WO2020110523A1 - Matériau composite photocatalytique, élément de protection pour capteurs, élément de protection pour matériaux de construction, élément de protection pour véhicules, élément de protection pour récipients de refroidissement, élément de protection pour caméras de sécurité, capteur, matériaux de construction, véhicule, récipient de refroidissement et caméra de sécurité - Google Patents

Matériau composite photocatalytique, élément de protection pour capteurs, élément de protection pour matériaux de construction, élément de protection pour véhicules, élément de protection pour récipients de refroidissement, élément de protection pour caméras de sécurité, capteur, matériaux de construction, véhicule, récipient de refroidissement et caméra de sécurité Download PDF

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Publication number
WO2020110523A1
WO2020110523A1 PCT/JP2019/041511 JP2019041511W WO2020110523A1 WO 2020110523 A1 WO2020110523 A1 WO 2020110523A1 JP 2019041511 W JP2019041511 W JP 2019041511W WO 2020110523 A1 WO2020110523 A1 WO 2020110523A1
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Prior art keywords
layer
photocatalyst
composite material
inorganic particle
protective member
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Ceased
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PCT/JP2019/041511
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English (en)
Japanese (ja)
Inventor
安永　正
裕之 八重樫
英宏 望月
充 倉沢
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Fujifilm Corp
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Fujifilm Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/395—Thickness of the active catalytic layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B5/00—Doors, windows, or like closures for special purposes; Border constructions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/05—Nuclear magnetic resonance [NMR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/34—Mechanical properties
    • B01J35/36—Mechanical strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/80—Catalysts, in general, characterised by their form or physical properties characterised by their amorphous structures

Definitions

  • the present disclosure relates to a photocatalyst composite material, a sensor protection member, a building material protection member, a vehicle protection member, a cooling container protection member, a surveillance camera protection member, a sensor, a building material, a vehicle, a cooling container and a surveillance camera.
  • Japanese Patent Application Laid-Open No. 9-262481 discloses a method for producing a photocatalyst body in which a catalyst is supported and fixed on a substrate, wherein the photocatalyst and an amorphous titanium peroxide sol are used. A method of making the body is described.
  • JP-A-2002-88276 discloses that an anatase-type titanium oxide fine particle is 0.025 wt% in an aqueous solution containing 0.5 wt% or more and 2.0 wt% or less (titanium oxide equivalent) of amorphous titanium oxide containing a peroxide group.
  • JP-A-2013-104035 contains (A) titanium oxide particles, (B) peroxotitanic acid as a binder component, (C) chelating agent, (D) water, and (E) alcohol.
  • a titanium oxide coating solution is described.
  • a functional layer on a layer containing a photocatalytic material is also being considered.
  • a photocatalyst layer containing a photocatalyst is formed on the surface of the base material.
  • the content of the organic substance in the functional layer is 10 to 40% by mass.
  • a photocatalyst film is formed on the surface of a base material, and a hydrophilic substance film is porously formed on the photocatalyst film.
  • an antifogging element using a coating agent in which photocatalyst particles are dispersed in a titanium peroxide solution obtained by allowing hydrogen peroxide to act on a titanium hydroxide gel (orthotitanic acid) is described.
  • JP-A-2014-111717 discloses an aqueous composition in which an epoxy group-containing alkoxysilane, an epoxy group-free alkoxysilane, and a metal complex are mixed, and the epoxy group-containing alkoxysilane
  • the ratio of the epoxy group-containing alkoxysilane to the total alkoxysilane consisting of the epoxy group-free alkoxysilane and the epoxy group-containing alkoxysilane is 20 to 85% by mass, and the ratio of the metal complex to the epoxy group-containing alkoxysilane.
  • Japanese Patent Publication No. 2012-521014 discloses an optical coating containing porous silica particles, having an average thickness of 75 to 400 nm and a refractive index of 1.0 to 1.4.
  • a functional layer is formed on a layer containing a photocatalytic material, and the function (for example, antireflection property) of the functional layer is provided.
  • the photocatalytic material may be covered with the functional layer, which may reduce the photocatalytic activity. Since a photocatalytic material such as titanium dioxide has a relatively high refractive index, it has a high light reflectance in the wavelength region from the near infrared region to the infrared region. If the desired photocatalytic activity can be achieved while the reflectance is kept low, it is expected that the applications will be expanded.
  • the present disclosure has been made in view of the above.
  • the problem to be solved by one embodiment of the present disclosure is to have excellent photocatalytic activity on the surface of the inorganic particle-containing layer side, and a photocatalytic composite material having excellent antireflection properties when light is incident from the inorganic particle-containing layer side.
  • a problem to be solved by another embodiment of the present disclosure is to have excellent photocatalytic activity on the surface, and excellent antireflection properties when light is incident from the inorganic particle-containing layer side, a protective member for sensor, for building materials
  • a photocatalyst layer containing anatase-type titanium oxide, and a siloxane resin containing an organic structure and an inorganic particle-containing layer containing inorganic particles has a refractive index of 1.5 or more and 2.5 or less measured by ellipsometry at a wavelength of 1000 nm
  • the inorganic particle-containing layer is a photocatalyst composite material having a thickness of 100 nm to 250 nm and a refractive index of less than 1.5 measured by ellipsometry at a wavelength of 1000 nm.
  • ⁇ 2> The photocatalyst composite material according to ⁇ 1>, wherein the photocatalyst layer is a layer containing the anatase-type titanium oxide particles and an amorphous titanium peroxide-type inorganic binder.
  • ⁇ 3> The photocatalyst composite material according to ⁇ 1> or ⁇ 2>, in which the organic structure in the siloxane resin containing an organic structure is a crosslinked structure.
  • ⁇ 4> The photocatalyst composite material according to any one of ⁇ 1> to ⁇ 3>, wherein the inorganic particle-containing layer is a layer that is a cured product of a composition containing an alkoxysilane compound and the inorganic particles. ..
  • ⁇ 5> The photocatalyst composite material according to ⁇ 4>, wherein the alkoxysilane compound contains an epoxy group-containing alkoxysilane compound and an epoxy group-free alkoxysilane compound.
  • ⁇ 6> The photocatalyst composite material according to any one of ⁇ 1> to ⁇ 5>, in which the inorganic particles contain silica particles.
  • An inorganic particle-containing layer is arranged on the photocatalyst layer, and a base material layer is further arranged on the opposite side of the photocatalyst layer from the side on which the inorganic particle-containing layer is arranged.
  • ⁇ 1> to ⁇ 6 > The photocatalyst composite material according to any one of items.
  • a protective member for a sensor including the photocatalytic composite material according to any one of ⁇ 1> to ⁇ 7>.
  • a protective member for building materials comprising the photocatalytic composite material according to any one of ⁇ 1> to ⁇ 7>.
  • a vehicle protection member including the photocatalytic composite material according to any one of ⁇ 1> to ⁇ 7>.
  • a protective member for a cooling container comprising the photocatalytic composite material according to any one of ⁇ 1> to ⁇ 7>.
  • a protective member for a surveillance camera comprising the photocatalytic composite material according to any one of ⁇ 1> to ⁇ 7>.
  • a sensor including the sensor protection member according to ⁇ 8>.
  • a photocatalyst composite material having excellent photocatalytic activity on the surface of the inorganic particle-containing layer side and having excellent antireflection property when light is incident from the inorganic particle-containing layer side is provided. ..
  • the photocatalytic activity on the surface is excellent, and the antireflection property when light is incident from the inorganic particle-containing layer side is also excellent, the sensor protective member, the building material protective member, and the vehicle.
  • a protective member for vehicle, a protective member for surveillance camera, a sensor, a building material, a vehicle, and a surveillance camera are provided.
  • a numerical range represented by “to” means a range including the numerical values before and after “to” as a lower limit value and an upper limit value.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another stepwise described numerical range. ..
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • (meth)acrylic is a term used as a concept including both acryl and methacryl
  • (meth)acryloxy is a term used as a concept including both acryloxy and methacryloxy. is there.
  • the term “process” is included in this term as long as the intended purpose of the process is achieved, not only when it is an independent process but also when it cannot be clearly distinguished from other processes.
  • the amount of each component of the composition means the total amount of the plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the layer, unless otherwise specified.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure are gels using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both manufactured by Tosoh Corporation). It is a molecular weight detected by a differential refractometer using THF (tetrahydrofuran) as a solvent with a permeation chromatography (GPC) analyzer and converted using polystyrene as a standard substance.
  • GPC permeation chromatography
  • the photocatalyst composite material according to the present disclosure includes a photocatalyst layer containing anatase-type titanium oxide and an inorganic particle-containing layer containing a siloxane resin having an organic structure and inorganic particles, and further has another layer as necessary. You may have.
  • the photocatalyst composite material according to the present disclosure preferably has a structure including an inorganic particle-containing layer and a photocatalyst layer in order from the light incident side.
  • the photocatalyst layer in the present disclosure has a refractive index of 1.5 or more and 2.5 or less measured by ellipsometry at a wavelength of 1000 nm
  • the inorganic particle-containing layer has a thickness of 100 nm to 250 nm and an ellipsometer at a wavelength of 1000 nm.
  • the index of refraction measured by metric is less than 1.5.
  • the photocatalyst composite material according to the present disclosure is excellent in photocatalytic activity on the surface of the inorganic particle-containing layer side due to having the above configuration, and antireflection property when light is incident from the inorganic particle-containing layer side. Is excellent in In particular, the photocatalyst composite material according to the present disclosure has excellent antireflection properties for light in the infrared region having a wavelength of 800 nm to 1500 nm.
  • the inorganic particle-containing layer in the present disclosure is provided on the light incident side of the photocatalyst layer and functions as an antireflection layer for incident light, and it is said that the antireflection property is improved when light is incident from the inorganic particle-containing layer side. effective.
  • the functional layer using the material used for the conventional antireflection layer is simply laminated on the conventional photocatalyst layer, the functional layer prevents the radicals generated in the photocatalyst layer from moving to the surface of the functional layer. In some cases, the photocatalytic activity on the surface on the side of the functional layer is lowered because of the deterioration.
  • the mechanism by which the above-mentioned decrease in photocatalytic activity occurs is probably not simple and is considered to involve multiple physical processes.
  • a specific inorganic particle-containing layer as a functional layer on the light incident side of the photocatalyst layer, and appropriately selecting the property (for example, thickness) of the inorganic particle-containing layer.
  • the inorganic particle-containing layer arranged on the light incident side of the photocatalyst layer contains a siloxane resin having an organic structure and inorganic particles, and is formed to have a thickness of 100 nm to 250 nm. I found it.
  • the thickness of the inorganic particle-containing layer is in the range of 100 nm to 250 nm, the reflectance with respect to light in the infrared region having a wavelength of 800 nm to 1500 nm can be suppressed low. This point is different from the behavior in visible light having a wavelength of 400 nm to 800 nm, for example. That is, since the inorganic particle-containing layer has a porous structure, the radicals generated in the photocatalyst layer pass through the pores of the inorganic particle-containing layer while maintaining the effect of reducing the reflection of light by the inorganic particle-containing layer. It is speculated that high photocatalytic activity is maintained by reaching the surface of the material.
  • the photocatalyst layer has a refractive index of 1.5 or more and 2.5 or less, and the inorganic particle-containing layer has a refractive index of less than 1.5, and thus has excellent antireflection properties. It is thought that it has become.
  • the photocatalyst layer in the present disclosure contains at least anatase type titanium oxide, preferably contains an amorphous binder, and may further contain other components as necessary.
  • the refractive index of the photocatalyst layer in the present disclosure is 1.5 or more and 2.5 or less, preferably 1.6 to 2.4, and more preferably 1.7 to 2.3.
  • “refractive index” is a value measured at 25° C. by ellipsometry at a wavelength of 1000 nm, unless otherwise specified.
  • the photocatalyst layer in the present disclosure contains at least one kind of anatase type titanium oxide.
  • the anatase type titanium oxide is not particularly limited, and a commercially available product on the market may be used.
  • the anatase-type titanium oxide may be used in a form contained in the photocatalyst layer as particles of the anatase-type titanium oxide (hereinafter referred to as the first aspect), or the photocatalyst layer is formed as a film of the anatase-type titanium oxide by vapor deposition or the like. It may be used in the above mode (hereinafter, second mode).
  • First Mode As a first mode, a mode in which the photocatalyst layer contains particles of anatase type titanium oxide (hereinafter, also referred to as “anatase type titanium oxide particles” or “titanium oxide particles”) will be described.
  • anatase type titanium oxide particles also referred to as “anatase type titanium oxide particles” or “titanium oxide particles”.
  • the anatase-type titanium oxide particles in the present disclosure are particles having photocatalytic activity.
  • the shape of the titanium oxide particles in the present disclosure is not particularly limited, but it is preferably substantially spherical.
  • the number average particle diameter of the titanium oxide particles is preferably 2 nm to 200 nm, more preferably 5 nm to 50 nm. In the present disclosure, unless otherwise specified, the number average particle diameter is a field emission scanning electron microscope (FE-SEM; for example, SU-8030 type FE-SEM manufactured by Hitachi High-Technologies Corporation (condition: accelerating voltage 2 kV, It is a value calculated by secondary electron image acquisition)).
  • FE-SEM field emission scanning electron microscope
  • the number average particle diameter can be calculated as the arithmetic mean value of the equivalent circle diameters obtained by measuring the projected area of 300 or more particles.
  • the number average particle diameter may be calculated from the commercially available product by the FE-SEM, and a material having a desired particle diameter may be selected and used.
  • the content of titanium oxide (TiO 2 ) in the titanium oxide particles is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more with respect to the total mass of the titanium oxide particles. Is more preferable, and 90% by mass or more is particularly preferable.
  • the components other than TiO 2 contained in the titanium oxide particles include SO 4 2 ⁇ and Na 2 O, but the components are not limited to these and may contain other components.
  • Tio Sky Coat A liquid manufactured by Tio Systems Co., Ltd.
  • anatase type titanium oxide particles can be used.
  • the content of titanium oxide particles in the present disclosure is preferably 5 mass% to 95 mass% and more preferably 10 mass% to 90 mass% with respect to the total mass of the photocatalyst layer.
  • the photocatalyst layer in the present disclosure may contain titanium oxide particles alone, or may contain two or more kinds of titanium oxide particles.
  • the photocatalyst layer in the present disclosure is preferably a layer containing an amorphous titanium peroxide type inorganic binder in addition to the anatase type titanium oxide particles.
  • the amorphous titanium peroxide type inorganic binder is an amorphous binder containing a Ti—O bond.
  • the amorphous titanium peroxide type inorganic binder is preferably obtained by heating peroxotitanic acid. Specifically, it is considered that by heating peroxotitanic acid at 100° C. to 150° C. for several hours, an oxygen atom or a hydroxy group is eliminated from peroxotitanic acid to obtain a titanium oxide.
  • the titanium oxide does not crystallize and exists as amorphous titanium oxide (amorphous titanium peroxide).
  • amorphous titanium oxide is referred to as an amorphous titanium peroxide type inorganic binder.
  • the anatase phase may be formed in at least a part of the amorphous titanium oxide by increasing the heating temperature of peroxotitanic acid, lengthening the heating time, or the like.
  • the peroxotitanic acid is not particularly limited, but can be obtained by reacting titanium hydroxide (orthotitanic acid) with hydrogen peroxide. Titanium hydroxide is obtained, for example, by reacting titanium tetrachloride with a base.
  • JP-A-9-262481 can be referred to.
  • the content of the amorphous titanium peroxide type inorganic binder is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, based on the total mass of the photocatalyst layer.
  • the photocatalyst layer in the present disclosure may contain one kind of amorphous titanium peroxide type inorganic binder alone, or may contain two or more kinds thereof.
  • the fact that the amorphous titanium peroxide type inorganic binder is contained in the photocatalyst layer can be judged by carrying out the structure identification by the analysis peak and the confirmation that the crystal peak does not appear by X-ray diffraction measurement or Raman spectroscopy measurement. it can.
  • the photocatalyst layer in the present disclosure may further contain other components.
  • known additives such as surfactants can be used without particular limitation.
  • the thickness of the photocatalyst layer is not particularly limited, and from the viewpoint of photocatalytic activity, it is preferably 50 nm or more, more preferably 100 nm or more, and further preferably 200 nm or more.
  • the thickness of the photocatalyst layer is preferably 2,000 nm or less, and preferably 1,000 nm or less, from the viewpoint of suppressing the occurrence of cracks and poor adhesion due to an increase in shrinkage stress during coating film formation. Is more preferable.
  • the thickness of the photocatalyst layer is a value measured using a contact-type film thickness meter (for example, contact-type film thickness meter manufactured by Anritsu Corporation).
  • the photocatalyst layer in the present disclosure can be formed by applying the composition for forming a photocatalyst layer to, for example, a substrate described below and heating the composition.
  • the composition for forming a photocatalyst layer preferably contains the above-mentioned titanium oxide particles and peroxotitanic acid.
  • the composition for forming a photocatalyst layer is prepared by adding titanium oxide particles to a composition containing peroxotitanic acid and a solvent and dispersing the particles.
  • a commercially available product can be used, and for example, TIO SKYCOAT A liquid (manufactured by Tio Systems Co., Ltd.) can be used.
  • a thickener can be added to the photocatalyst layer-forming composition.
  • the thickener include hydroxyalkyl (C1 to C3) cellulose and the like.
  • a method of applying the composition for forming the photocatalyst layer and heating (that is, drying) a plurality of times may be adopted.
  • the coating method for coating the composition for forming a photocatalyst layer is not particularly limited, and a known method may be used, and examples thereof include slit coating, spin coating, curtain coating, inkjet coating and the like.
  • the heating method for drying the photocatalyst layer-forming composition (coating film) after coating is not particularly limited, and a known method may be used. Examples of the heating method include a method using a heater, an oven, a hot plate, an infrared lamp, an infrared laser and the like. The heating time and the heating temperature at the time of heating may be appropriately adjusted in consideration of the heating time and the heating temperature in the production of the above-mentioned amorphous titanium peroxide type inorganic binder.
  • Second Mode As a second mode of the photocatalyst layer, a mode in which the photocatalyst layer is formed as a film of anatase type titanium oxide by a vapor deposition method or the like will be described.
  • the details other than the method such as the vapor deposition method are the same as those in the first aspect, and the preferable aspects are also the same.
  • the method for forming the anatase-type titanium oxide film is not particularly limited, and known methods such as vapor deposition can be used. For example, after a titanium oxide film is formed on a base material layer (for example, glass) described later by a known vapor deposition method or the like, heating is performed at a temperature of, for example, 400° C. or higher and 700° C. or lower to change the crystal structure of titanium oxide to anatase type. And the like.
  • a base material layer for example, glass
  • heating is performed at a temperature of, for example, 400° C. or higher and 700° C. or lower to change the crystal structure of titanium oxide to anatase type. And the like.
  • the method for making it porous is not particularly limited, and a known method can be used.
  • the thickness of the photocatalyst layer in the second aspect is the same as the thickness of the photocatalyst layer in the above-mentioned first aspect, and its preferable range is also the same.
  • the inorganic particle-containing layer contains a siloxane resin having an organic structure and inorganic particles.
  • the inorganic particle-containing layer preferably further contains a metal complex (curing agent), and may further contain other additives such as a surfactant, if necessary.
  • the inorganic particle-containing layer is the hard coat layer described below, the inorganic particle-containing layer is preferably the outermost layer in the photocatalyst composite material according to the present disclosure.
  • the photocatalyst composite material according to the present disclosure may further have a known protective layer such as a hard coat layer on the inorganic particle-containing layer.
  • the refractive index of the inorganic particle-containing layer in the present disclosure is less than 1.5, preferably 1.3 or more and less than 1.5, and more preferably 1.4 or more and less than 1.5.
  • the refractive index of the inorganic particle-containing layer depends on the type of siloxane resin having an organic structure, the material of the inorganic particles contained, the content of the inorganic particles, the structure of the inorganic particle-containing layer (porous structure, etc.), It can be adjusted depending on the thickness and the like.
  • the method for measuring the refractive index of the inorganic particle-containing layer is as described above.
  • the inorganic particle-containing layer in the present disclosure contains at least one kind of inorganic particles.
  • the inorganic particles may be crosslinked with a siloxane resin having an organic structure in the inorganic particle-containing layer.
  • examples of the inorganic particles include metal oxide particles that are transparent to light having a wavelength of 350 nm. Further, in applications such as sensors, building materials, vehicles, cooling containers, and surveillance cameras, which will be described later, the metal oxide particles are preferably transparent to light having a wavelength of 800 nm to 1500 nm (wavelength A). ..
  • being transparent to the light of wavelength A means having a transmittance of 50% or more for the light of wavelength A.
  • the transmittance is preferably 70% or more, more preferably 80% or more.
  • the reflectance is preferably less than 50%, more preferably less than 20%, even more preferably less than 10% with respect to the light of wavelength A.
  • “transparent to wavelengths A to B” means that when the transmittance of light having a wavelength between wavelength A and wavelength B is measured in steps of 10 nm, the arithmetic mean value of all transmittances is 50. % Or more.
  • the transmittance is preferably 70% or more, more preferably 80% or more. Further, the transmittance is measured using a spectrophotometer V670 (manufactured by JASCO Corporation).
  • the metal oxide particles include particles of silicon dioxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), and the like.
  • the metal oxide particles are preferably silica particles from the viewpoint of crosslinkability with an alkoxysilane compound described later. Further, the metal oxide particles are preferably silica particles from the viewpoint of further improving the antireflection property. Colloidal silica is preferable as the silica particles.
  • Commercially available products may be used as the silica particles. Examples of commercially available products include Snowtex series (colloidal silica; examples: Snowtex OXS, Snowtex OZL, Snowtex AK-A, etc.) manufactured by Nissan Chemical Industries, Ltd.
  • silica particles dry powdery silica produced by combustion of silicon tetrachloride can be used, but colloidal silica in which silicon dioxide or a hydrate thereof is dispersed in water is more preferable. Specific examples thereof include, but are not limited to, Snowtex series manufactured by Nissan Chemical Industries, Ltd. such as Snowtex O33.
  • the number average particle size of the colloidal silica is preferably 3 nm to 100 nm, more preferably 3 nm to 50 nm, further preferably 4 nm to 50 nm, further preferably 4 nm to 40 nm, further preferably 5 nm to 35 nm is particularly preferable.
  • the colloidal silica has a pH adjusted to a range of 2 to 7 when added to the composition for forming an inorganic particle-containing layer described below.
  • the pH is 2 to 7
  • the stability of silanol, which is a hydrolyzate of an alkoxysilane compound, is better, and the increase in viscosity of the coating liquid due to the rapid progress of the dehydration condensation reaction of the silanol can be suppressed. it can.
  • the number average particle diameter of the inorganic particles in the present disclosure is preferably 3 nm to 100 nm, more preferably 4 nm to 50 nm, further preferably 4 nm to 40 nm, and particularly preferably 4 nm to 20 nm. ..
  • the number average particle diameter may be calculated from the commercially available product by the above-mentioned FE-SEM, and a material having a desired particle diameter may be selected and used.
  • the shape of the inorganic particles in the present disclosure is not particularly limited, but from the viewpoint of dispersibility, it is preferably substantially spherical.
  • the inorganic particle-containing layer may contain one kind of inorganic particles or two or more kinds of inorganic particles.
  • the content of the inorganic particles in the inorganic particle-containing layer is preferably more than 0% by mass and 80% by mass or less, and preferably 1% by mass to 70% by mass, based on the total mass of the inorganic particle-containing layer. More preferably, it is more preferably 3% by mass to 65% by mass.
  • the inorganic particle-containing layer in the present disclosure contains at least one kind of siloxane resin having an organic structure.
  • the “organic structure” refers to a partial structure containing a carbon atom and bonded to —SiO— constituting the siloxane resin.
  • the “organic structure” in the siloxane resin containing an organic structure is preferably a crosslinked structure.
  • the “crosslinked structure” refers to a partial structure in which —SiO— skeletons are connected to each other to form a two-dimensional or three-dimensional network structure.
  • the siloxane resins may be crosslinked, or the siloxane resin and the inorganic particles may be crosslinked.
  • the organic structure can be confirmed by the intensity ratio of peak intensities calculated by a conventional method from nuclear magnetic resonance (NMR) spectrum measurement.
  • the crosslinked structure can be confirmed by not dissolving when the siloxane resin is dissolved in an organic solvent (for example, toluene).
  • the organic structure contained as the crosslinked structure is preferably a structure represented by any of the following formulas 1-1 to 1-3.
  • R 11 represents a single bond, an oxygen atom, an alkyleneoxy group, an aryleneoxy group, an alkyleneoxyalkylene group, an aryleneoxyalkylene group, or an alkylene group
  • R 12 to R 14 are Each independently represents a hydrogen atom or an alkyl group, at least two of R 12 to R 14 may be bonded to each other to form a ring structure
  • R 21 represents a single bond or an alkylene group
  • R 31 represents A single bond, an alkyleneoxycarbonyl group, an alkyleneaminocarbonyl group, an alkyleneoxy group, an oxygen atom or an arylene group
  • R 32 represents a hydrogen atom or an alkyl group
  • the structure represented by Formula 1-1 is formed, for example, by using an alkoxysilane compound having an epoxy group as the alkoxysilane compound described below.
  • R 11 is preferably an oxygen atom or an alkyleneoxy group.
  • R 12 to R 14 are hydrogen atoms.
  • R 12 or R 13 and R 14 bond together.
  • a hydrocarbon ring is preferable, and a cyclohexane ring is more preferable.
  • the target to which *, which is the binding site, is bound is not particularly limited, but is preferably a Si atom or an organic group contained in the siloxane resin, and more preferably a Si atom contained in the siloxane resin. preferable.
  • the target to which the binding site ** is bound is not particularly limited, but is preferably an oxygen atom contained in the siloxane resin.
  • the alkoxysilane compound * is bonded to the Si atom
  • R 11 is a propyleneoxy group
  • R 12 to R 14 are hydrogen atoms.
  • ** is bonded to an oxygen atom or the like in the siloxane resin.
  • the structure represented by Formula 1-2 is formed, for example, by using an alkoxysilane compound having an isocyanate group as the alkoxysilane compound described later.
  • R 21 represents a single bond or an alkylene group, and is preferably an alkylene group having 2 to 10 carbon atoms.
  • the target to which *, which is the binding site, is bound is not particularly limited, but is preferably a Si atom or an organic group contained in the siloxane resin, and more preferably a Si atom contained in the siloxane resin. preferable.
  • the object to which the binding site ** is bound is not particularly limited, but is preferably an oxygen atom contained in the siloxane resin.
  • R 31 preferably represents an alkyleneoxycarbonyl group, an alkyleneaminocarbonyl group or an arylene group, and has an alkyleneoxycarbonyl group having 2 to 10 carbon atoms, an alkyleneaminocarbonyl group having 2 to 10 carbon atoms or phenylene.
  • a group is more preferable, and an alkyleneoxycarbonyl group having 2 to 10 carbon atoms is further preferable.
  • the target to which the binding site * is bound is not particularly limited, but is preferably a Si atom or an organic group contained in the siloxane resin, and more preferably a Si atom contained in the siloxane resin. preferable.
  • the target to which **, which is the binding site, binds is not particularly limited, but it is preferably ** having a structure represented by another Formula 1-3.
  • 3-methacryloxypropylmethyldiethoxysilane is used as the alkoxysilane compound
  • * is bonded to the Si atom and R 31 is a propyleneoxycarbonyl group.
  • ** is bonded to a methacryloxy group in another 3-methacryloxypropylmethyldiethoxysilane.
  • the siloxane resin containing an organic structure used in the present disclosure may further have a group such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group, and a carboxy group as an organic structure.
  • the content ratio of the organic structure in the siloxane resin is preferably 90% by mass or less, and preferably 75% by mass or less, based on the total mass of the siloxane resin. More preferable.
  • the lower limit of the content ratio of the organic structure in the siloxane resin can be 5% by mass or more in terms of film strength.
  • the inorganic particle-containing layer may contain one type of siloxane resin containing an organic structure, or may use two or more types in combination.
  • the content of the siloxane resin containing an organic structure in the inorganic particle-containing layer is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 35% by mass or more, based on the total mass of the inorganic particle-containing layer. ..
  • the content of the siloxane resin containing an organic structure in the inorganic particle-containing layer is preferably 99% by mass or less, more preferably 97% by mass or less, and further preferably 90% by mass or less.
  • the inorganic particle-containing layer in the present disclosure can be formed by curing a composition containing at least a siloxane resin having an organic structure and inorganic particles (a composition for forming an inorganic particle-containing layer).
  • a layer obtained by curing an inorganic particle-containing layer forming composition containing at least inorganic particles is a preferred embodiment. That is, the siloxane resin containing an organic structure is preferably a hydrolysis-condensation product of an alkoxysilane compound.
  • the composition for forming an inorganic particle-containing layer is preferably an aqueous composition containing water as a solvent. Since both the titanium oxide particles in the photocatalyst layer and the amorphous titanium peroxide type inorganic binder have low solubility in water, the composition for forming an inorganic particle-containing layer contains water, so that after the formation of the photocatalyst layer, the inorganic material is formed on the photocatalyst layer. Mixing between layers is prevented even when the composition for forming a particle-containing layer is applied.
  • the composition for forming an inorganic particle-containing layer preferably contains substantially no organic solvent.
  • substantially free from means that the content is less than 1% by mass, and preferably less than 0.1% by mass.
  • the alkoxysilane compound As the alkoxysilane compound, it is preferable to use a water-soluble or water-dispersible material from the viewpoint of reducing environmental pollution due to VOC (volatile organic compounds).
  • the alkoxysilane compound preferably contains a crosslinkable group-containing alkoxysilane compound and a crosslinkable group-free alkoxysilane compound, an epoxy group-containing alkoxysilane compound, and an epoxy group-free alkoxysilane compound, It is more preferable to include
  • the crosslinkable group-containing alkoxysilane compound and the non-crosslinkable group-containing alkoxysilane compound each have a hydrolyzable group.
  • the hydrolyzable group is hydrolyzed in, for example, an acidic aqueous solution to produce silanol, and the silanols are condensed with each other to produce a siloxane resin.
  • a part of the crosslinkable group-containing alkoxysilane compound and the crosslinkable group-free alkoxysilane compound may be hydrolyzed.
  • crosslinkable group in the crosslinkable group-containing alkoxysilane compound examples include an epoxy group, an isocyanate group and a radical polymerizable group.
  • examples of the crosslinkable group-containing alkoxysilane compound include an epoxy group-containing alkoxysilane compound, an isocyanate group-containing alkoxysilane compound, and a radically polymerizable group-containing alkoxysilane compound, and an epoxy group-containing alkoxysilane compound is preferable.
  • Epoxy group-containing alkoxysilane compound is an alkoxysilane compound having an epoxy group.
  • the epoxy group-containing alkoxysilane compound may be one having at least one epoxy group in one molecule, and the number of epoxy groups is not particularly limited.
  • the epoxy group-containing alkoxysilane compound may further have groups such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group and a carboxy group in addition to the epoxy group.
  • Examples of the epoxy group-containing alkoxysilane compound used in the present disclosure include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and 2-(3,4 -Epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, Examples thereof include 3-glycidoxypropyltriethoxysilane. Examples of commercially available products include KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the isocyanate group-containing alkoxysilane compound is an alkoxysilane compound having an isocyanate group.
  • the isocyanate group-containing alkoxysilane compound may be one having at least one isocyanate group in one molecule, and the number of isocyanate groups is not particularly limited.
  • the isocyanate group-containing alkoxysilane compound may further have groups such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group and a carboxy group, in addition to the isocyanate group.
  • Examples of the isocyanate group-containing alkoxysilane compound used in the present disclosure include 3-isocyanatepropyltriethoxysilane and 3-isocyanatepropyltrimethoxysilane.
  • Examples of commercially available products include KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the radical polymerizable group-containing alkoxysilane compound is an alkoxysilane compound having a radical polymerizable group.
  • the radical polymerizable group-containing alkoxysilane compound may be one having at least one radical polymerizable group in one molecule, and the number of radical polymerizable groups is not particularly limited.
  • the radically polymerizable group is not particularly limited, and examples thereof include (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, vinyl group, and allyl group.
  • the radical-polymerizable group-containing alkoxysilane compound may further have groups such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group and a carboxy group, in addition to the radical-polymerizable group. ..
  • radical polymerizable group-containing alkoxysilane compound used in the present disclosure examples include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropyltrimethoxysilane. , 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane and the like.
  • compositions for forming an inorganic particle-containing layer contain a radically polymerizable group-containing alkoxysilane compound
  • the composition for forming an inorganic particle-containing layer may further contain a known radical polymerization initiator.
  • the content of the crosslinkable group-containing alkoxysilane compound, the stability of the inorganic particle-containing layer forming composition, and from the viewpoint of improving the alkali resistance of the resulting inorganic particle-containing layer, to the inorganic particle-containing layer forming composition is preferably 20% by mass to 85% by mass with respect to the total mass of the alkoxysilane compound contained.
  • the content of the crosslinkable group-containing alkoxysilane compound is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 30% by mass or more. Further, the content of the crosslinkable group-containing alkoxysilane compound is preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less.
  • the crosslinkable group-free alkoxysilane compound is an alkoxysilane compound having no crosslinkable group.
  • the crosslinkable group-free alkoxysilane compound may be any alkoxysilane compound having no crosslinkable group, and may have a group such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group or a carboxy group. You may have.
  • the crosslinkable group-free alkoxysilane compound is preferably a tetraalkoxysilane compound or a trialkoxysilane compound, or a mixture of a tetraalkoxysilane compound and a trialkoxysilane compound. Above all, a mixture of a tetraalkoxysilane compound and a trialkoxysilane compound is more preferable.
  • the crosslinkable group-free alkoxysilane compound is a mixture of a tetraalkoxysilane compound and a trialkoxysilane compound
  • the molar ratio of the tetraalkoxysilane compound to the trialkoxysilane compound is 25:75 to 85:15.
  • the ratio is more preferably 30:70 to 80:20, further preferably 30:70 to 65:35.
  • the degree of polymerization of the alkoxysilane compound can be easily controlled within a desired range, and the hydrolysis rate and the solubility of the aluminum chelate can be easily controlled.
  • the tetraalkoxysilane compound is a tetrafunctional alkoxysilane compound, and it is more preferable that each alkoxy group has 1 to 4 carbon atoms. Among them, a tetramethoxysilane compound or a tetraethoxysilane compound is more preferable.
  • the carbon number of the tetraalkoxysilane compound is 4 or less, the hydrolysis rate of the tetraalkoxysilane compound does not become too slow when mixed with the tetraalkoxysilane compound and acidic water, and a uniform aqueous solution is obtained. It takes less time to dissolve. Thereby, the production efficiency in producing the inorganic particle-containing layer can be increased.
  • Examples of commercially available tetraalkoxysilane compounds include KBE-04 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the trialkoxysilane compound is preferably a trifunctional alkoxysilane compound represented by the following formula A.
  • R-Si(OR 1 ) 3 ...
  • Formula A R represents an organic group containing no amino group and having 1 to 15 carbon atoms, and R 1 represents an alkyl group having 1 to 4 carbon atoms.
  • the trifunctional alkoxysilane compound represented by the formula A is preferable in that it does not contain an amino group as a functional group as described above. That is, a trifunctional alkoxysilane compound has an organic group R having no amino group, and when R does not have an amino group, it is produced when mixed with a tetrafunctional alkoxysilane compound and hydrolyzed. Dehydration condensation is not easily promoted between silanols, and the stability of the composition for forming an inorganic particle-containing layer is improved.
  • R may be any organic group having 1 to 15 carbon atoms. By setting the carbon number to 15 or less, the flexibility of the inorganic particle-containing layer does not become too large, and sufficient hardness can be obtained. Further, by setting the carbon number of R within the above range, an inorganic particle-containing layer excellent in brittleness can be obtained. Furthermore, the adhesion between the photocatalyst layer and the inorganic particle-containing layer can be enhanced. Further, R is preferably a group in which the Si atom in formula A and the carbon atom in R are directly bonded. The organic group represented by R may have a hetero atom such as oxygen, nitrogen or sulfur. Since the organic group has a hetero atom, the adhesion with the photocatalyst layer can be enhanced.
  • trialkoxysilane compounds include 3-chloropropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-ureidopropyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, and ethyl.
  • examples thereof include triethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane and phenyltrimethoxysilane.
  • methyltriethoxysilane and methyltrimethoxysilane are particularly preferably used.
  • the trialkoxysilane compound a commercially available commercially available product may be used, and examples of the commercially available product include KBE-13 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
  • the inorganic particle-containing layer forming composition contains at least one kind of inorganic particles.
  • the inorganic particles in the composition for forming an inorganic particle-containing layer are the same as the inorganic particles in the above-mentioned inorganic particle-containing layer, and the preferred embodiments are also the same.
  • the content of the inorganic particles in the composition for forming an inorganic particle-containing layer is, from the viewpoint of photocatalytic activity and alkali resistance of the inorganic particle-containing layer, the content of the inorganic particles with respect to the total solid content of the composition for forming an inorganic particle-containing layer is x.
  • x When it is defined as% by mass, it is preferable that 0% by mass ⁇ x% by mass ⁇ 80% by mass.
  • the x mass% is more preferably 1 mass% or more, further preferably 3 mass% or more. Further, x mass% is preferably 80 mass% or less, more preferably 70 mass% or less, and further preferably 65 mass% or less.
  • the content of the inorganic particles with respect to the total solid content of the composition for forming an inorganic particle-containing layer is x mass %
  • the content of the crosslinkable group-containing alkoxysilane compound with respect to the total mass of the alkoxysilane compound is y mass %.
  • y mass% ⁇ x mass% ⁇ 5 mass% is preferable
  • y mass% ⁇ x mass% is more preferable.
  • composition for forming an inorganic particle-containing layer preferably contains at least one kind of metal complex (curing agent).
  • the inorganic particle-containing layer in the present disclosure preferably contains a metal complex.
  • a metal complex having at least one metal selected from the group consisting of Al, Mg, Mn, Ti, Cu, Co, Zn, Hf and Zr is preferable, and these can be used in combination.
  • the metal complex can be easily obtained by reacting a metal alkoxide with a chelating agent.
  • a chelating agent include ⁇ -diketones such as acetylacetone, benzoylacetone and dibenzoylmethane; ⁇ -keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate.
  • metal complex examples include ethyl acetoacetate aluminum diisopropylate, aluminum tris(ethylacetoacetate), alkylacetoacetate aluminum diisopropylate, aluminum monoacetylacetate bis(ethylacetoacetate), aluminum tris(acetylacetate).
  • Acetonate and other aluminum chelate compounds
  • ethyl acetoacetate magnesium monoisopropylate magnesium bis(ethylacetoacetate), alkylacetoacetate magnesium monoisopropylate, magnesium bis(acetylacetonate) and other magnesium chelate compounds
  • zirconium tetraacetylacetate Examples include nato, zirconium tributoxyacetylacetonate, zirconium acetylacetonate bis(ethylacetoacetate), manganese acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, titanium acetylacetonate, and titanium oxyacetylacetonate.
  • aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate), magnesium bis(acetylacetonate), magnesium bis(ethylacetoacetate), and zirconium tetraacetylacetonate are preferable.
  • aluminum tris(acetylacetonate) and aluminum tris(ethylacetoacetate) which are aluminum chelate complexes are particularly preferable.
  • the metal complex may be a commercially available commercially available product, and examples of the commercially available product include aluminum chelate A (W), aluminum chelate D, aluminum chelate M (manufactured by Kawaken Fine Chemicals Co., Ltd.) and the like. ..
  • the content of the metal complex in the inorganic particle-containing layer forming composition is preferably 17 mol% to 70 mol% with respect to the total molar amount of the crosslinkable group-containing alkoxysilane compound.
  • the content of the metal complex is more preferably 20 mol% or more.
  • the content of the metal complex is preferably 70 mol% or less, more preferably 65 mol% or less, and further preferably 60 mol% or less.
  • excellent alkali resistance can be obtained when the metal particle-containing layer is formed.
  • the content of the metal complex is 70 mol% or less, the dispersibility of the metal complex in the composition for forming an inorganic particle-containing layer can be improved and the production cost can be suppressed.
  • the inorganic particle-containing layer forming composition used in the present disclosure, and the inorganic particle-containing layer may be added with a surfactant for the purpose of improving the smoothness of the layer and reducing the friction on the surface of the coating film. ..
  • a surfactant include the surfactants described in paragraphs 0039 to 0044 of JP-A-2014-111717.
  • the inorganic particle-containing layer may be colored by dispersing a pigment or dye, other particles and the like in the inorganic particle-containing layer.
  • an antioxidant or the like may be added to the composition for forming an inorganic particle-containing layer and the inorganic particle-containing layer used in the present disclosure for the purpose of improving weather resistance.
  • the thickness of the inorganic particle-containing layer is 100 nm to 250 nm, preferably 100 nm to 200 nm.
  • the thickness of the inorganic particle-containing layer can be controlled by adjusting the coating amount of the composition for forming an inorganic particle-containing layer.
  • the inorganic particle-containing layer can be formed by applying the composition for forming an inorganic particle-containing layer on the photocatalyst layer and drying the composition.
  • the method for applying the composition for forming an inorganic particle-containing layer is not particularly limited, and a known method can be used, and examples thereof include slit coating, spin coating, curtain coating, inkjet coating and the like.
  • the heating method for drying the composition (coating film) for forming an inorganic particle-containing layer after coating is not particularly limited, and a known method may be used. Examples of the heating method include a method using a heater, an oven, a hot plate, an infrared lamp, an infrared laser and the like.
  • the thickness of the layer containing the inorganic particles is a value measured by using Dektak150 manufactured by Bruker.
  • An easy-adhesion layer to be described later may be further provided between the inorganic particle-containing layer and the photocatalyst layer.
  • the inorganic particle-containing layer is preferably provided as an antireflection layer. Further, as the antireflection layer, it is possible to impart a plurality of functions such as an antireflection layer having excellent scratch resistance.
  • the refractive index is a value measured at 25° C. by ellipsometry at a wavelength of 1000 nm, unless otherwise specified.
  • the photocatalyst composite material according to the present disclosure preferably has a base material layer on the side of the photocatalyst layer opposite to the side having the inorganic particle-containing layer (inorganic particle-containing layer side). That is, the photocatalyst composite material according to the present disclosure preferably has an inorganic particle-containing layer/photocatalyst layer/base material layer laminated structure.
  • the base material layer is a layer formed of a base material, and examples of the base material in the base material layer include a resin base material, a glass base material, and a metal base material.
  • the resin base material is not particularly limited, but polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), polyarylate, polyether sulfone, polycarbonate, polyether Preferred are ketones, polysulfones, polyphenylene sulfides, polyester type liquid crystal polymers, triacetyl cellulose, cellulose derivatives, polypropylene, polyamides, polyimides, polycycloolefins and the like.
  • the resin substrate may be stretched and is preferably biaxially stretched.
  • Biaxial stretching refers to stretching in both directions by regarding the width direction and the longitudinal direction of the resin film as uniaxial.
  • the biaxially stretched resin base material has very excellent mechanical strength because the biaxial molecular orientation is sufficiently controlled.
  • the stretching ratio is not particularly limited, but the stretching ratio in one direction is preferably 1.5 times to 7 times, more preferably 2 times to 5 times.
  • a resin base material that has been biaxially stretched at a draw ratio of 2 to 5 times per uniaxial direction has very excellent mechanical strength because the molecular orientation is controlled more efficiently and effectively. Suitable as a resin base material.
  • the glass substrate is not particularly limited, but it is a transparent glass plate, a shaped glass plate, a netted glass plate, a wire-containing glass plate, a tempered glass plate, a heat-ray reflective glass plate, a heat-ray absorbing glass plate, Low-E (Low Emissivity, A glass substrate such as a (low reflection) glass plate may be used.
  • the metal base material is not particularly limited, and examples thereof include an aluminum plate, a steel plate, a copper plate, and other alloy plates.
  • the base material used as the base material layer may be surface-treated.
  • the surface treatment corona treatment and glow treatment are preferable from the viewpoint of process simplicity.
  • the surface treatment By applying the surface treatment, the surface of the base material is made hydrophilic and the wettability can be improved. Thereby, the adhesion with the photocatalyst layer or the adhesion with the easy-adhesion layer can be enhanced.
  • the corona treatment performed under normal pressure has a simpler process than the glow treatment performed under reduced pressure, but the glow treatment has a higher effect of improving the adhesion.
  • the photocatalyst composite material according to the present disclosure may have an easy-adhesion layer.
  • the adhesiveness between the base material layer and the photocatalyst layer or the adhesiveness between the photocatalyst layer and the inorganic particle-containing layer can be improved.
  • the easy-adhesion layer is, for example, a surface of the base material layer on which the photocatalyst layer is provided, or a surface of the photocatalyst layer on which the inorganic particle-containing layer is provided, with a coating liquid including a binder, a curing agent, and a surfactant. Can be applied to form.
  • the easy-adhesion layer may appropriately contain organic or inorganic particles.
  • the binder contained in the easy-adhesion layer is not particularly limited and is preferably at least one selected from polyester, polyurethane, acrylic resin, styrene-butadiene copolymer and polyolefin from the viewpoint of adhesiveness.
  • the binder is preferably at least one selected from polyester, polyurethane and polyolefin, and more preferably polyolefin.
  • a resin having water solubility or water dispersibility is particularly preferable in that the load on the environment is small.
  • the binder a commercially available commercial product may be used, and examples of the commercial product include Carbodilite (registered trademark) series (manufactured by Nisshinbo Co., Ltd.) such as Carbodilite V-02-L2 and Takelac WS-5100. Takerak WS series (manufactured by Mitsui Chemicals, Inc.), Arrow Base (registered trademark) series such as Arrow Base SE1013N (manufactured by Unitika Co., Ltd.), Hard Ren series such as Hard Ren NZ1004 (manufactured by Toyobo Co., Ltd.), etc. Be done.
  • the binder used for the easy-adhesion layer does not include the above-mentioned amorphous titanium peroxide type inorganic binder.
  • the particles are not particularly limited, but examples thereof include metal oxides, and specifically, tin oxide, zirconium oxide, zinc oxide, titanium oxide, cerium oxide, niobium oxide and the like are preferable.
  • the particles may be used alone or in combination of two or more.
  • commercially available products may be used, and examples of the commercially available products include ET series such as ET-500W, FT series such as FT-2000, SN series such as SN-100P and FS-10D.
  • FS series manufactured by Ishihara Sangyo Co., Ltd.
  • the thickness of the easy-adhesion layer is more preferably in the range of 0.01 ⁇ m to 5 ⁇ m. When the thickness is 0.01 ⁇ m or more, the adhesiveness tends to be good. Further, when the thickness is 5 ⁇ m or less, the easy-adhesion layer tends to have a uniform thickness.
  • the preferable thickness range of the easy-adhesion layer is 0.02 ⁇ m to 3 ⁇ m.
  • the thickness of the easy-adhesion layer can be appropriately adjusted by adjusting the coating amount.
  • the easily adhesive layer may be only one layer or two or more layers. When a plurality of easy-adhesion layers are stacked to form a multilayer, the total thickness of all the easy-adhesion layers is regarded as the thickness.
  • the photocatalyst composite material according to the present disclosure may have a shielding layer between the base material layer and the photocatalyst layer as a layer other than the above.
  • the light shielding layer it is considered that, for example, radicals generated in the photocatalyst layer are trapped in the shielding layer, and deterioration of the base material layer due to the radicals such as the resin base material is suppressed.
  • the shielding layer for example, a layer formed in the same manner as the inorganic particle-containing layer except that it does not contain inorganic particles can be used.
  • the photocatalyst composite material in the present disclosure is preferably a protective member, and is preferably a sensor protective member, a building material protective member, a vehicle protective member, a cooling container protective member, or a surveillance camera protective member.
  • the photocatalyst composite material according to the present disclosure has one or more of effects such as antifouling, antibacterial, antivirus, deodorant, and antifungal by including the photocatalyst layer.
  • the photocatalyst composite material according to the present disclosure has one or more of effects such as antireflection property and scratch resistance depending on the composition of the inorganic particle-containing layer and the like. Therefore, the photocatalyst composite material according to the present disclosure can be used as, for example, a protective member having excellent antifouling property, scratch resistance, and antireflection property.
  • the sensor protection member according to the present disclosure includes the photocatalyst composite material according to the present disclosure, and the sensor according to the present disclosure includes the sensor protection member according to the present disclosure.
  • the protective member for a sensor according to the present disclosure has excellent photocatalytic activity on the surface on the inorganic particle-containing layer side. Therefore, for example, by using the inorganic particle-containing layer as the outermost layer in the sensor, it is possible to prevent the attachment of dirt.
  • the photocatalyst composite material according to the present disclosure has excellent antireflection properties, it is possible to suppress reflection of light on the sensor and improve the sensor sensitivity by using it as a protective member for a sensor, for example.
  • the sensor examples include LiDAR (Light Detection and Ranging) using infrared rays.
  • LiDAR Light Detection and Ranging
  • the protective member for a sensor may be formed, for example, by providing a photocatalyst composite material in which a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the outermost part of a conventional sensor.
  • the sensor protection member is formed, for example, by using a resin film as a base material layer and attaching a photocatalyst composite material in which a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the base material layer to the outermost part of a conventional sensor. May be done.
  • the building material protection member according to the present disclosure includes the photocatalyst composite material according to the present disclosure, and the building material according to the present disclosure includes the building material protection member according to the present disclosure.
  • the protective member for a building material according to the present disclosure has excellent photocatalytic activity on the surface on the inorganic particle-containing layer side. Therefore, for example, by using the inorganic particle-containing layer as the outermost surface of the building material, it is possible to prevent the adhesion of dirt. Further, since the photocatalyst composite material according to the present disclosure has excellent antireflection properties, by using it as a building material protection member, it is possible to suppress light reflection on the surface of the building material and improve the visibility of the display image. Become.
  • the building material protection member may be formed, for example, by providing a photocatalyst composite material in which a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the building material.
  • the protective member for building materials may be formed by, for example, using a resin film as a base material layer, and adhering to the building material a photocatalyst composite material in which a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the base material layer.
  • the building material is not particularly limited, and examples thereof include a window of a building and a glass window lining film.
  • a high visible light transmittance and an infrared radiation for example, heat dissipation from indoors to outdoors
  • an infrared radiation for example, heat dissipation from indoors to outdoors
  • building materials building exteriors, ceiling members, wall materials, wood for construction, laminated plywood, gypsum board, glass, tiles, plastic films, building members for wall signboards (having a concealing effect of light and a visible light transmittance) ), outdoor display boards, and the like.
  • the effect of preventing malfunction of the remote controller or the like due to infrared noise can be obtained.
  • the vehicle protection member according to the present disclosure includes the photocatalyst composite material according to the present disclosure, and the vehicle according to the present disclosure includes the vehicle protection member according to the present disclosure.
  • the vehicle protection member according to the present disclosure is excellent in photocatalytic activity on the surface of the inorganic particle-containing layer side, and therefore, for example, by using the inorganic particle-containing layer as the outermost surface of the vehicle body (body) or the window of the vehicle, contamination of the Adhesion can be prevented.
  • the photocatalyst composite material according to the present disclosure has excellent antireflection properties, it is used as a vehicle protection member to suppress light reflection on the surface of the vehicle body (body) or the window of the vehicle, and to have an appropriate thickness, for example. By selecting, it becomes possible to obtain the effect of radiating infrared rays (for example, radiating heat from the inside of the vehicle to the outside of the vehicle) while having visible light transmittance.
  • the vehicle protection member may be formed, for example, by providing a photocatalyst composite material in which a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the vehicle body or the window of the vehicle.
  • the vehicle protection member is formed, for example, by using a resin film as a base material layer, and adhering a photocatalyst composite material in which a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the base material layer to a vehicle body or a vehicle window. May be done.
  • the vehicle is not particularly limited, and examples thereof include automobiles and railways.
  • a cooling container protection member according to the present disclosure includes the photocatalyst composite material according to the present disclosure, and a cooling container according to the present disclosure includes the cooling container protection member according to the present disclosure.
  • the protective member for a cooling container according to the present disclosure has excellent photocatalytic activity on the surface of the inorganic particle-containing layer side, and therefore, for example, by setting the inorganic particle-containing layer as the outermost surface of the cooling container, it is possible to prevent the adhesion of dirt. it can.
  • the photocatalyst composite material according to the present disclosure is excellent in antireflection property, so that it is used as a protective member for a cooling container to suppress reflection of light on the surface of the cooling container, for example, by selecting an appropriate thickness, It is possible to obtain the effect of radiating infrared rays (for example, radiating heat from the inside of the container to the outside of the container) while having visible light transparency.
  • the protective member for a cooling container may be formed, for example, by providing a photocatalyst composite material in which a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the cooling container.
  • the protective member for a cooling container may be formed by, for example, using a resin film as a base material layer, and adhering to the cooling container a photocatalyst composite material in which a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the base material layer.
  • a resin film as a base material layer
  • adhering to the cooling container a photocatalyst composite material in which a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the base material layer.
  • Examples of the cooling container include a showcase for freezing or refrigeration.
  • the surveillance camera protection member according to the present disclosure includes the photocatalyst composite material according to the present disclosure, and the surveillance camera according to the present disclosure includes the surveillance camera protection member according to the present disclosure. Since the protective member for a surveillance camera according to the present disclosure has excellent photocatalytic activity on the surface of the inorganic particle-containing layer side, for example, by forming the inorganic particle-containing layer as the outermost surface of the surveillance camera, adhesion of dirt can be prevented. it can. Further, since the photocatalyst composite material according to the present disclosure has excellent antireflection properties, it can be used as a vehicle protection member to suppress light reflection on the surface of the surveillance camera and improve the visibility of the display image.
  • the protection member for a surveillance camera may be formed, for example, by providing a surveillance camera with a photocatalyst composite material in which a photocatalyst layer and an inorganic particle-containing layer are laminated in this order.
  • the protective member for a surveillance camera may be formed by, for example, using a resin film as a base material layer, and adhering to the surveillance camera a photocatalytic composite material in which a photocatalyst layer and an inorganic particle-containing layer are laminated in this order on the base material layer.
  • the surveillance camera is a surveillance camera that is installed indoors or outdoors, and any type is applicable, and it may be provided as the outermost layer of the camera cover.
  • the protective member including the photocatalyst composite material according to the present disclosure includes a shade tent, a shade monument, a decorative tent, a tent warehouse, an event tent, a truck hood, an agricultural and horticultural sheet, a blind, a sheet shutter, a partition, a lighting shade, and a light. It is also suitably used as a protective member for ceiling membrane materials, membrane materials for internally illuminated signboards, and the like. In these applications, for example, cooling effect and infrared noise removing effect are expected.
  • the composition was thickened by mixing Tiosky Coat A liquid and a 10% aqueous solution of hydroxyalkyl (C1 to C3) cellulose, which is a thickener. Specifically, in the case where the thickness formed per spin for 30 seconds at 500 rpm is 500 nm, the above-mentioned thickener is added to the Tiosky coat A liquid, and the total mass of the Tiosky coat A liquid and the thickener is added. 30.7% was added.
  • Tio Sky Coat A liquid (manufactured by Tio Systems) is an aqueous composition mainly composed of anatase type (crystalline) titanium oxide particles having a number average particle size of 5 nm to 20 nm and peroxotitanic acid.
  • the X-ray diffraction measurement was performed on the formed photocatalyst layer, no crystal peak appeared, so it was determined to be a layer containing an amorphous titanium peroxide type inorganic binder. Further, the titanium oxide contained in the formed photocatalyst layer was confirmed to be anatase type titanium oxide by X-ray diffraction measurement.
  • Epoxy group-containing alkoxysilane compound 80 parts by mass (3-glycidoxypropyltriethoxysilane (crosslinkable group-containing alkoxysilane compound), Shin-Etsu Chemical Co., Ltd., KBE-403) Tetraalkoxysilane: 20 parts by mass (tetraethoxysilane (alkoxysilane compound containing no crosslinkable group), Shin-Etsu Chemical Co., Ltd., KBE-04) -Acetic acid aqueous solution (manufactured by Daicel Chemical Industries, Ltd., 1% aqueous solution of acetic acid for industrial use): 100 parts by mass-Aluminum chelate complex: 22.1 parts by mass (Kawaken Fine Chemical Co., Ltd., Aluminum chelate D) -Inorganic particles described in Table 1: 200 parts by mass-Surfactant A: 0.2 parts by mass (10% diluted solution of Sanded BL manufactured by Sanyo Kasei Co.
  • the above preparation was performed by the following procedure.
  • An epoxy group-containing alkoxysilane compound (KBE403) was added to 100 parts by mass of a 1% acetic acid aqueous solution and sufficiently hydrolyzed, and then tetraalkoxysilane (KBE04) was added.
  • the aluminum chelate complex was added to the epoxy group-containing alkoxysilane compound in the required amount by mass, and the inorganic particles shown in Table 1 were added thereto.
  • 0.2 part by mass of 10% diluted solution of surfactant A (Sandet BL) and 10% diluted solution of surfactant B (narrow acty CL-95) were added to a solid concentration of 15%. Water was added so as to obtain a composition for forming an inorganic particle-containing layer.
  • the inorganic particle-containing layer had a crosslinked structure (organic structure).
  • the inorganic particle-containing layer was dissolved in toluene, and it was confirmed that the siloxane resin did not dissolve. From this, it was determined that the inorganic particle-containing layer had a crosslinked structure.
  • Example 5 A photocatalyst layer was formed in the same manner as in Example 1 except that the method for forming the photocatalyst layer was changed to the following, to prepare a photocatalyst composite material.
  • the Tiosky coat A liquid was a 1:1 (mass ratio) mixed liquid of the Tiosky coat A liquid and the Tiosky coat C liquid (simply referred to as “A+C liquid” in Table 1).
  • the photocatalyst layer was formed by the same method as in Example 1 except that
  • Tio Sky Coat C liquid (manufactured by Tio Systems) is an aqueous composition containing peroxotitanic acid as a main component (not containing titanium oxide particles).
  • Example 6 A photocatalyst layer was formed in the same manner as in Example 1 except that the method for forming the photocatalyst layer was changed to the following, to prepare a photocatalyst composite material. -Formation of photocatalyst layer- After the surface of the glass substrate was previously irradiated with plasma for surface treatment, a vapor deposition film of TiO 2 was formed by a known vapor deposition method. The vapor deposition was performed with reference to the description in JP 2012-73542 A.
  • the oxygen:argon ratio volume ratio
  • the oxygen gas inflow amount the acceleration voltage, the ion current, the ultimate pressure, and the irradiation atmosphere were appropriately set so that the thickness of the deposited film was the value described in Table 1. ..
  • Example 8 A photocatalyst layer was formed in the same manner as in Example 1 except that the method for forming the photocatalyst layer was changed to the following, to prepare a photocatalyst composite material.
  • -Formation of photocatalyst layer A photocatalyst layer was prepared in the same manner as in Example 1 except that the glass substrate was replaced with a polyethylene terephthalate substrate (PET substrate; Cosmoshine A4100 (thickness: 100 ⁇ m), manufactured by Toyobo Co., Ltd.) which was not surface-treated. Formed.
  • PET substrate polyethylene terephthalate substrate
  • Cosmoshine A4100 thinness: 100 ⁇ m
  • UV irradiation and evaluation of water contact angle An ultraviolet irradiator equipped with a low-pressure mercury lamp was used to irradiate the surface of the photocatalyst composite material on the inorganic particle-containing layer side with ultraviolet light at an irradiation intensity of 2.0 mW/cm 2 .
  • the wavelength of the ultraviolet rays to be applied was 365 nm.
  • UVGL-25 manufactured by UVP mentioned above or the like was used as the ultraviolet irradiator.
  • the water contact angle is measured every 1 hour from the start of irradiation with ultraviolet rays, and the time from the time when the water contact angle reaches a peak to when the water contact angle becomes 10° or less (arrival time; h) is measured.
  • B The time until the water contact angle becomes 10° or less is more than 10 hours and 100 hours or less.
  • C The time until the water contact angle becomes 10° or less exceeds 100 hours.
  • D There is no peak value in the water contact angle, and there is no change from the initial value.
  • the surface on the side opposite to the glass substrate refers to the surface of the inorganic particle-containing layer side, inorganic
  • the reflectance on the surface on the photocatalyst layer side is measured.
  • the reflectance is measured using an ultraviolet-visible infrared spectrophotometer (model number: UV3100PC, manufactured by Shimadzu Corporation), and the reflectance (%) in light having a wavelength of 800 nm to 1500 nm is measured using an integrating sphere.
  • the infrared reflectance was an average value of wavelengths of 800 nm to 1500 nm.
  • the measurement results of infrared reflectance are shown in Table 1. It can be said that the lower the numerical value of the infrared reflectance, the more excellent the antireflection property.
  • the numerical value of infrared reflectance is preferably less than 8.0%.
  • “B. Visible light reflectance” measurement the reflectance was measured in the same manner except that the wavelength of light used for the measurement was changed from 800 nm to 1500 nm to 400 nm to 800 nm.
  • the average value of wavelengths of 400 nm to 800 nm was defined as the visible light reflectance.
  • Table 1 shows the measurement results of the visible light reflectance. It can be said that the lower the numerical value of the visible light reflectance, the more excellent the antireflection property. Further, the numerical value of the visible light reflectance is preferably less than 10.0%.
  • the photocatalyst composite materials of Examples are excellent in photocatalytic activity on the surface of the inorganic particle-containing layer side and excellent in antireflection property when light is incident from the inorganic particle-containing layer side. Recognize.
  • the photocatalyst composite material according to the present disclosure has a low infrared reflection, and has low visible light reflection and excellent visible light transparency, so that, for example, building materials, agricultural materials, etc. It is considered to be suitable for applications in which infrared rays are easily transmitted (e.g., emitted from indoors to outdoors).
  • Comparative Example 1 it is understood that the reflectance is high because the inorganic particle-containing layer is not formed.
  • Comparative Example 2 since the inorganic particle-containing layer was formed as a layer containing no inorganic particles, it was found that the photocatalytic activity was poor.
  • Comparative Example 3 since the thickness of the inorganic particle-containing layer is less than 100 nm, the antireflection property is not sufficient and the reflectance is high.
  • Comparative Example 4 on the contrary, since the thickness of the inorganic particle-containing layer is thicker than 250 nm, it can be seen that the photocatalytic activity is poor.

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  • Physics & Mathematics (AREA)
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Abstract

La présente invention concerne un matériau composite photocatalytique qui comprend une couche de photocatalyseur qui contient de l'oxyde de titane anatase et une couche contenant des particules inorganiques qui contient des particules inorganiques et une résine de siloxane contenant une structure organique, et qui est configuré de telle sorte que : la couche de photocatalyseur a un indice de réfraction de 1,5 à 2,5 (inclus) telle que déterminée par ellipsométrie à une longueur d'onde de 1 000 nm; et la couche contenant des particules inorganiques a une épaisseur de 100 nm à 250 nm, tout en ayant un indice de réfraction inférieur à 1,5 tel que déterminé par ellipsométrie à une longueur d'onde de 1000 nm. La présente invention concerne également des utilisations de ce matériau composite photocatalytique.
PCT/JP2019/041511 2018-11-28 2019-10-23 Matériau composite photocatalytique, élément de protection pour capteurs, élément de protection pour matériaux de construction, élément de protection pour véhicules, élément de protection pour récipients de refroidissement, élément de protection pour caméras de sécurité, capteur, matériaux de construction, véhicule, récipient de refroidissement et caméra de sécurité Ceased WO2020110523A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004337740A (ja) * 2003-05-15 2004-12-02 Teio Techno:Kk 光触媒体
JP2013107926A (ja) * 2011-11-17 2013-06-06 Kaneka Corp 被膜形成用組成物およびその製造方法ならびにそれを用いた太陽電池モジュール
WO2018042804A1 (fr) * 2016-08-29 2018-03-08 信越化学工業株式会社 Stratifié photocatalyseur
WO2018190105A1 (fr) * 2017-04-12 2018-10-18 富士フイルム株式会社 Film antireflet et élément optique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004337740A (ja) * 2003-05-15 2004-12-02 Teio Techno:Kk 光触媒体
JP2013107926A (ja) * 2011-11-17 2013-06-06 Kaneka Corp 被膜形成用組成物およびその製造方法ならびにそれを用いた太陽電池モジュール
WO2018042804A1 (fr) * 2016-08-29 2018-03-08 信越化学工業株式会社 Stratifié photocatalyseur
WO2018190105A1 (fr) * 2017-04-12 2018-10-18 富士フイルム株式会社 Film antireflet et élément optique

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