloride, tetradecylmethylbenzylammonium chloride, dioleyldimethylammonium chloride, 1-hydroxyethyl Alkyl-2-alkyl imidazoline quaternary salt, alkyl isoquinoline bromide, polymeric amine, octadecyltrimethylammonium chloride, alkyltrimethylammonium chloride, dodecyl three Methyl ammonium chloride , cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, alkylimidazolinium quaternary salt, dialkyldimethylammonium chloride, octadecylamine acetate, fourteen A cationic surfactant such as an alkylamine acetate, an alkyl propylene diamine acetate or a dimercaptodimethylammonium chloride. In the present invention, the coating liquid for preparing the intermediate layer may appropriately contain a viscosity adjusting agent, an antifoaming agent, a pH adjusting agent, and the like. Substrate When the substrate used in the present invention is a material on which a photocatalyst layer can be formed, 'whether an inorganic material or an organic material, various materials may be used, and the shape thereof is not limited." From the viewpoint of materials, the substrate is Preferred examples are metal, ceramic, glass, plastic, rubber, stone, cement, concrete, fiber, cloth, wood, paper, combinations of these, laminates thereof, and at least one layer of film on the surface. In view of the fact that the expansion and deformation due to water absorption are allowed, it is more preferably a cement or a concrete, and more preferably a metal or a resin from the viewpoint of expansion deformation due to heat. Preferred examples of the substrate include an exterior wall, a roof, a soundproof wall, a guardrail, and a bridge. Building materials include, for example, exterior walls and roofs. The shape of the substrate is not particularly limited. It is not limited to a flat shape, and may be used for a curved surface - 34 - 201210695. Any of these substrates may be appropriately combined with each of the above structures. Particularly, the present invention can be suitably used for a substrate having at least a surface formed of an organic material. Here, the substrate whose surface is formed of an organic material also includes any one of which the base material is entirely composed of an organic material, and the surface of the base material made of an inorganic material is covered with an organic material (for example, a cosmetic board). Use of the coated body The coated body of the present invention can ensure the adhesion between the substrate and the photocatalyst layer even if cracks are formed on the photocatalyst film, and the occurrence of cracks on the surface side and the substrate side can be remarkably suppressed from being propagated or developed. At the same time, it also has excellent performance for photocatalytic functions such as gas decomposition. Therefore, the coated body of the present invention is not limited to the following, and is particularly suitable for, for example, (1) vibration applied by a bridge or the like, and (2) the substrate is an unglazed ceramic, concrete, cement board, wood, stone, etc. The material is used, and the photocatalyst coating body is exposed to an atmosphere having a temperature of 〇 ° C or less, and (3) the substrate is a flexible material such as a metal material, a rubber or a flexible film resin, and the photocatalyst coating system is (4) When the photocatalyst layer is formed, it is formed by bending, (4) When the temperature changes in a day is greater than 20 °C, (5) The substrate is made of metal, resin, rubber, or epoxy sealant. In the case of a material having a coefficient of thermal expansion of 1 〇·5Κ·1 or more, and (6) at least one of the temperature difference of the temperature of 30 ° C or more, and the surface of the photocatalyst layer A case where light from a light source that can photoexcite photocatalyst light such as sunlight is irradiated. The above-mentioned coated body can be used in the environment where the surface of the photocatalyst layer may occasionally rain, and can also be used as a self-cleaning function with rainfall. Further, by setting the initial stage of the coating film, the contact angle with the water is less than 20°, more preferably less than 10. More preferably, it is less than 5. By virtue of the hydrophilicity, it is possible to exhibit a self-cleaning function which is excellent in precipitation immediately after application of the coating film, and maintains its hydrophilicity for a long period of time. [Embodiment] [Examples] Preparation of Photocatalyst Coating Liquid Photocatalyst Coating Liquid 1 A water-dispersed colloidal cerium oxide as an inorganic oxide (aqueous particle: 30 to 60 nm) as a photocatalyst The average particle size: 20~3 Onm) and water are mixed to obtain a solid concentration of 5. A composition having a colloidal cerium oxide content of 90% by mass in the solid content and a photocatalyst content of 1% by mass in the solid content. Further, 3 parts by mass of the nonionic surfactant is mixed with respect to the mass portion of the photocatalyst coating agent, and when the photocatalyst coating liquid is applied, the wettability to the substrate is obtained to obtain a photocatalyst coating liquid. Photocatalyst coating liquid 2 A titanium dioxide aqueous dispersion (average particle diameter: 30 to 60 nm) as a photocatalyst, a water-dispersible colloidal cerium oxide (average particle diameter: 20 to 3 Onm) as an inorganic oxide, and four B The mixture of oxydecane and water gives a concentration of -36 to 201210695 to a solid concentration of 5. 5 mass%, colloidal ceria content in the solid component is 66. The content of 2% by mass and tetraethoxydecane is in the solid content. 5 mass%, the photocatalyst content is 7. 4% by mass of the composition. In addition, with respect to 100 parts by mass of the photocatalyst coating agent, 0. When the photocatalyst coating liquid is applied in an amount of 3 parts by mass of the nonionic surfactant, the wettability to the substrate is obtained, and a photocatalyst coating liquid is obtained. Photocatalyst coating liquid 3 A titanium dioxide aqueous dispersion (average particle diameter: 30 to 60 nm) as a photocatalyst, a water-dispersible colloidal cerium oxide (average particle diameter: 20 to 30 nm) as an inorganic oxide, and tetraethoxy decane Mix with water to obtain a solid concentration of 5. The content of the colloidal cerium oxide was 31% by mass in the solid component and the content of the tetraethoxy decane in the solid content was 62% by mass. 1% by mass and the photocatalyst content is 6. 9 mass% of the composition. In addition, with respect to 100 parts by mass of the photocatalyst coating agent, 0. 3 parts by mass of the nonionic surfactant, when the photocatalyst coating liquid is applied, the wettability to the substrate is obtained, and the photocatalyst coating liquid is obtained. The photocatalyst coating liquid 4 is a photocatalyst aqueous dispersion of titanium dioxide (average Particle size: 30 to 60 nm), water-dispersed colloidal cerium oxide (average particle diameter: 20 to 30 nm) as an inorganic oxide, and alkoxy oligomer and water are mixed to obtain a solid concentration of 5. 5 mass%, the colloidal ceria content is 86 in the solid component. 9 mass%, alkoxy oligomer content is 3. 5 -37- 201210695% by mass, photocatalyst content is 9. 7 mass% of the composition. In addition, with respect to 100 parts by mass of the photocatalyst coating agent, 0. When the photocatalyst coating liquid is applied in an amount of 3 parts by mass of the nonionic surfactant, the wettability to the substrate is obtained to obtain a photocatalyst coating liquid. The photocatalyst coating liquid 5 was mixed with a titanium dioxide aqueous dispersion (average particle diameter: 30 to 6 Onm) as a photocatalyst, tetraethoxy decane as an inorganic oxide, and water to obtain a solid concentration of 5. The content of 5% by mass and tetraethoxy decane is 78. 3% by mass, the photocatalyst content is 2 in the solid content. 7 mass% of the composition. In addition, with respect to 100 parts by mass of the photocatalyst coating agent, 0. 3 parts by mass of the nonionic surfactant, when the photocatalyst coating liquid is applied, the wettability to the substrate is obtained, and the photocatalyst coating liquid is obtained. The photocatalyst coating liquid 6 is used as a photocatalyst aqueous dispersion of titanium dioxide (average Particle size: 3 0 to 6 0 nm), an alkoxy oligomer as an inorganic oxide and water are mixed to obtain a solid concentration of 5. 5质量%, alkoxy oligomer content in the solid component is 26. 5 mass%, photocatalyst content in the solid component is 73. 5 mass% of the composition. In addition, with respect to 100 parts by mass of the photocatalyst coating agent, 0. When the photocatalyst coating liquid is applied in an amount of 3 parts by mass of the nonionic surfactant, the wettability to the substrate is obtained, and a photocatalyst coating liquid is obtained. Preparation of intermediate layer coating liquid -38 - 201210695 The aqueous component of the acrylic oxime resin dispersion used in the following examples has a solid concentration of 35 %, and the aqueous urethane polyether resin dispersion has a solid concentration of 30 %. Further, the following is a measurement of the loss tangent of the coating film at 25 °C. In other words, the intermediate layer coating liquid was applied to a Teflon (registered trademark) sheet by a bar coater #20 and dried. Next, the intermediate coating liquid was repeatedly applied to the obtained coating film by a bar coater #2 0 and dried. Repeat this operation until. The dry-film thickness was about 20 μm. The obtained coating film was cut into strips of 5 mm x 50 mm, peeled off from a Teflon (registered trademark) sheet, and placed on a solid viscoelasticity measuring apparatus, and measured in a tensile mode at a frequency of 1 Hz. In the intermediate layer coating liquid 1 , 202 parts by mass of the aqueous urethane polyether resin dispersion is sequentially added to 100 parts by mass of the water-based acrylic oxime resin dispersion in which the content of oxime is 75% by mass in terms of SiO 2 . 14 parts by mass of filming aid, 5. 4 parts by weight of hardener, 82 parts by mass of water. The resulting mixture was stirred with a stirrer for 30 minutes to obtain an intermediate layer coating liquid 1 having a solid content concentration of 25% by mass. The ratio of the polyoxymethane of this intermediate layer coating liquid 1 was 30% by mass. Further, the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is shown in Fig. 1 of the aqueous urethane polyether resin dispersion used herein. As shown, the spectral peak is -30 °C. Moreover, the loss tangent of the obtained coating film at 25 ° C is 0. 28. Intermediate layer coating liquid 2 -39- 201210695 875 parts of aqueous urethane polyether resin dispersion are sequentially added to 1 part of water-based acrylic oxime resin dispersion having 75% oxygen content. 45 parts of filming aid, 5. 4 parts hardener, 187 parts water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 2 having a solid concentration of 25% was obtained. The intermediate layer coating liquid 2 had a polyoxane ratio of 10%. Further, the aqueous urethane polyether resin dispersion used herein has a spectral peak of -30 ° C which is a temperature change curve of the loss elastic modulus measured by a solid viscoelasticity measuring apparatus according to JIS K7244-4. Further, the loss tangent of the coating film obtained from the intermediate layer coating liquid 2 at 25 ° C was 0. 48. The intermediate layer coating liquid 3 is added with 1 8 85 parts of the aqueous urethane polyether resin dispersion, 90 parts, in one part of the water-based acrylic oxime resin dispersion having a nitrogen content of 75%. Membrane auxiliaries, 5. 4 parts hardener, 343 parts water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 3 having a solid concentration of 25 % was obtained. The intermediate layer coating liquid 3 had a polyoxyxane ratio of 5%. One of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is -3 〇 ° C, for the water-based urethane polyether resin dispersion used herein. Further, the loss tangent of the coating film obtained from the intermediate layer coating liquid 3 at 25 ° C was 0. 52. The intermediate layer coating liquid 4 is added in the order of 1 part (the solid content concentration of 35°/.) of the water-based acrylic oxime resin dispersion having a 矽oxygen content of 75%, and sequentially adds 1 03 00 parts of the water system-40-201210695 Acrylate resin emulsion, 779 parts of filming aid, 5. 4 parts hardener, 95 7 8 parts water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 4 having a solid concentration of 25% was obtained. The ratio of the polyoxane of the intermediate layer coating liquid 4 is 0. 5%. Further, one of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is 2 °C. Further, the coating film obtained from the intermediate layer coating liquid 4 had a loss tangent of 0·60 at 25 °C. The intermediate layer coating liquid 5 was added with 1 1444 parts of a water-based acrylate-based resin emulsion and 779 parts in 100 parts of a water-based acrylic oxime resin dispersion (solid content: 35%) having a nitrogen oxide content of 75%. Filming aids, 5. 4 parts hardener, 843 3 parts water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 5 having a solid concentration of 25% was obtained. The ratio of the polyoxymethane of the intermediate layer coating liquid 5 is 0. 5%. Further, one of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is 3-5 °C. Further, the coating film obtained from the intermediate layer coating liquid 5 has a loss tangent of 0 at 25 ° C. 48. The intermediate layer coating liquid 6 is added in an amount of 100 parts of water-based acrylate-based resin emulsion and -41 - 201210695 779 parts in 100 parts of a water-based acrylic oxime resin dispersion having a nitrogen content of 75%. Additives, 5. 4 parts of hardener, 9576 parts of water. The resulting mixture was stirred with a stirrer for 3 minutes to thereby obtain a solid. The intermediate layer coating liquid 6 having a component concentration of 25%. The ratio of the polyoxane of the intermediate layer coating liquid 6 is 0. 5%. Further, one of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is 24 °C. Further, the loss tangent of the coating film obtained from the intermediate layer coating liquid 6 at 25 ° C was 1. 00. The intermediate layer coating liquid 7 was added with 9346 parts of a water-based acrylate-based resin emulsion and 776 parts of a film-forming auxiliary agent in one part of a water-based acrylic oxime resin dispersion having a nitrogen content of 75%. . 4 parts of hardener, 10,495 parts of water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 7 having a solid concentration of 25% was obtained. The ratio of the polyoxane of the intermediate layer coating liquid 7 is 0. 6%. Further, one of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is 24 °C. Further, the loss tangent of the coating film obtained from the intermediate layer coating liquid 7 at 25 ° C was 0. 49. The intermediate layer coating liquid 8 was added to 159 parts of the aqueous urethane polyether resin dispersion in an amount of 1 part by weight of a water-based acrylic oxirane resin dispersion having a niobium oxide content of 30%, and 14 parts of the composition. Membrane additives, 7. 7 parts hardener, 100 parts water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 8 having a solid concentration of -42 to 201210695 25% was obtained. The intermediate layer coating liquid 8 had a polyoxane ratio of 15%. One of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is -30 °C. Further, the loss tangent of the coating film obtained from the intermediate layer coating liquid 8 at 25 ° C was 〇 _48. in. Inter-layer coating liquid 9 (Comparative Example) 67 parts of water-based urethane polyether resin dispersion was sequentially added to 1 part of water-based acrylic oxime resin dispersion having a 矽 oxygen content of 75%. 8. 3 parts of filming aid, 5. 4 parts hardener, 61 parts water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 9 having a solid concentration of 25% was obtained. The intermediate layer coating liquid 9 had a polyoxane ratio of 50%. Further, one of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is -3 0 ° C. . Further, the loss tangent of the coating film obtained from the intermediate layer coating liquid 9 at 25 ° C was 0. 13. Intermediate layer coating liquid 1 比较 (Comparative Example) 34 parts of water-based urethane polyether resin dispersion was sequentially added to 1 part of water-based acrylic oxime resin dispersion having a 矽 oxygen content of 75%. , 6 · 8 parts of filming aids, 5. 4 parts of hardener, 56 parts of water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 10 having a solid concentration of 25 % was obtained. The ratio of the polyoxane of this intermediate layer coating liquid was 60%. Further, the coating film obtained from the intermediate layer coating liquid was damaged at 25 ° C -43 - 201210695 and the tangent was 0. 09. The intermediate layer coating liquid 1 1 (Comparative Example) was sequentially added in 100 parts of a water-based acrylic oxime resin dispersion having a helium oxygen content of 30%. 2 parts of filming aid, 7. 9 parts of hardener, 76. 5 parts of water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 11 having a solid content concentration of 25% was obtained. The interlayer liquid coating liquid 11 had a polyoxane ratio of 30%. Further, one of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is 60 °C. Further, the loss of the coating film obtained from the intermediate layer coating liquid 1 at 25 ° C is 0. 10. Production and Evaluation of Photocatalyst Coating Body The aqueous acrylic resin coating was spray-coated on a flexible sheet so that the dried film thickness was about 20 μm, and dried at 8 (TC for 30 minutes. Next, the dried film thickness was made The aqueous urethane acrylate resin coating was spray-coated at about 200 μm, and dried at 8 (TC for 30 minutes to obtain a primer for the adhesion test. Next, the dry film thickness was 10 μm. The intermediate layer coating liquid 1 to 1 1 was spray-coated on a primer substrate for adhesion test which was previously heated to about 50 ° C, and dried at 90 t for 2 minutes, and then dried to a thickness of 0. 3~0. The photocatalyst coating liquids 1 to 6 were spray-coated in a manner of 7 μm to obtain a photocatalyst coated body. The combination of the intermediate layer coating liquid and the photocatalyst coating liquid is as shown in the following table - 44 - 201210695. 0 Adhesion performance evaluation The photocatalyst coating body thus obtained was evaluated for adhesion performance as follows. First, the photocatalyst-coated body was placed in a solar weathering tester (manufactured by SUGA Tester, S-3 00C) prescribed by Jis B7753, and taken out 100 hours later. Then, it was immersed in water at 60 ° C for 1 hour, and then dried at 1 Torr (TC for 1 hour, followed by a germicidal lamp (manufactured by Toshiba Litech) (wavelength 254 nm), and the illuminance of the surface of the test piece was set to 10 W/m 2 . The 12-hour step was repeated 8 times in total, and the total test time was 184 hours. The contact angle of the obtained coated body with water was measured by a contact angle meter (CA-X1 50 type manufactured by Kyowa Interface Science Co., Ltd.), followed by scanning electron microscopy. (Manufacturing, S 800) The surface of the obtained coated body was observed 100 times to visually evaluate the approximate residual ratio of the photocatalyst layer. The heat-resistant cold test was carried out as follows. First, the photocatalyst-coated body was placed in JIS. The solar weathering tester (manufactured by SUGA Test Machine, S-3 00C) specified in B775 3 was taken out after 100 hours, then heated at 1 ° C for 1 hour, followed by -2 (TC cooling for 1 hour). The total of the test was repeated for 1 hour, and the total test time was 20 hours. The obtained coated body was placed in a solar weathering tester (manufactured by SUGA Test Machine, S_3〇〇c) prescribed in JIS B7753, and taken out after '100 hours'. Contact angle The contact angle with water was measured (CA-X 15 0 type manufactured by Kyowa Interface Science Co., Ltd.) -45- 201210695 Bending resistance test The bending resistance test was carried out as follows. First, the photocatalyst coated body was placed in accordance with JIS B7753. The daylight weathering tester (manufactured by SUGA Tester 'S-300C) was taken out after 1 hour. Then, the obtained coated body was bent at 180° for 180°. Then, the crack was observed by visual observation. The angle meter (CA-X1 5 0 type manufactured by Kyowa Interface Science Co., Ltd.) measures the contact angle between the bent portion and the water. The vibration resistance test is carried out as follows. First, the photocatalyst coated body is placed in accordance with JIS B 775 3 The sunlight weathering tester (manufactured by SUGA Test Machine, S-3 00C) was taken out 100 hours later. The obtained coated body was fixed on a vibration tester and applied for 10 minutes under the conditions of a vibration number of 5 Hz and a vibration acceleration of 1 G. Vibration. The contact angle of the coated body with water after vibration was measured by a contact angle meter (CA-XI 50 type manufactured by Kyowa Interface Science Co., Ltd.) The above results are shown in the following table. -46- 201210695 [Table 1] Photocatalyst Coating liquid Intermediate layer Coating liquid Adhesion performance evaluation Heat-resistant cold Bending resistance Vibration resistance After test Contact angle Residual film residual rate After test Contact angle Bending part cracking Bending part Contact angle After test Contact angle 1 1 1 <20* 75» <20· none <20* <20* 2 2 <20· 100» <20· none <20· <20· 3 3 <20·100Χ <20· none <20· <20* 4 4 . <20· 100% <20· none <20· <20· 5 5 <20·100Χ <20* no <20· <20* 6 β <20* 100Χ <20· none <20· <20· 7 7 <20· 100% <20· none <20· <20· 8 8 <20· 100% <20· none <20· <20* 11 2 1. <20· 100% <20· none <20· <20· 12 2 2 <2〇·100Κ <20· none <20· <20· 13 2 3 <20·100Κ <20· none <20· <20· 14 2 4 <20· 100K <20· none <20· <20· 15 2 5 <20· 100X <20· none <20· <20· 16 2 6 <20· 100» <20· none <20· <20· 17 2 7 <20' 100X <20· none <20· <20· 18 2 8 <20· 100% <20· none <20* <20· 21 3 1 <20* 100% <20· . No <20· <20· 22 3 2 <20· 100% <20· none <20. <20· 23 3 3 <20· 100% <20· none <20· <20· 24 3 4 <20· 100% <20· none <20· <20· 25 3 5 <20· too% <20· none <20. <20· 26 3 . Θ <20·100%. <20· none <20· <20· 27 3 7 <20· too% <20· none <20· <20· 28 3 8 <20· 100% <20· none <20· <20· -47- 201210695 [Table 2] Example Photocatalyst Coating Liquid Intermediate Layer Coating Liquid Adhesion Performance Evaluation Heat Resistance Cold Resistance Bending Resistance Vibration Resistance Test Contact Angle Coating Residual Rate Test Contact Angle Bending Crack Contact angle with or without bending contact angle test 31 4 1 <20· \m <20* no <20· <20· 32 4 2 <20· m% <20· none <20· <20· 33 4 3 <20· ιοοχ <20* no <20. <20· 34 4 4 <20· 100X <20· none <20* <20· 35 4 S <20· fOOX <20* no <20* <20. 3Θ 4 β <20· 100X <20· none <20* <20· 37 .4 7 <20· 100» <20· none <20· <20· 38 4 8 <Ζ09 100X <20· none <20· <20· 41 5 <20· 100X <20· none <20· <20_ 42 5 2 <20· 100X <20· none <20* <20_ 43 5 3 <20· too% <20· none <20· <20· 44 5 4 <20· 100% <20· none <20· <20· 45 5 5 <20· 100% <20·· none <20· <20· 4Θ 5 6 <20· 100» * <20· none <20· <20* 47 5 7 <20* 100%. <20· none <20· <20· 48 S θ <20· 100% <20· none <20· <20· 61 6 1 <20. 100X <20· none <20· <20* 62 β 2 <20β 100% <20* no <20· <20· 53 6 3 <20· too% <20. none <20· <20_ 54 6 4 <20· 100% <20* no <20· <20· 55 6 5 <20· 100H <20· • none <20· <20. 58 β β <20· 100H <20· none <20* <20· 57 8 7 <20* 100S, <20. none <20· <20· 58 β β <20· Ι00Χ <20· . No <20· <20·Comparative Example 1 1 θ- 60· <10% <20· has <20· <20· Comparative Example 2 .1 10 80* <!0% <20· has <20· <20* Comparative Example 3 1 11 80* <10% <20* has <20· <20· The electron micrograph of the coating film after the adhesion evaluation test is shown in Fig. 2 . In Fig. 2, photographs 1 to 5 are electron micrographs of the coating films of Examples 1 to 3 and Comparative Examples 1 and 2, respectively. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] shows the temperature change of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4, which is the dispersion of the aqueous urethane polyether resin used in Example 1. Graph. -48- 201210695 [Fig. 2] Photograph of the coated film electronics! 1 to 5 are the adhesion evaluation tests of the respective examples 1 to 3, 7 and 8. -49-

Claims (1)

201210695 VII. Application for Patent Park: 1· A photocatalyst coated body comprising: a substrate; a photocatalyst layer comprising a photocatalyst; being interposed between the substrate and the photocatalyst layer, and being set to be photocatalyst a photocatalyst-coated body formed by an intermediate layer that is in contact with the lower layer, wherein the intermediate layer is made of a resin component, and the resin component is made of a non-oxygen component and a soft non-oxygen component, and the intermediate layer is The loss tangent measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 at 25 ° C is less than 0.2, which is less than 1.5, and the intermediate layer is determined by the solid viscoelasticity measuring apparatus according to JIS K7 2 44-4. At least one of the spectral peaks in the temperature change curve of the loss elastic modulus exceeds -80 degrees and is 30 degrees or less. 2. For the photocatalyst coating body of claim 1, wherein the aforementioned loss tangent is more than 0.2 and less than 1.0. 3. The photocatalyst coated body of claim 1, wherein the soft non-oxygenated component is a soft non-oxygenated resin or a soft non-oxygenated film. 4. The photocatalyst coated body according to any one of claims 1 to 3, wherein the spectral peak in the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 It is -40 degrees or more and 30 degrees or less. 5. The photocatalyst-coated body according to any one of claims 1 to 4, wherein the photocatalyst layer contains photocatalyst particles as particles and inorganic oxide particles, and the particle component contains 70% by mass or more. • 50- 201210695. 6. The photocatalyst-coated body according to any one of claims 1 to 5, wherein the surface of the photocatalyst layer is excited by light of the photocatalyst to exhibit hydrophilicity. 7. The photocatalyst coated body of claim 6, wherein the surface of the photocatalyst layer is excited by light of the photocatalyst, and is converted to a hydrophilicity of less than 20° with respect to a contact angle with water. 8. The photocatalyst-coated body according to any one of claims 1 to 7, wherein the ratio of the photocatalyst in the photocatalyst layer is 1% by mass or more and less than 20% by mass. 9. The photocatalyst coated body according to any one of claims 2 to 8, wherein the photocatalyst particles have an average particle diameter of 10 nm or more and less than 100 nm 〇10. The photocatalyst coated body according to any one of the preceding claims, wherein the photocatalyst particles have an average particle diameter of 10 nm or more and less than 100 nm 〇11. The photocatalyst coated body according to any one of claims 1 to 10. Wherein the photocatalyst is crystalline titanium oxide. The photocatalyst coating body according to any one of claims 2 to 11, wherein the inorganic oxide particles have an average particle diameter of 5 nra or more and less than 100 nm. The photocatalyst coated body according to any one of claims 2 to 2, wherein the inorganic oxide particles are cerium oxide particles. The photocatalyst coating -51 - 201210695, wherein the photocatalyst layer has a film thickness of 3 μm or less, as described in any one of claims 1 to 12. The photocatalyst coating body according to any one of claims 2 to 14, wherein the photocatalyst layer has a particle gap, and the particle gap is 20% by volume or more and 35% by volume or less based on the photocatalyst layer. The photocatalyst-coated body according to any one of the above-mentioned claims, wherein the ratio of the oxygen component in the resin component is 0.5% by mass or more and 30% by mass or less in terms of SiO 2 . The photocatalyst-coated body according to any one of the first aspect, wherein the amount of the soft non-oxygen component is from 20% by mass to 100,000% by mass based on the amount of Si in the oxygen-containing component. . The photocatalyst coated body according to any one of the preceding claims, wherein the soft non-oxygenated component is selected from the group consisting of polyurethane polyether, polyurethane polyester, and poly A component of at least one of a urethane polycarbonate, a polyether, a polyester, a polyacrylate, a polymethacrylate, a polyacrylic acid, a polymethacrylic acid, and a polyvinyl group. The photocatalyst coated body according to any one of claims 1 to 18, wherein the soft non-oxygenated component is selected from the group consisting of polyurethane polyethers, polyurethane polyesters, A component of at least one of a polyether and a polyacrylate group. The use of the photocatalyst coated body according to any one of claims 1 to 19, wherein the surface of the photocatalyst layer is irradiated with sunlight, and the surface of the photocatalyst layer is irradiated with sunlight. . The use of a photocatalyst coated body according to any one of claims 1 to 19, wherein the substrate is a porous substrate, and the photocatalyst-52-201210695 coated body is disposed at a temperature of In an atmosphere below 0 ° c, and the surface of the photocatalyst layer is exposed to sunlight. The use of the photocatalyst coated body according to any one of claims 1 to 19, wherein the substrate is a flexible substrate, and after the photocatalyst layer is formed, the photocatalyst coating layer is formed. The use of a photocatalyst coating body according to any one of claims 1 to 19, wherein the photocatalyst coating body is used in an environment in which the surface of the photocatalyst layer is irradiated with sunlight. The coated body is disposed in a place where the temperature of the day changes to 20 ° C or higher, and the surface of the photocatalyst layer is exposed to sunlight. The use of a photocatalyst coated body according to any one of claims 1 to 19, wherein the substrate is a material having a linear expansion ratio of ΙΟ-Ι·1 or more, and the surface of the photocatalyst layer is irradiated Used in the environment of sunlight. The use of the photocatalyst coating body according to any one of claims 1 to 19, wherein the photocatalyst coating body is disposed at a temperature difference of 30 ° C or more, and the photocatalyst is The surface of the layer is used in an environment where sunlight is exposed. 26. The use of a photocatalyst coating body according to claim 20, wherein the substrate is a bridge. 27. The use of a photocatalyst coating body according to claim 21, wherein the substrate is an unglazed ceramic, concrete, cement board, wood, stone. 28. The use of a photocatalyst coated body according to claim 22, wherein the substrate is at least -53-201210695 of a metal material, a rubber or a flexible film resin. 2 9. The use of a photocatalyst coated body according to claim 23, wherein the substrate is at least one of a metal, a resin, a rubber, a silicone sealant, and a seal coat. -54-