TWI480099B - Photocatalyst coating body - Google Patents

Description

Photocatalyst coating body

[Related application]

The present application claims the priority of the Japanese Patent Application No. 2010-070197, filed on March 25, 2010, and the priority of the International Application No. PCT/JP2010/068790, filed on Oct. 18, 2010. The description of these applications is part of the disclosure of this case.

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.

In recent years, photocatalysts such as titanium oxide have been used in many applications such as building materials. By utilizing the activity of the photocatalyst excited by the light energy to decompose various harmful substances or to hydrophilize the surface of the substrate coated with the photocatalyst, 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 can be obtained, for example, as follows.

The photocatalyst film which is formed on the composite material having a photocatalyst hydrophilic function is, for example, a photocatalyst particle composed of a metal oxide as shown in International Publication No. 98/03607 (Patent Document 1); and is selected from the group consisting of cerium oxide microparticles. A film composed of at least one of a group of a silicone resin film precursor forming a silicone resin film and a cerium oxide film precursor capable of forming a cerium oxide film. In view of the hydrophilicity at the initial stage of the formation of the coating film, the cerium oxide fine particles or the cured product of the 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, A technique in which an intermediate layer having photocatalytic corrosion resistance such as xenon is interposed between a substrate and a photocatalyst hydrophilic film is used.

Further, a technique for preventing cracking of a photocatalyst layer having corrosion resistance to a photocatalyst in an intermediate layer between a substrate and photocatalyst particles has been proposed. For example, JP-A-2007-168135 (Patent Document 3) discloses that the surface of the substrate 1 of the kiln system is coated with the organic coating film 2, the inorganic coating film 3, and the inorganic coating film 4 containing the photocatalyst. The package, wherein the inorganic coating film 3 has a fracture elongation of 0.8 to 3.0%. In the inorganic coating film 4 containing a photocatalyst, the inorganic coating agent uses a cerium oxide resin film precursor which can form a cerium oxide resin film which is prepared with a photocatalyst, and for the 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.

In addition, as disclosed in Japanese Laid-Open Patent Publication No. Hei 10-202794 (Patent Document 4), a sheet-like material coated with a silicone elastomer is disclosed, and the silicone elastic property is disclosed. The surface layer portion is adhered to a silicone elastomer coated sheet characterized by photocatalytic titanium oxide powder. The method for producing the cerium oxygen elastomer composition is characterized in that the cerium oxide elastomer composition is coated on the sheet, and then the titanium oxide powder having photocatalytic energy is supported on the surface thereof.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] International Publication No. 98/03607

[Patent Document 2] International Publication No. 97/00134

[Patent Document 3] JP-A-2007-168135

[Patent Document 4] Japanese Patent Publication No. Hei 10-202794

[Patent Document 5] JP-A-2008-272718

The present inventors have now obtained the knowledge that a photocatalyst coated body having good elasticity can be obtained by providing a layer of a specific physical property under the photocatalyst. 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.

The photocatalyst coated body of the present invention comprises: a substrate; a photocatalyst layer comprising a photocatalyst; and an intermediate layer interposed between the substrate and the photocatalyst layer and disposed in contact with the underside of the photocatalyst layer; The photocatalyst 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, and the intermediate layer is formed at 25 ° C according to JIS K7244. The loss tangent measured by the solid viscoelasticity measuring device of -4 is more than 0.2, which is less than 1.5, and the spectrum of the intermediate layer by the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus of JIS K7244-4 At least one of the peaks exceeds -80 degrees and is less than 30 degrees.

The photocatalyst coating system of the invention has excellent weather resistance and good elasticity. Specifically, in the photocatalyst-coated body of the present invention, for example, even if it is applied outdoors, the temperature of the surface of the coating film changes due to seasonal changes, and cracks occur in the photocatalyst film, thereby ensuring the denseness of the substrate and the photocatalyst layer. 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.

[Formation of the Invention]

Photocatalyst coating body

The photocatalyst coated body of the present invention basically comprises: a substrate; a photocatalyst layer comprising a photocatalyst; an intermediate layer interposed between the substrate and the photocatalyst layer and disposed in contact with the underside of the photocatalyst layer; The structure of the formation. 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 loss tangent measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 at 25 ° C of the intermediate layer. More than 0.2, less than 1.5. The photocatalyst coating system of the 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 base material. In other words, (1) a structure such as a bridge that vibrates, (2) an unglazed ceramic, a concrete, a cement board, a wood, a stone, or the like, and a member having an atmosphere having a temperature of 0 ° C or less, (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 large temperature change of 20 ° C or more per day. (a) a member made of a material used in a place, (5) a metal, a resin, a rubber, a silicone sealant, a sealant, or the like, which has a linear expansion coefficient of 10 ^-5 K ^-1 or more and a material having a large thermal expansion coefficient, (6) The member used in an environment where the temperature difference is 30 °C or more. The surface of such members is illuminated by light such as sunlight that is photoexcitable to the 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 has such a configuration, 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 of a 25 ° C tangent of the intermediate layer in contact with the underlying 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 material 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 on 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. When the loss tangent of 25 ° C of the intermediate layer in contact with the underside of the photocatalyst layer 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 the 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 coating body of the present invention is preferably subjected to photoexcitation of the photocatalyst, and is preferably hydrophilic in a contact angle with water of less than 20°. This provides excellent self-cleaning performance with rainfall.

The ratio of the photocatalyst 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-coated body is preferably 10 nm or more, less than 1000 nm, more preferably 10 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 100 particles in a field of view of 20,000 to 200,000 times, and is calculated as a number average. 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 roughly calculated as ((long diameter + short diameter)/2). When the average particle diameter of the photocatalyst particles is within the above range, the amount of aeration and the gas decomposition activity in the photocatalyst layer can be sufficiently exhibited, and sufficient photocatalyst 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 100 nm, more preferably 10 nm, and 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 the length of any 100 particles entering the field of view of 200,000 times is measured by a scanning electron microscope. The average of the numbers is calculated. When the average particle diameter of the inorganic oxide particles is in the above range, the air 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 coating 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 0.2 μm or more, more preferably 0.5 μm or more. The film thickness of the photocatalyst layer is 0.2 μm or more, and it exhibits good hydrophilicity. Further, the ultraviolet rays reaching the interface between the photocatalyst layer and the substrate are sufficiently attenuated, so that 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 coating 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 cross-sectional side can be suppressed.

The particle gap in the photocatalyst-coated body of the present invention is preferably 20% by volume or more and 35% by volume or less. 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 improved. When the gap is mixed, the progress of the crack on 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-3000 manufactured by Otsuka Electronics Co., Ltd., and to measure 5 points or more per sample, preferably 10 points or more, and obtain the average value. The order is as follows.

Sequence 1. The refractive index of the glass plate is determined

1-1. Measure the reflectance of the glass plate at a wavelength of 230 to 800 nm according to the following conditions.

Measuring method Absolute reflectance

Lens Refrec.25X

Standard reflector A1-S-13

Filter

Slit 0.2mm×2mm

Sampling time 1000msec

Accumulated 9 times

Gain normal

1-2. The Fresnel amplitude reflection coefficient of the air/glass plate interface when the light incident from the air side is reflected by the glass plate and n-Cauchy by the medium = air, glass plate, and light incident angle Φ =0° The dispersion method calculates the reflectance of the glass plate at a wavelength of 230 to 800 nm. In the above-mentioned n-Cauchy dispersion formula, the initial values of the constants (C _m1 , C _m2 , C _m3 ) are C _m1 =1.5, C _m2 =0, C _m3 =0, the refractive index of air is 1, and the extinction of air The extinction coefficient is 0 (Mr. Xiaoshan, “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 C _m1 , C _m2 , and C _{m3 when the} sum of squared residuals is minimized are obtained. At this time, the upper limit of the sum of squares of the residuals is 0.02.

1-4. Substituting C _m1 , C _m2 , and C _m3 obtained in 1-3 into the dispersion of n-Cauchy, the refractive index nm of the glass plate is determined.

Sequence 2. Determination of void ratio of photocatalyst layer

2-1. Measure the reflectance of the photocatalyst layer at a wavelength of 230 to 800 nm according to the following conditions.

Measuring method Absolute reflectance

Lens Refrec.25X

Standard reflector Al-S-13

Filter

Slit 0.2mm×2mm

Sampling time 1000msec

Accumulated 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 a single layer of film incident on the air side, and light transmitted through a single layer of film The Fresnel amplitude reflection coefficient of the air/single-film interface of the photo-timed multiple photoreactions on the underside of the single-layer film (air/single-film interface, single-layer film/glass plate interface) and Bruggeman's approximation This calculation yields a reflectance of the photocatalyst layer at a wavelength of 230 to 800 nm (Mr. Xiaoshan, "Basic Theory of Optical Films" p20~65, (2003, optronics), DE A spnes, Thin Solid Films, 89, 249 (1982)) . The initial values of C ₁ (volume fraction of SiO ₂ ), C ₂ (volume fraction of TiO ₂ ), and C ₃ (volume fraction of air) were 0.70, 0.05, and 0.25, respectively. In addition, the refractive index of air is 1, and the extinction coefficient of air is zero. The refractive indices (n ₁ , n ₂ ) and extinction coefficients (k ₁ , k ₂ ) of SiO ₂ and TiO ₂ are cited in ED Palik, "Handbook of Optical Constants of Solids", (1998, Academic Press, San Diego).

2-3. Changing the film thickness d, SiO ₂ , TiO ₂ , the volume fraction of air C ₁ , C ₂ , C ₃ , the measured reflectance (2-1) and the calculated reflectance (2-2) Find C ₁ , C ₂ , and C ₃ when the sum of squared residuals becomes minimum. The sum of the squares of the residuals is less than 0.02, and C _{3 is the} smallest when it becomes the void ratio. Other conditions are as follows.

Film thickness retrieval method optimization method

Search range (wavelength) 400~800nm

Search range (film thickness) 0~2000nm

Film thickness stage 10nm

C ₃ obtained herein is used as the void ratio (% by volume) in the photocatalyst layer of the present invention.

The proportion of the soft non-oxygen resin in the resin component of the photocatalyst coating 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-oxygen 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 . When the ratio of the oxygen component in the resin component 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 a photocatalyst particle, in addition to a completely film shape, a state in which a portion is formed into a film shape, for example. 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%, still more preferably 90 mass% or more.

In the present invention, the particle component means a component accompanying the shape. The particle component is composed of photocatalyst particles and inorganic oxide particles as essential components, and may be contained 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, SnO ₂ , SrTiO ₃ , WO ₃ or Bi ₂ O _{3 can be used.} And at least one of metal oxides of Fe ₂ O ₃ . It is possible to use only one type or a combination of a plurality of types. A preferred combination of plural kinds includes, for example, crystalline titanium oxide and SnO ₂ , crystalline titanium oxide, and WO ₃ . Any of the metal oxides exemplified herein is also suitable for each constituent combination described later.

The photocatalyst particles are preferably crystalline titanium oxide particles. The crystalline titanium oxide has better water resistance than ZnO. Further, when compared with SnO ₂ , it is possible to exhibit photocatalytic function such as gas decomposition in a large amount of light having a wavelength of 380 nm to 420 nm in sunlight. Further, in comparison with SrTiO ₃ , it is easier to obtain nano-sized fine particles, and therefore has a large specific surface area, and it is easy to obtain practically sufficient photocatalytic activity. In addition, compared to WO ₃ , Bi ₂ O ₃ , and Fe ₂ O ₃ , 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 photocatalytic function such as gas decomposition. The anatase-type titanium oxide particles as the photocatalyst particles can be appropriately combined with each of the above-described respective components, and the above-described effects can be exhibited without impeding the effects.

As the inorganic oxide particles, cerium oxide particles, alumina particles, zirconia 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 a metal compound, a surfactant, or the like.

The photocatalyst layer contains other particles which can be used as an optional component, for example, resin particles such as fluororesin particles, latex, acrylic beads, coloring pigment particles, whiskey fibers, fillers, and the like, mica, talc, glass balls, etc. Creative material particles and so on.

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; zirconium carbonate, zirconium acetate, zirconium formate, etc., which can form a cured product of a precursor of a zirconia 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 Cu ₂ O, CuO or the like, an Ag compound such as Ag or Ag ₂ O, a Pt or Pt compound, Fe or Fe compound, Pd or Pd compound, and the like.

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 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. , polyoxynity nonionic surfactant.

The photocatalyst used in the present invention receives photoexcitation of the hydrophilized system for 1 night without light irradiation, and the change in the contact angle with the water in the hydrophobic direction can be recovered by the solar carbon arc lamp type weather resistance test for 24 hours. Just fine. The daylight carbon arc lamp type weather resistance test was carried out by SUGA Test Machine Co., Ltd. (conditions: light irradiation 30 W/m ² , atmospheric temperature 60 ° C, water irradiation for 120 minutes, water spray for 18 minutes, water temperature 16 ± 5 ° C). The contact angle with water was measured by the method described in JIS R1703-1.

middle 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 cerium oxide component and a soft non-oxygenated resin, and the loss tangent at 25 ° C exceeds 0.2 and does not reach 1.5, preferably exceeds 0.2 and does not reach 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 - Non-Resonance Method") The obtained value was measured in a tensile mode at a frequency of 1 Hz on a solid viscoelasticity measuring apparatus.

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 only of 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, mixing, and crosslinking the above two components or the above two components and other resins or fragments.

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 20,000% by mass or less, and more preferably 200% by mass based on the amount of Si in the cerium oxide component. % or more is 16,000 mass% or less.

Soft non-oxygenated resins may utilize, for example, urethane polyethers, urethane polyesters, urethane polycarbonates, polyethers, polyesters, polyacrylates, polymethacrylates, poly Acrylic acid, polymethacrylic acid, polyethylene, composites of these, such as those modified by oxime or halogen.

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 preferably uses argon which is represented by the following average composition formula (1):

R ¹ _p Si(OR ² ) _q O _(4-pq)/2 (1)

Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group, and R ² is selected from the group consisting of 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; The hydrocarbon group, p and q are those satisfying 0 < p < 4, 0 < q < 4, 0 < (p + q) < 4.

In the above formula, the unsubstituted or substituted one-valent hydrocarbon group of R ¹ is preferably a carbon number of 1 to 18, and the unsubstituted one-valent 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 alkenyl group such as a vinyl group, an allyl group, a 5-hexenyl group or a 9-nonenyl group; an aryl group such as a phenyl group; An aralkyl group such as a phenylethyl group or the like. Further, a part or all of a hydrogen atom substituted with a monovalent hydrocarbon group which is an unsubstituted one-valent hydrocarbon group is substituted with a substituent, and the substituent may be 1) a halogen atom such as fluorine or chlorine, 2) a glycidyloxy group, An epoxy functional group such as an epoxycyclohexyl group; 3) a (meth)acrylic acid functional group such as a methacrylic group or an acrylic group; 4) an amine group, an aminoethylamino group, a phenylamino group, and a dibutylamino group. An amine functional group, 5) a sulfur-containing functional group such as a mercapto group or a tetrasulfide group, an alkyl ether group such as 6) a polyoxyalkylene alkyl ether group, and 7 an anionic group such as a carboxyl group or a sulfonyl group. 8) A group containing a quaternary ammonium salt structure, etc., preferably 2) or 3) as the reactive group, particularly preferably having 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-(N-phenylamino)propyl, 3-dibutylaminopropyl, 3-mercaptopropyl, polyoxyethyloxy A propyl 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, and a phenyl group are preferred.

Examples of the unsubstituted or substituted one-valent hydrocarbon group having 1 to 6 carbon atoms of R ² 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 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.

Further, the oxygen-containing fragment is also the same as described above, and it is preferred to use the oxygen which is represented by the following average composition formula (1):

R ¹ _p Si(OR ² ) _q O _(4-pq)/2 (1)

(wherein R ¹ is an unsubstituted or substituted one-valent hydrocarbon group, and R ² is selected from the group consisting of a hydrogen atom, an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; The hydrocarbon group, p and q are those satisfying 0 < p < 4, 0 < q < 4, 0 < (p + q) < 4.

In the above formula, the unsubstituted or substituted monovalent hydrocarbon group of R ¹ is preferably a carbon number of 1 to 18, and specific examples of the unsubstituted one-valent hydrocarbon group are a methyl group, an ethyl group, a propyl group, an isopropyl group, and 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 alkenyl group such as a vinyl group, an allyl group, a 5-hexenyl group or a 9-nonenyl group; an aryl group such as a phenyl group; An aralkyl group such as a phenylethyl group or the like. Further, the substituted one-valent hydrocarbon group is partially or wholly substituted with one or more of the hydrogen atoms of the unsubstituted one-valent hydrocarbon group, and the substituent may be 1) a halogen atom such as fluorine or chlorine, 2) a glycidyloxy group or a ring. An epoxy functional group such as an oxycyclohexyl group; 3) a (meth)acrylic acid functional group such as a methacrylic group or an acrylic group; 4) an amine group, an aminoethylamino group, a phenylamino group, and a dibutylamino group. An amine functional group, 5) a sulfur-containing functional group such as a mercapto group or a tetrasulfide group, an alkyl ether group such as 6) a polyoxyalkylene alkyl ether group, and 7 an anionic group such as a carboxyl group or a sulfonyl group. 8) A group containing a quaternary ammonium salt structure, etc., preferably 2) or 3) as the reactive group, particularly preferably having an epoxy functional group. 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, N-(2-Aminoethyl)aminopropyl, 3-(N-phenylamino)propyl, 3-dibutylaminopropyl, 3-mercaptopropyl, polyoxyethyloxy Propyl, 3-hydroxycarbonylpropyl, 3-tributylammoniumpropyl and 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 R ² 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 oxygen-containing fragment, a difunctional decane derivative monomer (having two hydrolyzable groups X per molecule and two oxygen atoms bonded to each of the ruthenium atoms) may be contained. A monomer forming a difunctional siloxane chain). 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 that has been modified by halogen or halogen.

Further, in the present invention, the intermediate layer may contain fragments other than the above two, such as a polyester segment, a polyacrylate segment, 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 material, an extender pigment, a bright light adjusting agent, an ultraviolet absorber, a light stabilizer, a film forming aid, a hardener, a surfactant, a viscosity adjuster, 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, barium sulfate Carbonate such as calcium hydride or sedimentary calcium carbonate, metal silicate such as hydrous citrate, limestone or ultramarine, carbonaceous such as carbon black, aluminum powder, bronze powder, zinc powder, and mica ‧Pearl pigments such as titanium oxide.

As the organic pigment, a nitroso pigment such as naphthol green B, a nitro pigment system such as naphthol S, Lithhol Red, Lake Red C, FAST YELLOW, naphthalene can be used. Azo pigments such as phenol red, Alkali blue red, Rhodamine red, Quinacridone Red, Dioxazine violet, isoindolinone yellow, etc. Condensed polycyclic pigment system.

Disperse dyes, basic dyes, direct dyes, 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.

As the brightening adjuster, for example, an inorganic bright light adjusting agent, an organic bright light adjusting agent, or the like can be used. 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 organic light modulating agent, a resin ball such as an acrylic resin ball, a urethane resin ball, a silicone resin powder, or a fluororesin 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, octabenzone, and 2-hydroxy- 4-propoxy benzophenone, 2-hydroxy-4-methylpropoxy benzophenone, 2-hydroxy-5-propoxy benzophenone, 2-hydroxy-5-methyl propylene oxide Benzophenone, 2-hydroxy-4-(acryloxy-ethoxy)benzophenone, 2-hydroxy-4-(acryloxy-ethoxy)benzophenone, 2-hydroxy- 4-(Methacryloxy-diethoxy)benzophenone, 2-hydroxy-4-(acryloxy-triethoxy)diphenyl And other polymerizable benzophenone ultraviolet absorbers or their (co) polymer.

The above benzotriazole-based ultraviolet absorber, specifically, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tributyl) Phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2-hydroxy-5-t-octylbenzene 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-(2H-benzotriazol-2-yl)-4-hydroxyphenyl] Condensate of propionate and polyethylene glycol (molecular weight 300), isooctyl-3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl 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-third-pentylphenyl)benzotriazole, 2-(2'-hydroxy-4 '-Octyloxyphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3",4",5",6"-tetrahydrobenzidine imine methyl)-5' -methylphenyl]benzotriazole, 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2- Phenol], 2-(2H-benzotriazol-2-yl)- 4,6-bis(1-methyl-1-phenylethyl)phenol, and 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxyethyl-3-tert-butylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryl Oxypropyl-3-tert-butylphenyl)-5-chloro-2H-benzotriazole, 3-methylpropenyl-2-hydroxypropyl-3-[3'-(2"- A polymerizable benzotriazole-based ultraviolet absorber such as benzotriazolyl-4-hydroxy-5-tert-butyl]phenylpropionate or the like (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, the weather resistance can be further improved by the effect of multiplying the ultraviolet ray absorbing agent, which is preferable.

Specific examples of hindered amine light stabilizers are bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethylpiperidine). 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- Mixture of 4-piperidinyl) sebacate with methyl-1,2,2,6,6-pentamethyl-4-piperidinyl-sebacate, bis(1-octyloxy-2) , 2,6,6-tetramethyl-4-piperidinyl) sebacate, and 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2 , 2,6,6-pentamethyl-4-piperidyl acrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetra Methyl-4-piperidinyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidinyl methacrylate, 2,2,6,6-tetramethyl- 4-iminopiperidinyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-cyano-1,2,2 , 6,6-pentamethyl-4-piperidyl methacrylate A hindered amine-based ultraviolet absorber or such (co)polymer.

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 aspect of the invention, the intermediate layer fluid may also contain a film forming aid in order to improve its formability. The film-forming auxiliary agent is, for example, isoamyl acetate, oxoacetate acetate, methyl methoxybutyl acetate, ethyl ethoxy propionate, ethylene glycol monobutyl ether acetate, diethylene glycol single Ethyl acetate, diethylene glycol monobutyl ether acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1 , 3-pentanediol diisobutyrate, 2,2,4-trimethyl-1,3-pentanediol mono-2-ethylhexanoate, 2,2,4-trimethyl-1, An ester-based organic solvent such as 3-pentanediol di-2-ethylhexanoate; benzyl alcohol, 2,2,4-trimethyl-1,3-pentanediol isobutyrate (TEXANOL), diethyl Alcohol-based organic solvent such as diol, isotridecyl alcohol, 1,3-octanediol or glycerin; ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monoethyl ether, two An ether-based organic solvent such as ethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol mono 2-ethylhexyl ether, propylene glycol monophenyl ether or tripropylene glycol methyl ether. Can be used alone or in combination.

In accordance with 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.

Specific examples of the curing agent include a compound having a stanol group and/or a hydrolyzable alkyl group, a polyepoxy compound, a polyoxazoline compound, a polyisocyanate, and 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) An organic trialkoxy decane such as propylene methoxy propyl trimethoxy decane; dimethyl dimethoxy decane, dimethyl diethoxy decane, dimethyl di-n-butoxy decane, diethyl two a diorganodialkoxynonane such as methoxydecane, diphenyldimethoxydecane, methylcyclohexyldimethoxydecane or methylphenyldimethoxydecane; methyltrichlorodecane, B Trichlorodecane, phenyltrichlorodecane, vinyltrichlorodecane, 3-(methyl)propenyloxypropyltrichlorodecane, dimethyldichlorodecane, diethyldichlorodecane or diphenyl Various chlorodecanes such as dichlorodecane, or partially hydrolyzed condensates thereof, among which organoalkoxynes are preferably used. Silane organic dialkoxy or di-Silane. These decane compounds may be used singly or in combination of two or more. Other examples are 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidyloxygen Propylmethyldiethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, and the like, and the like, and the like.

The polyepoxy compound may have, for example, an aliphatic or alicyclic polyol structure derived from ethylene glycol, hexanediol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol, hydrogenated bisphenol A or the like. Polyglycidyl ethers; polyglycidyl ethers of aromatic diols such as bisphenol A, bisphenol S, and bisphenol F; polyether polyols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol Glycidyl ether; polyglycidyl ether of ginseng (2-hydroxyethyl) isocyanurate; aliphatic or aromatic of adipic acid, butane tetracarboxylic acid, phthalic acid, terephthalic acid, etc. Polyglycidyl esters of polycarboxylic acids; diepoxides of hydrocarbon-based dienes such as cyclooctadiene and vinylcyclohexene; bis(3,4-epoxycyclohexylmethyl)adipate An alicyclic polyepoxide such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate.

As the above oxazoline compound, for example, 2,2'-p-phenylene-bis(1,3-oxazoline), 2,2'-butylene-bis(1,3-oxazoline), 2,2'-Exenyl-bis(2-oxazoline), 2-isopropenyl-1,3-oxazoline, or such polymers.

As the polyisocyanate, for example, an aromatic diisocyanate such as toluene diisocyanate or diphenylmethane-4,4'-diisocyanate; m-xylene diisocyanate, α,α,α',α'-tetramethyl- can be used. Aralkyl diisocyanates such as m-xylene diisocyanate; hexamethylene diisocyanate, diazonic acid diisocyanate, 1,3-bisisocyanate methylcyclohexane, 2-methyl-1,3-diisocyanate Cyclohexane, 2-methyl-1,5-diisocyanate cyclohexane, isophorone diisocyanate, and the like.

Further, 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 containing an isocyanate group can be used.

The isocyanate group of the polyisocyanate which is a curing agent can be blocked by a conventionally known blocking agent such as methanol, if necessary.

The intermediate layer of the photocatalyst coating material of the present invention can be formed by drying or baking using a coating liquid in which the above components are dispersed in a solvent.

The coating liquid may also contain a surfactant to improve its coatability. As the surfactant, a sulfonic acid polyoxyethylidene ethyl phenyl ether salt, a sulfonic acid polyoxyethylene ethyl phenyl ether salt, a sodium fatty acid sodium soap, a fatty acid potassium soap, a dioctyl sulfobutyl group can be used. Sodium, alkyl sulfate, alkyl ether sulfate, sodium alkyl sulfate, alkyl ether sulfate, polyoxyethylene ethyl ether sulfate, polyoxyethylene ethyl ether sulfate, Alkyl sulfate TEA salt, polyoxyethylene ethyl ether sulfate TEA salt, sodium 2-ethylhexyl alkyl sulfate, sodium mercaptomethyl taurate, sodium lauryl methyl taurate, Sodium dodecylbenzene sulfonate, sodium lauryl sulfosuccinate, polyoxyethylene ethyl sulfosuccinate, sodium lauryl 2, polycarboxylic acid, oleic acid creatinine, indoleamine sulfate An anionic surfactant such as lauryl salicyl salicylate or sulfo-FA ester sodium salt; polyoxy-extension ethyl lauryl ether, polyoxy-extension ethyl tridecyl ether, polyoxy-extension ethyl cetyl wax Ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethylene ethyl ether, polyoxyethylene ethyl ester, polyoxyethylene ethyl phenol ether, Polyoxyethylene ethyl phenyl ether, Oxyethyl octyl phenyl ether, polyoxyethylene ethyl laurate, polyoxyethylene ethyl stearate, polyoxyethylene ethyl phenyl ether, polyoxyethylene ethyl oleate, sorbus Alcoholic anhydride alkyl esters, polyoxyethylene ethyl sorbitan alkyl esters, polyether modified oxime, polyester modified oxime, sorbitan laurate, sorbitan stearate , sorbitan palmitate, sorbitan oleate, sorbitan sesquioleate, polyoxyethyl sorbitan laurate, polyoxyethyl sorbitol Fatty acid ester, polyoxyethylene ethyl sorbitan palmitate, polyoxyethylene sorbitan oleate, glyceryl stearate, polyglycerol fatty acid ester, alkyl alkanolamine, laurel Acid diethanol decylamine, oleic acid diethanol decylamine, oxy extended ethyl dodecylamine, polyoxyethylene ethyl dodecylamine, polyoxyethylidene amine, polyoxyethyl ether Nonionic surfactants such as alkylamine, polyoxyethylene ethyl propylene diamine, polyoxyethylene ethyl propyl block polymer, polyoxyethylene ethyl stearate; dimethyl alkane Betaine, Amphoteric surfactants such as lysine, guanamine, imidazoline, octadecyldimethylbenzylammonium chloride, alkyldimethylbenzylammonium chloride, tetradecylmethylbenzyl Ammonium chloride, dioleyl dimethyl ammonium chloride, 1-hydroxyethyl-2-alkyl imidazoline quaternary salt, alkyl isoquinolinium bromide, polymeric amine, octadecyl trimethyl Ammonium chloride, alkyltrimethylammonium chloride, dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, alkylimidazolinetetra Cationic interface such as grade salt, dialkyldimethylammonium chloride, octadecylamine acetate, tetradecylamine acetate, alkyl propylenediamine acetate, dimercaptodimethylammonium chloride Active agent.

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

The substrate used in the present invention may be any material as long as it is a material on which a photocatalyst layer can be formed, and the shape thereof is not limited. From the viewpoint of materials, preferred examples of the substrate are metal, ceramic, glass, plastic, rubber, stone, cement, concrete, fiber, cloth, wood, paper, combinations of these, laminates thereof, The surface has at least one layer of film on the surface. From the viewpoint of allowing expansion deformation due to water absorption, it is more preferably a metal or a resin from the viewpoint of expansion deformation due to heat, and cement or concrete.

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, and is not limited to a flat shape, and may be used for a curved surface. Any of these substrates may be appropriately combined with each of the above structures.

In particular, the present invention can be suitably used for a substrate having at least a surface formed of an organic material. Here, the base material whose surface is formed of an organic material also includes any one of the base material 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 painted body

Even if the coating body of the present invention is cracked on the photocatalyst film, the adhesion between the substrate and the photocatalyst layer can be ensured, and the crack generated to the surface side and the substrate side can be remarkably suppressed from being propagated or developed, and at the same time, the gas is decomposed. Photocatalytic functions such as functions also have excellent performance. Therefore, the coated body of the present invention is not limited to the following, and is particularly suitable for, for example, (1) vibration application of a bridge or the like, and (2) 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 0 ° C or less. (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 formed. (4) When the photocatalyst layer is formed by bending, (4) When the temperature changes in a day is 20 ° C or more, (5) The substrate is made of metal, resin, rubber, silicone sealant, gasket, etc. At least one of the case where the coefficient of thermal expansion is 10 ^-5 K ^-1 or more, and (6) the temperature difference of the temperature is 30 ° C or more, and the surface of the photocatalyst layer is irradiated from the sun. A situation in which light such as light can excite light of a light source of photocatalyst light.

The above-mentioned coated body may be used in an environment where the surface of the photocatalyst layer may occasionally rain, and may also function as a self-cleaning function with rainfall. Further, by setting the initial stage of the coating film, the contact angle with water is less than 20°, more preferably less than 10°, more preferably less than 5°, whereby a substantially coating film can be exerted. It is excellent in self-cleaning function accompanying rainfall immediately after coating, and it can maintain its hydrophilicity for a long period of time.

[Examples]

Photocatalyst coating liquid modulation

Photocatalyst coating solution 1

A titanium dioxide aqueous dispersion (average particle diameter: 30 to 60 nm) as a photocatalyst, a water-dispersible colloidal ceria (average particle diameter: 20 to 30 nm) as an inorganic oxide, and water are mixed to obtain a solid concentration of 5.5. The mass% and the colloidal cerium oxide content were 90% by mass in the solid content, and the photocatalyst content was 10% by mass in the solid content. In addition, 0.3 parts by mass of the nonionic surfactant is mixed with 100 parts by mass of the photocatalyst coating agent, and when the photocatalyst coating liquid is applied, wettability to the substrate is obtained, and a photocatalyst coating liquid is obtained.

Photocatalyst coating solution 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 30 nm) as an inorganic oxide, tetraethoxy decane, and water are mixed. The composition of the solid content was 5.5% by mass, the colloidal ceria content was 66.2% by mass in the solid content, the tetraethoxydecane content was 26.5% by mass in the solid content, and the photocatalyst content was 7.4% by mass in the solid content. Things. In addition, 0.3 parts by mass of the nonionic surfactant is mixed with 100 parts by mass of the photocatalyst coating agent, and when the photocatalyst coating liquid is applied, wettability to the substrate is obtained, and a photocatalyst coating liquid is obtained.

Photocatalyst coating solution 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, tetraethoxy decane, and water are mixed. A composition having a solid content concentration of 5.5% by mass, a colloidal cerium oxide content of 31% by mass in the solid content, a tetraethoxy decane content of 62.1% by mass in the solid content, and a photocatalyst content of 6.9% by mass in the solid content was obtained. Things. In addition, 0.3 parts by mass of the nonionic surfactant is mixed with 100 parts by mass of the photocatalyst coating agent, and when the photocatalyst coating liquid is applied, wettability to the substrate is obtained, and a photocatalyst coating liquid is obtained.

Photocatalyst coating solution 4

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 an alkoxy oligomer and water are mixed. The solid content concentration was 5.5% by mass, the colloidal ceria content was 86.9 mass% in the solid content, the alkoxy oligomer content was 3.5% by mass in the solid content, and the photocatalyst content was 9.7% by mass in the solid content. Composition. In addition, 0.3 parts by mass of the nonionic surfactant is mixed with 100 parts by mass of the photocatalyst coating agent, and when the photocatalyst coating liquid is applied, wettability to the substrate is obtained, and a photocatalyst coating liquid is obtained.

Photocatalyst coating solution 5

The titanium dioxide aqueous dispersion (average particle diameter: 30 to 60 nm) as a photocatalyst, tetraethoxy decane as an inorganic oxide, and water were mixed to obtain a solid concentration of 5.5% by mass and a tetraethoxy decane content in a solid. The composition was 78.3 mass% in the composition, and the photocatalyst content was 21.7% by mass in the solid content. In addition, 0.3 parts by mass of the nonionic surfactant is mixed with 100 parts by mass of the photocatalyst coating agent, and when the photocatalyst coating liquid is applied, wettability to the substrate is obtained, and a photocatalyst coating liquid is obtained.

Photocatalyst coating liquid 6

The titanium dioxide aqueous dispersion (average particle diameter: 30 to 60 nm) as a photocatalyst, an alkoxy oligomer as an inorganic oxide, and water are mixed to obtain a solid content concentration of 5.5% by mass and an alkoxy oligomer content. The composition was 26.5% by mass in the solid content, and the photocatalyst content was 73.5% by mass in the solid content. In addition, 0.3 parts by mass of the nonionic surfactant is mixed with 100 parts by mass of the photocatalyst coating agent, and when the photocatalyst coating liquid is applied, wettability to the substrate is obtained, and a photocatalyst coating liquid is obtained.

Modulation of the intermediate layer coating solution

The aqueous acrylic oxime resin dispersion used in the following examples had a solid content concentration of 35%, and the aqueous urethane polyether resin dispersion had 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 onto 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 #20 and dried. This operation was repeated until the dry film thickness became about 20 μm. The obtained coating film was cut into a strip shape of 5 mm × 50 mm, and 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.

Intermediate layer coating solution 1

20 parts by mass of an aqueous urethane polyether resin dispersion and 14 parts by mass of a water-based urethane resin polyether dispersion in an amount of 75% by mass in terms of SiO ₂ . A film auxiliary agent, 5.4 parts by mass of a hardener, and 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 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. Further, the loss of the obtained coating film at 25 ° C was 0.28.

Intermediate layer coating solution 2

875 parts of water-based urethane polyether resin dispersion, 45 parts of film-forming auxiliary agent, and 5.4 parts of hardening were added to 100 parts of water-based acrylic oxime resin dispersion containing 75% oxygen content. Agent, 187 parts of 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.

Intermediate layer coating solution 3

Adding 1885 parts of aqueous urethane polyether resin dispersion, 90 parts of film-forming auxiliary agent, and 5.4 parts of hardening to 100 parts of water-based acrylic oxime resin dispersion containing 75% oxygen content. Agent, 343 parts of 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 ratio of the polyoxymethane of the intermediate layer coating liquid 3 was 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 -30 ° C, for the water-based urethane polyether resin dispersion used herein. Further, the coating film obtained from the intermediate layer coating liquid 3 had a loss tangent of 0.52 at 25 °C.

Intermediate layer coating solution 4

10 parts of water-based acrylate-based resin emulsion, 779 parts of film-forming auxiliary agent, and 5.4 parts were added to 100 parts of water-based acrylic acid-oxygen resin dispersion (solid content: 35%) having a nitrogen content of 75%. Hardener, 9576 parts of 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 polyoxymethane of the intermediate layer coating liquid 4 was 0.5%. In addition, 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.

Intermediate layer coating solution 5

In 100 parts of a water-based acrylic oxime resin dispersion (solid content: 35%) having a nitrogen content of 75%, 11444 parts of a water-based acrylate-based resin emulsion, 779 parts of a film-forming auxiliary agent, and 5.4 parts were sequentially added. Hardener, 8433 parts of 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 this intermediate layer coating liquid 5 was 0.5%. In addition, 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 -35 ° C. Moreover, the loss tangent of the coating film obtained from the intermediate layer coating liquid 5 at 25 ° C was 0.48.

Intermediate layer coating solution 6

10 parts of water-based acrylate-based resin emulsion, 779 parts of film-forming auxiliary agent, 5.4 parts of hardening agent, and 9778 parts were added to 100 parts of water-based acrylic oxime resin dispersion containing 75% oxygen content. water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 6 having a solid concentration of 25% was obtained. The ratio of the polyoxymethane of this intermediate layer coating liquid 6 was 0.5%. In addition, 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 coating film obtained from the intermediate layer coating liquid 6 had a loss tangent at 25 ° C of 1.00.

Intermediate layer coating solution 7

In 100 parts of a water-based acrylic oxime resin dispersion having a 矽oxygen content of 75%, 9346 parts of a water-based acrylate-based resin emulsion, 776 parts of a film-forming auxiliary agent, 5.4 parts of a hardening agent, and 10,495 parts were sequentially added. 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 polyoxymethane of this intermediate layer coating liquid 7 was 0.6%. In addition, 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.

Intermediate layer coating solution 8

In 100 parts of water-based acrylic oxime resin dispersion containing 30% oxygen content, 159 parts of aqueous urethane polyether resin dispersion, 14 parts of film-forming auxiliary agent, and 7.7 parts of hardening were sequentially added. Agent, 100 parts of water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 8 having a solid concentration of 25% was obtained. The ratio of the polyoxymethane of this intermediate layer coating liquid 8 was 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 0.48.

Intermediate layer coating liquid 9 (comparative example)

In 100 parts of water-based acrylic oxime resin dispersion containing 75% oxygen content, 67 parts of water-based urethane polyether resin dispersion, 8.3 parts of film-forming auxiliary agent, and 5.4 parts of hardening were sequentially added. Agent, 61 parts of 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 -30 ° C. Further, the coating film obtained from the intermediate layer coating liquid 9 had a loss tangent at 25 ° C of 0.13.

Intermediate layer coating liquid 10 (comparative example)

In 100 parts of water-based acrylic oxime resin dispersion containing 75% oxygen content, 34 parts of water-based urethane polyether resin dispersion, 6.8 parts of film-forming auxiliary agent, and 5.4 parts of hardening were sequentially added. Agent, 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 intermediate layer coating liquid 10 had a polyoxane ratio of 60%. Further, the loss tangent of the coating film obtained from the intermediate layer coating liquid 10 at 25 ° C was 0.09.

Intermediate layer coating liquid 11 (comparative example)

In 100 parts of the water-based acrylic oxime resin dispersion having a cerium oxygen content of 30%, 7.2 parts of a film-forming auxiliary agent, 7.9 parts of a curing agent, and 76.5 parts of water were sequentially added. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 11 having a solid concentration of 25% was obtained. The intermediate layer 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 coating film obtained from the intermediate layer coating liquid 11 had a loss tangent at 25 ° C of 0.10.

Fabrication and evaluation of photocatalyst coating body

The aqueous acrylic resin coating was spray-coated on a flexible sheet so that the dried film thickness became about 20 μm, and dried at 80 ° C for 30 minutes. Then, the aqueous urethane acrylate resin coating material was spray-coated so that the dry film thickness became about 200 μm, and dried at 80 ° C for 30 minutes to obtain a primer coating substrate for adhesion test.

Then, the intermediate layer coating liquids 1 to 11 were spray-coated on the primer substrate for adhesion test which was previously heated to about 50 ° C so that the dry film thickness was 10 μm, and dried at 90 ° C for 2 minutes. Then, the photocatalyst coating liquids 1 to 6 were spray-coated so that the dried film thickness was 0.3 to 0.7 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.

Adhesion performance evaluation

With respect to the photocatalyst-coated body thus obtained, adhesion performance evaluation was performed as follows. First, the photocatalyst-coated body was placed in a solar weathering tester (manufactured by SUGA Test Machine, S-300C) prescribed in JIS B7753, and taken out 100 hours later. Subsequently, it was immersed in water at 60 ° C for 10 hours, and then dried at 100 ° C for 1 hour, and then placed under 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 for 12 hours. The procedure 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 (Model CA-X150 manufactured by Kyowa Interface Science Co., Ltd.). Next, the surface of the obtained coated body was observed 100 times by a scanning electron microscope (manufactured by Hitachi, S800), and the approximate residual ratio of the photocatalyst layer was visually evaluated.

Heat resistant cold test

The heat-resistant cold test was carried out as follows. First, the photocatalyst-coated body was placed in a solar weathering tester (manufactured by SUGA Test Machine, S-300C) prescribed in JIS B7753, and taken out 100 hours later. Subsequently, the mixture was heated at 100 ° C for 1 hour, and then cooled at -20 ° C for 1 hour, and the mixture was repeated 10 times in total for a total test time of 20 hours. The obtained coated body was placed in a solar weathering tester (manufactured by SUGA Test Machine, S-300C) prescribed in JIS B7753, and taken out 100 hours later. The contact angle meter (CA-X150 type manufactured by Kyowa Interface Science Co., Ltd.) was used. ) Determine the contact angle with water.

Bending resistance test

The bending resistance test was carried out as follows. First, the photocatalyst-coated body was placed in a solar weathering tester (manufactured by SUGA Test Machine, S-300C) prescribed in JIS B7753, and taken out 100 hours later. Next, the obtained coated body was bent at 180 Φ by 10 Φ , and then the crack was observed by visual observation. Then, the contact angle of the bent portion with water was measured by a contact angle meter (Model CA-X150 manufactured by Kyowa Interface Science Co., Ltd.).

Vibration resistance test

The vibration resistance test was carried out as follows. First, the photocatalyst-coated body was placed in a solar weathering tester (manufactured by SUGA Test Machine, S-300C) prescribed in JIS B7753, and taken out 100 hours later. The obtained coated body was fixed to a vibration tester, and vibration was applied for 10 minutes under the conditions of a vibration number of 5 Hz and a vibration acceleration of 1 G. The contact angle of the coated body with water after vibration application was measured by a contact angle meter (Model CA-X150 manufactured by Kyowa Interface Science Co., Ltd.).

The above results are shown in the table below.

Further, an 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.

Fig. 1 is a graph showing the temperature change of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4, in which the aqueous urethane polyether resin used in Example 1 is dispersed.

[Fig. 2] Photographs 1 to 5 are electron microscopic observation photographs of coating films after adhesion evaluation tests of Examples 1 to 3, 7 and 8 of the respective Examples.

Claims (29)

A photocatalyst coated body comprising: a substrate; a photocatalyst layer comprising a photocatalyst; a photocatalyst formed between the substrate and the photocatalyst layer and disposed in an intermediate layer in contact with the photocatalyst layer The 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, and the intermediate layer is formed at 25 ° C according to JIS K7244-4. The loss tangent measured by the solid viscoelasticity measuring apparatus exceeds 0.2, which is less than 1.5, and the spectral peak of the intermediate layer by the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus of JIS K7244-4 At least one of more than -80 degrees and less than 30 degrees. For example, in the photocatalyst coating body of claim 1, wherein the aforementioned loss tangent is more than 0.2 and less than 1.0. The photocatalyst coated body of claim 1, wherein the soft non-oxygenated component is a soft non-oxygenated resin or a soft non-oxygenated fragment. 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 is - 40 degrees or more and 30 degrees or less. The photocatalyst coating body according to the first aspect of the invention, wherein the photocatalyst layer is formed by containing photocatalyst particles and inorganic oxide particles as a particle component, and the particle component is contained in an amount of 70% by mass or more. The photocatalyst coated body according to claim 1, wherein the surface of the photocatalyst layer is excited by light of the photocatalyst to exhibit hydrophilicity. The photocatalyst coated body according to claim 6, wherein the surface of the photocatalyst layer is excited by light of the photocatalyst, and exhibits hydrophilicity in a contact angle with water of less than 20°. The photocatalyst coated body according to claim 1 or 5, wherein a ratio of the photocatalyst in the photocatalyst layer is 1% by mass or more and less than 20% by mass. The photocatalyst coated body according to claim 5, wherein the photocatalyst particles have an average particle diameter of 10 nm or more and less than 1000 nm. The photocatalyst coated body according to claim 5, wherein the photocatalyst particles have an average particle diameter of 10 nm or more and less than 100 nm. The photocatalyst coated body according to claim 1, wherein the photocatalyst is crystalline titanium oxide. The photocatalyst coated body according to claim 5, wherein the inorganic oxide particles have an average particle diameter of 5 nm or more and less than 100 nm. The photocatalyst coated body according to claim 5, wherein the inorganic oxide particles are cerium oxide particles. The photocatalyst coated body according to claim 1, wherein the photocatalyst layer has a film thickness of 3 μm or less. The photocatalyst coated body according to claim 5, 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 of the first aspect of the invention, wherein the proportion 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 the first aspect of the invention, 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 coating body of claim 1, wherein the soft non-oxygenated component is selected from the group consisting of polyurethane polyethers, polyurethane polyesters, and polyurethane polyurethanes. A component of at least one of an ester, a polyether, a polyester, a polyacrylate, a polymethacrylate, a polyacrylic acid, a polymethacrylic acid, and a polyvinyl group. The photocatalyst coated body according to claim 1, wherein the soft non-oxygenated component is selected from the group consisting of polyurethane polyethers, polyurethane polyesters, polyethers, and polyacrylate groups. At least one ingredient. A photocatalyst coated body according to any one of claims 1 to 19, which is used in an environment in which vibration is applied to the coated body and the surface of the photocatalyst layer is irradiated with sunlight. The photocatalyst coated body according to any one of claims 1 to 19, wherein the substrate is a porous substrate, and the photocatalyst coated body is disposed in an atmosphere having a temperature of 0 ° C or less. And the surface of the photocatalyst layer is used in an environment where sunlight is irradiated. The photocatalyst coated body according to any one of claims 1 to 19, wherein the substrate is a flexible substrate, and the photocatalyst coated body is bent after forming the photocatalyst layer It is processed and used in the environment where 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 photocatalyst coated body is disposed in a place where the temperature of the day changes to 20 ° C or more, and the surface of the photocatalyst layer Used in an environment 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 coefficient of 10 ^-5 K ^-1 or more, and the surface of the photocatalyst layer is irradiated with sunlight. Used in the environment. The photocatalyst coated body according to any one of claims 1 to 19, wherein the photocatalyst coated body is disposed at a temperature difference of 30 ° C or more, and the surface of the photocatalyst layer is Use in an environment exposed to sunlight. The use of a photocatalyst coating body according to claim 20, wherein the substrate is a bridge. For example, the use of the photocatalyst coating body in the scope of claim 21, wherein the substrate is an unglazed ceramic, concrete, cement board, wood, stone. The photocatalyst coated body according to claim 22, wherein the substrate is at least one of a metal material, a rubber, and a flexible film resin. The 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.