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WO2012011367A1 - Liquide de revêtement photocatalyseur et produit présentant une fonctionnalité photocatalytique - Google Patents

Liquide de revêtement photocatalyseur et produit présentant une fonctionnalité photocatalytique Download PDF

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Publication number
WO2012011367A1
WO2012011367A1 PCT/JP2011/064679 JP2011064679W WO2012011367A1 WO 2012011367 A1 WO2012011367 A1 WO 2012011367A1 JP 2011064679 W JP2011064679 W JP 2011064679W WO 2012011367 A1 WO2012011367 A1 WO 2012011367A1
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mass
photocatalyst
parts
particles
coating liquid
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Japanese (ja)
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仁 高見
酒谷　能彰
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • 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
    • B01J35/39—Photocatalytic 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/71—Photocatalytic coatings

Definitions

  • the present invention relates to a photocatalyst coating liquid and a photocatalytic functional product.
  • tungsten oxide is a photocatalyst that exhibits high photocatalytic action under illumination of a fluorescent lamp.
  • Patent Document 1 an adhesive layer is provided on a substrate, a binder component made of a metal oxide gel or a metal hydroxide gel is mixed with a photocatalyst coating liquid containing a photocatalyst, and the photocatalyst coating liquid is applied to the adhesive layer. It is disclosed that a photocatalyst-supporting structure in which photocatalyst particles are less likely to fall off when applied on top is obtained.
  • the adhesive strength between the adhesive layer and the base material or the adhesive strength between the photocatalyst body layer and the adhesive layer is not always sufficient, and the photocatalyst body is easily peeled off from the base material, and a high photocatalyst. No activity was expressed.
  • the problem of the present invention is that when a photocatalyst layer is formed on the surface of the substrate, a photocatalyst layer having excellent adhesion to the substrate is obtained, and the photocatalyst layer is irradiated with a practical light source such as a fluorescent lamp.
  • a photocatalyst coating liquid exhibiting high photocatalytic activity and a photocatalytic functional product having a photocatalyst layer on the surface are provided.
  • this invention consists of the following structures.
  • the oxide equivalent content is 0 to 200 parts by mass with respect to 100 parts by mass of the oxide equivalent of (4), and the oxide equivalent content of (3) is the oxidation of (4).
  • the present invention is also a photocatalytic functional product comprising a photocatalyst layer on a substrate surface, wherein the photocatalyst layer is formed using the photocatalyst coating liquid according to any one of (I) to (IV).
  • a photocatalytic functional product comprising a photocatalyst layer on a substrate surface, wherein the photocatalyst layer is formed using the photocatalyst coating liquid according to any one of (I) to (IV).
  • the photocatalyst coating liquid of the present invention since it contains niobium oxide, colloidal silica, and silicon alkoxide as binders in an optimum composition, it can be adhered even if directly applied to a substrate without providing an adhesive layer on the substrate. It is possible to form a photocatalyst layer that exhibits excellent strength and exhibits sufficient photocatalytic activity. Furthermore, the photocatalyst layer can also provide a photocatalytic functional product that exhibits excellent surface hardness and excellent hydrophilicity and maintains the original excellent photocatalytic action.
  • the photocatalyst coating liquid of the present invention contains photocatalyst particles, niobium oxide sol particles, colloidal silica particles, silicon alkoxide and a solvent in a predetermined ratio, and the solid content of the photocatalyst coating liquid is set to a predetermined ratio.
  • the photocatalyst particles in the present invention are oxides having a photocatalytic action, and examples thereof include titanium oxide particles and tungsten oxide particles.
  • tungsten oxide particles are irradiated with visible light (wavelength of about 400 nm to about 800 nm). Since it exhibits high photocatalytic activity, it is suitable for the present invention.
  • Titanium oxide particles are particulate titanium oxides that exhibit particularly high photocatalytic activity when irradiated with ultraviolet light.
  • examples of the titanium oxide particles include metatitanic acid particles, titanium dioxide [TiO 2 ] particles whose crystal types are anatase type, brookite type, rutile type, and the like.
  • Metatitanic acid particles can be obtained, for example, by the following method (A).
  • the titanium dioxide particles can be obtained, for example, by any one of the following methods (B-1) to (B-3).
  • Method (B-1) A method of obtaining a precipitate by adding a base to an aqueous solution of titanyl sulfate or titanium chloride without heating, and firing the obtained precipitate.
  • Method of (B-3) Method of calcining metatitanic acid by adding water, aqueous solution of acid or base solution to obtain precipitate, and calcining the resulting precipitate
  • the titanium dioxide particles obtained by the above methods (B-1) to (B-3) can be obtained as anatase type, brookite type or rutile type crystal types depending on the baking temperature and baking time at the time of baking.
  • titanium oxide can be obtained by, for example, the sulfuric acid method and the chlorine method described in “Titanium oxide” (Gaku Kiyono, published by Gihodo Publishing), JP-A-2001-72419, No. 2001-190953, JP-A No. 2001-316116, JP-A No. 2001-322816, JP-A No. 2002-29749, JP-A No. 2002-97019, WO 01/10552, JP-A No. 2001. No. -21457, JP 2002-239395 A, WO 03/080244, WO 02/053501, JP 2007-69093 A, Chemistry Letters, Vol.32, No.2, P.196.
  • the titanium oxide obtained by the above method may be used alone or in combination of two or more.
  • the average dispersed particle size is used as the particle size of the titanium oxide particles. From the viewpoint of effectively exhibiting photocatalytic action, the average dispersed particle size is usually 20 nm to 150 nm, preferably 40 nm to 100 nm.
  • the BET specific surface area of the titanium oxide particles is usually 100 m 2 / g to 500 m 2 / g, preferably 300 m 2 / g to 400 m 2 / g, from the viewpoint of effectively exhibiting photocatalytic action.
  • the tungsten oxide particles are particulate tungsten oxides that exhibit high photocatalytic action even when irradiated with visible light (wavelength of about 400 nm to about 800 nm).
  • the tungsten oxide particles usually include tungsten trioxide [WO 3 ] particles.
  • the tungsten trioxide particles can be obtained, for example, by adding an acid to an aqueous solution of tungstate to obtain tungstic acid as a precipitate, and firing the obtained tungstic acid. Moreover, it can also obtain by the method of thermally decomposing by heating ammonium metatungstate and ammonium paratungstate.
  • the average dispersed particle size is used as the particle size of the tungsten oxide particles. From the viewpoint of effectively exhibiting photocatalytic action, the average dispersed particle size is usually 50 nm to 200 nm, preferably 80 nm to 130 nm.
  • the BET specific surface area of the tungsten oxide particles is usually 5 m 2 / g to 100 m 2 / g, preferably 20 m 2 / g to 50 m 2 / g, from the viewpoint of effectively exhibiting photocatalytic action.
  • the average particle diameter of the niobium oxide sol particles in the present invention is usually 50 nm or less, preferably 30 nm or less, and may be crystalline or amorphous. Further, in order to improve the dispersion stability of the niobium oxide sol particles, a material in which the surface of the niobium oxide sol particles is appropriately modified with a dispersant may be used. Examples of such niobium oxide sol particles include niobium oxide sol “Nb-X-10” manufactured by Taki Chemical Co., Ltd.
  • the oxide equivalent content of the niobium oxide sol particles is 0 to 200 parts by mass, preferably 20 to 140 parts by mass, and more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the oxide equivalent of the silicon alkoxide. It is.
  • the content of the niobium oxide sol particles in terms of oxide exceeds 200 parts by mass, the adhesion between the resulting photocatalyst layer and the substrate is lowered, and the photocatalyst layer is too soft and may cause a problem.
  • the oxide equivalent content of the niobium oxide sol particles exceeds 140 parts by mass, the photocatalyst layer is easily damaged, and when the oxide equivalent content of the niobium oxide sol particles is less than 20 parts by mass, the photocatalyst is obtained.
  • the hydrophilicity of the body layer is significantly reduced.
  • the oxide equivalent content of the niobium oxide sol particles exceeds 80 parts by mass, the hydrophilicity corresponding to the hardness of the photocatalyst layer cannot be obtained, and the oxide equivalent content of the niobium oxide sol particles is 30 masses. If it is less than the part, the hydrophilicity of the photocatalyst layer is lowered.
  • the oxide equivalent content of niobium oxide sol particles means the content of Nb 2 O 5 when all the niobium components in the niobium oxide sol are converted to Nb 2 O 5 , and the oxide equivalent of silicon alkoxide, all the silicon component in the silicon alkoxide means the content of SiO 2 in the case of conversion into SiO 2, and so on.
  • colloidal silica particles The average particle size of the colloidal silica particles in the present invention is usually 50 nm or less, preferably 30 nm or less.
  • the oxide equivalent content of the colloidal silica particles is 0 to 280 parts by mass, preferably 160 to 260 parts by mass, more preferably 170 to 230 parts by mass with respect to 100 parts by mass of the oxide equivalent of the silicon alkoxide. It is. When the content of the colloidal silica particles in terms of oxide exceeds 280 parts by mass, the adhesion between the resulting photocatalyst layer and the substrate is lowered, and the photocatalyst layer is too soft and may cause problems.
  • the oxide equivalent content of the colloidal silica particles exceeds 260 parts by mass, the adhesion of the photocatalyst layer is lowered, and when the oxide equivalent content of the colloidal silica particles is less than 160 parts by mass, The hydrophilicity of the photocatalyst layer is significantly reduced. Further, when the oxide equivalent content of the colloidal silica particles exceeds 230 parts by mass, the photocatalyst layer tends to be damaged, and when the oxide equivalent content of the colloidal silica particles is less than 170 parts by mass, The hydrophilicity of the body layer is reduced. Note that the oxide equivalent of the colloidal silica particles, all silicon component in the colloidal silica means a content of SiO 2 in the case of conversion into SiO 2, and so on.
  • the total oxide content of the niobium oxide sol particles and colloidal silica particles in the photocatalyst coating liquid of the present invention is 0 to 480 parts by mass with respect to 100 parts by mass of the oxide equivalent of silicon alkoxide, The amount is preferably 200 to 330 parts by mass, more preferably 210 to 310 parts by mass. If the total oxide content of the niobium oxide sol particles and colloidal silica particles exceeds 480 parts by mass, the adhesion between the resulting photocatalyst layer and the substrate will be lowered, and the photocatalyst layer will be too soft. May occur.
  • niobium oxide sol particles and colloidal silica particles exceeds 330 parts by mass, the hydrophilicity of the photocatalyst layer is remarkably reduced, and the oxide conversion of niobium oxide sol particles and colloidal silica particles is also reduced. If the sum total of content is less than 200 mass parts, the adhesiveness of a photocatalyst body layer will fall, and also a photocatalyst body layer will become easy to be damaged.
  • the hydrophilicity of the photocatalyst layer is lowered, and the oxide conversion of niobium oxide sol particles and colloidal silica particles is reduced.
  • the photocatalyst layer is easily damaged.
  • the total of the oxide equivalent content of niobium oxide sol particles, colloidal silica particles, and silicon alkoxide in the photocatalyst coating liquid of the present invention is 100 parts by mass of the photocatalyst particle content in the photocatalyst coating liquid of the present invention.
  • it is usually 20 to 500 parts by mass, but the photocatalyst layer obtained from the photocatalyst coating liquid may be 100 to 450 parts by mass for the purpose of obtaining good adhesion to the substrate.
  • niobium oxide sol particles, colloidal silica particles, and silicon alkoxide in terms of oxides is less than 20 parts by mass, the adhesion between the photocatalyst layer and the substrate decreases, while 500 parts by mass is reduced. If it exceeds, the photocatalyst particles are buried in a binder component such as niobium oxide sol particles, making it difficult to obtain a photocatalyst layer having sufficient photocatalytic activity.
  • silicon alkoxide examples include tetraethoxysilane (ethyl silicate), tetramethoxysilane (methyl silicate), methyltriethoxysilane, methyltriethoxysilane, and hydrolyzates and polymers such as silicon alkoxide. .
  • an aqueous medium containing water as a main component specifically, a solvent containing 50% by mass or more of water is used, water may be used alone, or a mixed solvent of water and a water-soluble organic solvent. May be used.
  • the water-soluble organic solvent include water-soluble alcohol solvents such as methanol, ethanol, propanol, and butanol, acetone, methyl ethyl ketone, methyl cellosolve, and ethyl cellosolve.
  • the content in terms of solid oxide obtained by volatilizing a volatile component such as a solvent from the photocatalyst coating liquid is usually 0. 5 to 30 parts by weight (that is, 0.5 to 30% by weight with respect to the total amount of the photocatalyst coating liquid), preferably 1 to 20 parts by weight (1 to 20% by weight), more preferably Is used by diluting with water or other solvent so as to be about 2 to 10 parts by mass (2 to 10% by mass).
  • the solid content is less than 0.5 parts by mass, it becomes difficult to form a photocatalyst layer having a sufficient thickness, and when the solid content exceeds 30 parts by mass, the transparency of the resulting photocatalyst layer is impaired.
  • the mixing order and mixing method of the photocatalyst particles, niobium oxide sol particles, colloidal silica particles, silicon alkoxide and solvent when preparing the photocatalyst coating liquid of the present invention are not particularly limited.
  • colloidal silica particles A method of mixing niobium oxide sol particles with a binder liquid in which silicon alkoxide and a solvent are mixed, and further mixing a photocatalyst dispersion liquid in which the photocatalyst particles are dispersed in a solvent alone, (b) the photocatalyst particles are a solvent alone
  • the photocatalyst particles are a solvent alone
  • examples include a method in which niobium oxide sol particles, colloidal silica particles, and silicon alkoxide are sequentially added to the photocatalyst dispersion dispersed in and mixed, and may be performed with stirring or heating as necessary. May be.
  • the hydrogen ion concentration of the photocatalyst dispersion in which the photocatalyst particles are dispersed alone in a solvent is usually pH 2.0 to pH 7.0, preferably pH 3.0 to pH 6.0.
  • the hydrogen ion concentration is less than pH 2.0, the acidity is too strong and the handling is troublesome.
  • the pH exceeds 7.0 when the photocatalyst particles are tungsten oxide particles, the tungsten oxide particles may be dissolved.
  • the hydrogen ion concentration of the photocatalyst dispersion liquid can be usually adjusted by adding an acid. Examples of the acid that can be used include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, and succinic acid.
  • the photocatalyst dispersion liquid can be obtained by adding a photocatalyst particle to a solvent in the presence of a suitable dispersant as necessary and subjecting it to a dispersion treatment.
  • the dispersion treatment can be performed, for example, by an ordinary method using a medium stirring type disperser.
  • the addition of the photocatalyst particles to the solvent may be performed, for example, by adding the photocatalyst particles directly to the solvent and mixing them. Usually, however, the photocatalyst particles are dispersed in the dispersion medium in advance in the solvent.
  • dispersion medium examples include the solvents described above.
  • the photocatalyst particles in the present invention preferably have a noble metal supported on the surface in order to improve the photocatalytic activity.
  • a method for supporting the noble metal on the surface of the photocatalyst particles for example, a method in which a sacrificial agent is dissolved in the above-described photocatalyst dispersion liquid and light irradiation is performed on the photocatalyst particle dispersion, or And a method of irradiating with light in an aqueous solution in which is dissolved.
  • the noble metal precursor one that can be dissolved in a solvent is used.
  • the noble metal element constituting the precursor usually becomes a noble metal ion having a positive charge and exists in the solvent.
  • the noble metal ions are reduced to zero-valent noble metal by the photocatalytic action of the photocatalyst particles by light irradiation, and are supported on the surfaces of the photocatalyst particles.
  • the noble metal include Cu, Pt, Au, Pd, Ag, Ru, Ir, and Rh.
  • the precursor include hydroxides, nitrates, sulfates, halides, organic acid salts, carbonates, and phosphates of these noble metals.
  • the noble metal is preferably Cu, Pt, Au, or Pd.
  • Examples of the Cu precursor include copper nitrate (Cu (NO 3 ) 2 ), copper sulfate (CuSO 4 ), copper chloride (CuCl 2 , CuCl), copper bromide (CuBr 2 , CuBr), copper iodide ( CuI), copper iodate (CuI 2 O 6 ), ammonium copper chloride (Cu (NH 4 ) 2 Cl 4 ), copper oxychloride (Cu 2 Cl (OH) 3 ), copper acetate (CH 3 COOCu, (CH 3 COO) 2 Cu), copper formate ((HCOO) 2 Cu), copper carbonate (CuCO 3 ), copper oxalate (CuC 2 O 4 ), copper citrate (Cu 2 C 6 H 4 O 7 ), copper phosphate ( CuPO 4 ) and the like.
  • Examples of the precursor of Pt include platinum chloride (PtCl 2 , PtCl 4 ), platinum bromide (PtBr 2 , PtBr 4 ), platinum iodide (PtI 2 , PtI 4 ), and platinum potassium chloride (K 2 (PtCl 4).
  • Au precursor examples include gold chloride (AuCl), gold bromide (AuBr), gold iodide (AuI), gold hydroxide (Au (OH) 2 ), tetrachloroauric acid (HAuCl 4 ), tetra
  • Au precursor examples include gold chloride (AuCl), gold bromide (AuBr), gold iodide (AuI), gold hydroxide (Au (OH) 2 ), tetrachloroauric acid (HAuCl 4 ), tetra
  • Au precursor examples include gold chloride (AuCl), gold bromide (AuBr), gold iodide (AuI), gold hydroxide (Au (OH) 2 ), tetrachloroauric acid (HAuCl 4 ), tetra
  • K chloroaurate K tetrabromoaurate (KAuBr 4 ).
  • Examples of the precursor of Pd include palladium acetate ((CH 3 COO) 2 Pd), palladium chloride (PdCl 2 ), palladium bromide (PdBr 2 ), palladium iodide (PdI 2 ), palladium hydroxide (Pd ( OH) 2 ), palladium nitrate (Pd (NO 3 ) 2 ), palladium sulfate (PdSO 4 ), potassium tetrachloropalladate (K 2 (PdCl 4 )), potassium tetrabromopalladate (K 2 (PdBr 4 )) , Tetraammine palladium chloride (Pd (NH 3 ) 4 Cl 2 ), tetraammine palladium bromide (Pd (NH 3 ) 4 Br 2 ), tetraammine palladium nitrate (Pd (NH 3 ) 4 (NO 3 ) 2 ), tetraammine palladium tetra
  • Precious metal precursors may be used alone or in combination of two or more.
  • the amount used is usually 0.01 parts by mass or more, in terms of cost, in terms of sufficiently improving the photocatalytic action with respect to 100 parts by mass of the photocatalyst particles in terms of precious metal atoms. Is usually 1 part by mass or less, preferably 0.05 to 0.6 parts by mass.
  • a sacrificial agent When a noble metal is supported on the surface of the photocatalyst particles, a sacrificial agent is used, for example, added to the photocatalyst dispersion.
  • the sacrificial agent include alcohols such as ethanol, methanol, and propanol, ketones such as acetone, and carboxylic acids such as oxalic acid.
  • the sacrificial agent is added after the photocatalyst dispersion liquid is irradiated with light for a certain period of time, and further irradiated with light.
  • the amount of the sacrificial agent is usually 0.001 to 0.3 times by mass, preferably 0.005 to 0.1 times by mass, with respect to the solvent in the photocatalyst dispersion. If the amount of the sacrificial agent used is less than 0.001 times by mass, the noble metal is insufficiently supported on the photocatalyst particles, and if it exceeds 0.3 times by mass, the amount of sacrificial agent is excessive and an effect commensurate with the cost cannot be obtained. .
  • the photocatalyst dispersion liquid may be irradiated with light while stirring the photocatalyst dispersion liquid. Irradiation may be performed from inside or outside the tube while passing through a transparent glass or plastic tube, or this may be repeated.
  • the light source is not particularly limited as long as it can irradiate light having energy higher than the band gap of the photocatalyst particles. Specific examples include a germicidal lamp, a mercury lamp, a light emitting diode, a fluorescent lamp, a halogen lamp, a xenon lamp, and a solar light. Light or the like can be used.
  • the wavelength of the irradiated light is usually 180 nm to 500 nm.
  • the time for performing the light irradiation is such that a sufficient amount of noble metal can be supported on the photocatalyst particles, so that it is usually 20 minutes or longer, preferably 1 hour or longer, usually 24 hours or shorter, preferably 6 hours or shorter before and after the addition of the sacrificial agent. is there.
  • the time exceeds 24 hours most of the precursors of the noble metal have become noble metals and are supported on the photocatalyst particles, and an effect commensurate with the cost of light irradiation cannot be obtained.
  • noble metal is not uniformly supported on the photocatalyst particles, and high photocatalytic activity cannot be obtained.
  • Examples of the base include aqueous solutions of ammonia, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lanthanum hydroxide, etc. Among them, ammonia water and water Sodium oxide is preferably used.
  • Noble metal-supported photocatalyst particles Irradiate light while adjusting the pH, and after adding the sacrificial agent, further irradiate light, whereby the noble metal precursor becomes a noble metal and is supported on the surface of the photocatalyst particle to obtain the desired noble metal-supported photocatalyst particle. .
  • the noble metal-supported photocatalyst particles are dispersed in the solvent used without settling.
  • the photocatalyst coating liquid prepared as described above may contain an additive as long as the dispersibility of the photocatalyst particles and / or noble metal-supported photocatalyst particles is not impaired.
  • the additive examples include those added for the purpose of improving the photocatalytic action, specifically, silicon compounds such as water glass, aluminum compounds such as amorphous alumina, alumina sol, and aluminum hydroxide, zeolites Alkaline earth metal oxides such as kaolinite, magnesium oxide, calcium oxide, strontium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, etc.
  • alkaline earth metal water examples thereof include oxides, calcium phosphates, molecular sieves, activated carbon, polycondensates of organic polysiloxane compounds, phosphates, fluorine-based polymers, silicon-based polymers, acrylic resins, polyester resins, melamine resins, urethane resins, and alkyd resins. These additives are used alone or in combination of two or more.
  • the photocatalyst functional product of the present invention has a photocatalyst layer formed on the surface using the photocatalyst coating liquid obtained as described above.
  • the photocatalyst layer is formed, for example, by applying a photocatalyst coating liquid onto the surface of a substrate (product) by spin coating, dip coating, doctor blade, spraying or brushing, and then room temperature to 150 ° C., preferably room temperature to 90 ° It can be formed by a conventionally known film forming method such as drying and evaporating the solvent in the temperature range of ° C. and volatilizing the volatile component.
  • the film thickness of the photocatalyst body layer is not particularly limited, and it is usually set appropriately from several hundred nm to several mm according to its use.
  • the photocatalyst layer may be formed on any part as long as it is an inner surface or an outer surface of the base material (product).
  • the photocatalyst layer is a surface irradiated with light (visible light), and a malodorous substance. It is preferably formed on a surface that is continuously or intermittently connected to a place where the occurrence of a pathogen or a pathogen is present.
  • the material of the base material (product) is not particularly limited as long as the formed photocatalyst layer can be held at a strength that can be practically used.
  • a known barrier layer made of, for example, a silica component can be formed between the photocatalyst layer and the substrate.
  • thermosetting resin for example, aramid resin, polyimide resin, epoxy resin, unsaturated polyester resin, phenol resin, urea resin, polyurethane resin, melamine resin, benzoguanamine resin, silicone resin, melamine urea resin
  • thermoplastic resin examples thereof include a condensation polymerization resin and a resin obtained by polymerizing a vinyl monomer.
  • condensation polymerization resin examples include polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polylactic acid, biodegradable polyester, and polyester liquid crystal polymer; ethylenediamine-adipic acid polycondensate (nylon-66), nylon-6 And polyamide resins such as nylon-12 and polyamide liquid crystal polymers; polyether resins such as polycarbonate resins, polyphenylene oxide, polymethylene oxide, and acetal resins; polysaccharide resins such as cellulose and derivatives thereof;
  • resins obtained by polymerizing vinyl monomers include polyolefin resins; polystyrene, poly- ⁇ -methylstyrene, styrene-ethylene-propylene copolymers (polystyrene-poly (ethylene / propylene) block copolymers), Styrene-ethylene-butene copolymer (polystyrene-poly (ethylene / butene) block copolymer), styrene-ethylene-propylene-styrene copolymer (polystyrene-poly (ethylene / propylene) -polystyrene block copolymer), Unsaturated aromatic-containing resins such as ethylene-styrene copolymers; polyvinyl alcohol resins such as polyvinyl alcohol and polyvinyl butyral; polymethyl methacrylate, methacrylic acid ester, acrylic acid ester, methacrylic acid amide as monomers Acrylic resins
  • the photocatalytic functional product of the present invention has a high photocatalytic effect by light irradiation not only outdoors but also in an indoor environment that receives only light from a visible light source such as a fluorescent lamp, an incandescent bulb, a light emitting diode, and a sodium lamp.
  • a visible light source such as a fluorescent lamp, an incandescent bulb, a light emitting diode, and a sodium lamp.
  • the photocatalyst coating liquid of the present invention is, for example, a building material such as a ceiling material, tile, glass, wallpaper, wall material, floor, automobile interior material (automobile instrument panel, automobile seat, automobile ceiling material), Light applied by indoor lighting when applied to the surface of base materials that are in contact with an unspecified number of people, such as household appliances such as refrigerators and air conditioners, textile products such as clothes and curtains, train straps, elevator buttons, etc.
  • Irradiation reduces the concentration of volatile organic substances such as formaldehyde and acetaldehyde, aldehydes, mercaptans, ammonia and other malodorous substances, nitrogen oxides, and Staphylococcus aureus, Escherichia coli, anthrax, tuberculosis, cholera, diphtheria , Kill, decompose, and remove pathogens such as tetanus, plague, shigella, botulinum, and legionella Bets can be can be further harmless allergens such as mite allergen and cedar pollen allergen.
  • volatile organic substances such as formaldehyde and acetaldehyde, aldehydes, mercaptans, ammonia and other malodorous substances, nitrogen oxides, and Staphylococcus aureus, Escherichia coli, anthrax, tuberculosis, cholera, diphtheria , Kill, decompose, and remove pathogen
  • the photocatalytic functional product of the present invention is not only capable of exhibiting sufficient hydrophilicity and exhibiting antifogging properties when irradiated with visible light, but also can be easily wiped off by simply applying water to the dirt. In addition, charging can be prevented.
  • BET Specific Surface Area The BET specific surface area of the platinum-supported tungsten oxide particles was measured by a nitrogen adsorption method using a specific surface area measuring device [“Monosorb” manufactured by Yuasa Ionics Co., Ltd.].
  • Average dispersed particle size Measure the particle size distribution of the sample using a sub-micron particle size distribution analyzer (“N4Plus” manufactured by Coulter, Inc.), and automatically disperse the result of monodisperse mode analysis using the software provided with this device. The diameter.
  • Hardness test The hardness of the photocatalyst layer was measured by a pencil hardness test method (JIS 5600-5-4).
  • Adhesiveness of the photocatalyst layer to the base material is determined when the adhesive cellophane tape ("CT405AP-24" manufactured by Nichiban Co., Ltd.) is applied to the surface of the photocatalyst layer and then quickly peeled off. It evaluated by whether it peeled simultaneously.
  • the lifting speed of the dip coater was 10 mm / second, and the immersion time was 10 seconds.
  • the test piece coated with oleic acid was included in the fluorescent lamp from the top of the photocatalyst layer through an acrylic resin plate (“N169” manufactured by Nitto Resin Co., Ltd.) using a commercially available white fluorescent lamp as a light source.
  • the measurement was performed so that the visible light was irradiated, and the contact angle ⁇ of the water droplet after a predetermined time elapsed was measured using a contact angle meter (“CA-A type” manufactured by Kyowa Interface Science Co., Ltd.).
  • the measurement of the contact angle ⁇ of the water droplet was performed 5 seconds after the water droplet (about 0.4 ⁇ L) was placed on the photocatalyst layer of the test piece in each case.
  • the irradiation with visible light was such that the illuminance in the vicinity of the photocatalyst layer was 6000 lux (measured with an illuminometer “T-10” manufactured by Minolta).
  • T-10 illuminometer manufactured by Minolta
  • oleic acid is decomposed by the photocatalytic action of the photocatalyst body layer, and the contact angle of the water droplet decreases.
  • the angle at which the decrease in the contact angle reaches saturation is defined as the critical contact angle. It can be said that the smaller the limit contact angle, the higher the photocatalytic activity of the photocatalyst layer, that is, the photoinduced hydrophilicity and the organic substance decomposing performance.
  • Volatile organic matter decomposition activity (measurement of acetaldehyde resolution) The photocatalytic activity was evaluated by measuring a first-order reaction rate constant in the decomposition reaction of acetaldehyde under irradiation of light from a fluorescent lamp. That is, in a glass petri dish (outer diameter 70 mm, inner diameter 66 mm, height 14 mm, capacity about 48 mL), the obtained photocatalyst coating liquid has a dripping amount in terms of solid content per unit area of the bottom surface of 1 g / m 2. It was dripped so that it was uniformly formed on the entire bottom of the petri dish. Next, the petri dish was dried by holding it in the air at 110 ° C.
  • the photocatalyst layer is irradiated with UV light from a black light so that the UV intensity is 2 mW / cm 2 (measured by attaching a UV receiver “UD-36” to Topcon's UV intensity meter “UVR-2”). This was irradiated for 16 hours and used as a photocatalytic activity measurement sample.
  • the sample for photocatalytic activity measurement is placed in a gas bag (internal volume 1 L) together with the petri dish, and then the inside of the gas bag is evacuated, and then the volume ratio of oxygen to nitrogen is 1: 4.
  • the volume ratio of oxygen to nitrogen is 1: 4.
  • the illuminance in the vicinity of the measurement sample is 1000 lux through the acrylic resin plate (“N169” manufactured by Nitto Resin Co., Ltd.) (illuminance meter “T-10 manufactured by Minolta Co., Ltd.).
  • Example 1 Preparation of precious metal-supported photocatalyst dispersion
  • tungsten oxide particles manufactured by Nippon Inorganic Chemical Industry Co., Ltd.
  • ion-exchanged water 4 kg
  • This mixture was dispersed using a wet medium stirring mill to obtain a tungsten oxide particle dispersion.
  • tungsten oxide particle dispersion To this tungsten oxide particle dispersion, an aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) is added so that hexachloroplatinic acid is 0.12 parts by mass with respect to 100 parts by mass of tungsten oxide particles in terms of platinum atoms, A hexachloroplatinic acid-containing tungsten oxide particle dispersion was obtained as a raw material dispersion.
  • the solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was 17.6 parts by mass (solid content concentration 17.6% by mass). Thereafter, the pH of this dispersion was 2.0.
  • a light irradiation device comprising a glass tube (inner diameter: 37 mm, height: 360 mm) equipped with a pot and equipped with an underwater sterilization lamp (“GLD15MQ” manufactured by Sankyo Electric Co., Ltd.) While dispersing 1200 g of the raw material dispersion adjusted to a solid content concentration of 12.0% by mass at a rate of 1 L / min, the pH of the dispersion was adjusted to 3.5.
  • Light irradiation (ultraviolet irradiation) is performed for 2 hours while circulating the raw material dispersion, and methanol is further added so that the concentration thereof is 1% by mass of the total solvent, and light irradiation is performed for 3 hours while circulating the raw material dispersion.
  • methanol is further added so that the concentration thereof is 1% by mass of the total solvent
  • light irradiation is performed for 3 hours while circulating the raw material dispersion.
  • the pH was constant at 3.5.
  • An aqueous ethanol solution was added to the obtained platinum-supported tungsten oxide particle dispersion to obtain a platinum-supported photocatalyst dispersion.
  • the content of the platinum-supported tungsten oxide particles with respect to 100 parts by mass of the platinum-supported photocatalyst dispersion liquid was 5 parts by mass, and the content of ethanol was 30 parts by mass.
  • Niobium oxide sol particles ("Nb-X-10" manufactured by Taki Chemical Industry Co., Ltd., solid content concentration of 10% by mass in terms of oxide) were diluted with an aqueous ethanol solution to obtain an ethanol-containing niobium oxide sol.
  • the contents of ethanol and niobium oxide sol particles in terms of oxide with respect to 100 parts by mass of the ethanol-containing niobium oxide sol were 30 parts by mass and 5 parts by mass, respectively.
  • ethanol-containing niobium oxide sol 100 g was added to 700 g of binder, and 200 g of a platinum-supported photocatalyst dispersion (solid content concentration 5 mass%) was further added to obtain a photocatalyst coating liquid. All of these were performed at room temperature and in the atmosphere, and each component was added with stirring.
  • the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass (5% by mass) with respect to 100 parts by mass of the photocatalyst coating liquid. Further, the total solid content of 100 parts by mass includes platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate oxide conversions of 20 parts by mass, 10 parts by mass, 47 parts by mass, and 23, respectively. Part by mass was included.
  • the niobium oxide sol particles, colloidal silica particles, and the total content thereof were 43 parts by mass, 204 parts by mass, and 248 parts by mass, respectively, in terms of oxide with respect to 100 parts by mass of oxide silicate in ethyl silicate. It was.
  • the total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
  • Example 2 The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 10 parts by mass, respectively.
  • a photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the content was 45 parts by mass and 25 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
  • Niobium oxide sol particles, colloidal silica particles, and the total content thereof were 40 parts by mass, 180 parts by mass, and 220 parts by mass, respectively, in terms of oxides with respect to 100 parts by mass of ethyl silicate in terms of oxides. It was.
  • the total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
  • a photocatalyst layer was prepared in the same manner as in Example 1, and the pencil hardness was measured to be 5-6H. Further, when the adhesion of the photocatalyst layer was examined using an adhesive cellophane tape, no peeling of the photocatalyst layer was observed, and the adhesion was good. Further, when the limit contact angle was measured in the same manner as in Example 1, it was 4 degrees.
  • Example 3 The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 10 parts by mass, respectively.
  • a photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the content was 50 parts by mass and 20 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
  • the niobium oxide sol particles, colloidal silica particles, and the total content thereof were 50 parts by mass, 250 parts by mass, and 300 parts by mass, respectively, in terms of oxide with respect to 100 parts by mass of ethyl silicate in terms of oxide. It was.
  • the total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
  • a photocatalyst layer was prepared in the same manner as in Example 1, and the pencil hardness was measured to be 3-4H. Moreover, when the adhesiveness of the photocatalyst layer was examined using an adhesive cellophane tape, no peeling of the photocatalyst layer was observed, and the adhesiveness was good. Further, when the limit contact angle was measured in the same manner as in Example 1, it was 4 degrees.
  • Example 4 The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 20 parts by mass, respectively.
  • a photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the content was 40 parts by mass and 20 parts by mass.
  • the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
  • the niobium oxide sol particles, colloidal silica particles, and the total content thereof were 100 parts by mass, 200 parts by mass, and 300 parts by mass, respectively, in terms of oxides with respect to 100 parts by mass of ethyl silicate in terms of oxides. It was.
  • the total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
  • a photocatalyst layer was prepared in the same manner as in Example 1, and the pencil hardness was measured to be 5-6H. Further, when the adhesion of the photocatalyst layer was examined using an adhesive cellophane tape, no peeling of the photocatalyst layer was observed, and the adhesion was good. Further, when the limit contact angle was measured in the same manner as in Example 1, it was 6 degrees.
  • Example 5 The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 30 parts by mass, respectively.
  • a photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the content was 33 parts by mass and 17 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
  • the niobium oxide sol particles, colloidal silica particles, and the total content thereof were 176 parts by mass, 194 parts by mass, and 371 parts by mass, respectively, in terms of oxide with respect to 100 parts by mass of ethyl silicate in terms of oxide. It was.
  • the total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
  • a photocatalyst layer was prepared in the same manner as in Example 1, and the pencil hardness was measured to be 3-4H. Moreover, when the adhesiveness of the photocatalyst layer was examined using an adhesive cellophane tape, no peeling of the photocatalyst layer was observed, and the adhesiveness was good. Further, when the limit contact angle was measured in the same manner as in Example 1, it was 12 degrees.
  • the content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 40 parts by mass, respectively.
  • a photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the content was 27 parts by mass and 13 parts by mass.
  • the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
  • the niobium oxide sol particles, colloidal silica particles, and the total content thereof were 308 parts by mass, 208 parts by mass, and 515 parts by mass, respectively, in terms of oxide with respect to 100 parts by mass of ethyl silicate in terms of oxide. It was.
  • the total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
  • a photocatalyst layer was prepared in the same manner as in Example 1, and when pencil hardness was measured, scratches were generated just by rubbing with an eraser, and the pencil hardness was less than 6B. .
  • the content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 50 parts by mass, respectively.
  • a photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the content was 20 parts by mass and 10 parts by mass.
  • the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
  • the niobium oxide sol particles, colloidal silica particles, and the total content thereof were 500 parts by mass, 200 parts by mass, and 700 parts by mass, respectively, in terms of oxides with respect to 100 parts by mass of ethyl silicate in terms of oxides. It was.
  • the total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
  • a photocatalyst layer was prepared in the same manner as in Example 1, and when pencil hardness was measured, scratches were generated just by rubbing with an eraser, and the pencil hardness was less than 6B. .
  • the content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 10 parts by mass, respectively.
  • a photocatalyst coating liquid was prepared in the same manner as in Example 1 except that 52.5 parts by mass and 17.5 parts by mass were used. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
  • the niobium oxide sol particles, colloidal silica particles, and the total content thereof were 57 parts by mass, 300 parts by mass, and 357 parts by mass, respectively, in terms of oxide with respect to 100 parts by mass of ethyl silicate in terms of oxide. It was.
  • the total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
  • a photocatalyst layer was prepared in the same manner as in Example 1, and when pencil hardness was measured, scratches were generated just by rubbing with an eraser, and the pencil hardness was less than 6B. .
  • the content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 20 parts by mass, respectively.
  • a photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the content was 45 parts by mass and 15 parts by mass.
  • the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
  • the niobium oxide sol particles, colloidal silica particles, and the total content thereof were 133 parts by mass, 300 parts by mass, and 433 parts by mass, respectively, in terms of oxide with respect to 100 parts by mass of ethyl silicate in terms of oxide. It was.
  • the total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
  • a photocatalyst layer was prepared in the same manner as in Example 1, and when pencil hardness was measured, scratches were generated just by rubbing with an eraser, and the pencil hardness was less than 6B. .
  • the content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 30 parts by mass, respectively.
  • a photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the amount was 37.5 parts by mass and 12.5 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
  • the niobium oxide sol particles, colloidal silica particles, and the total content thereof were 240 parts by mass, 300 parts by mass, and 540 parts by mass, respectively, in terms of oxides with respect to 100 parts by mass of ethyl silicate in terms of oxides. It was.
  • the total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
  • a photocatalyst layer was prepared in the same manner as in Example 1, and when pencil hardness was measured, scratches were generated just by rubbing with an eraser, and the pencil hardness was less than 6B. .
  • the content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 0 parts by mass, respectively.
  • a photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the amount was 65 parts by mass and 15 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
  • the niobium oxide sol particles, colloidal silica particles, and the total content thereof were 0 parts by mass, 433 parts by mass, and 433 parts by mass, respectively, in terms of oxide with respect to 100 parts by mass of ethyl silicate in terms of oxide. It was.
  • the total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
  • a photocatalyst layer was prepared in the same manner as in Example 1, and the pencil hardness was measured to be 5-6H. Further, when the adhesion of the photocatalyst layer was examined using an adhesive cellophane tape, the photocatalyst layer was not peeled and the adhesion was good, but the limit contact angle was measured in the same manner as in Example 1. Then, it was 20 degrees.
  • the content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 25 parts by mass and 10 parts by mass, respectively.
  • a photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the content was 65 parts by mass and 0 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
  • the total content of niobium oxide sol particles, colloidal silica particles, and oxide-converted ethyl silicate was 300 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
  • a photocatalyst layer was prepared in the same manner as in Example 1, and when pencil hardness was measured, scratches were generated just by rubbing with an eraser, and the pencil hardness was less than 6B. .
  • Example 6 When the photocatalytic activity of the photocatalyst layer formed using the photocatalyst coating liquid obtained in Example 1 was evaluated, the first-order rate constant was 0.11 h ⁇ 1 .
  • a photocatalyst layer By applying and drying the photocatalyst coating liquid obtained in Examples 1 to 5 on the tiles applied to the indoor wall surface, a photocatalyst layer can be formed on the tile surface.
  • Light irradiation can reduce the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in indoor spaces, can kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, Allergens such as mite allergens and cedar pollen allergens can also be rendered harmless.
  • the surface of the tile becomes hydrophilic, so that dirt can be easily wiped off, and charging can be prevented.
  • a photocatalyst layer By applying the photocatalyst coating liquid obtained in Examples 1 to 5 to the indoor side surface of the window glass and drying, a photocatalyst layer can be formed on the glass surface, whereby light irradiation by indoor lighting is performed.
  • allergens such as cedar pollen allergens can also be rendered harmless.
  • the surface of the window glass becomes hydrophilic, so that dirt can be easily wiped off, and further charging can be prevented.
  • a photocatalyst layer By applying the photocatalyst coating liquid obtained in Examples 1 to 5 to the indoor floor surface and drying, a photocatalyst layer can be formed on the floor surface, and thus, indoors can be formed by light irradiation with indoor lighting. It can reduce the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in the space, kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, and mite allergens and cedar Allergens such as pollen allergens can also be rendered harmless. Furthermore, the surface of the floor becomes hydrophilic, so that dirt can be easily wiped off and charging can be prevented.
  • volatile organic substances for example, formaldehyde, acetaldehyde, acetone, toluene, etc.
  • kill pathogenic bacteria such as Staphylococcus aureus and Escherichia
  • a photocatalyst layer By applying the photocatalyst coating liquid obtained in Examples 1 to 5 to the surface of the air conditioner and drying it, a photocatalyst layer can be formed on the surface of the air conditioner. It can reduce the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in the space, kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, and mite allergens and cedar Allergens such as pollen allergens can also be rendered harmless. Furthermore, the surface of the air conditioner becomes hydrophilic, so that dirt can be easily wiped off, and charging can be prevented.
  • volatile organic substances for example, formaldehyde, acetaldehyde, acetone, toluene, etc.
  • kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli
  • a photocatalyst layer can be formed in the refrigerator by applying the photocatalyst coating liquid obtained in Examples 1 to 5 to the refrigerator and drying it.
  • the surface in the refrigerator compartment becomes hydrophilic, so that dirt can be easily wiped off and charging can be prevented.
  • a photocatalyst layer can be formed on the inside, thereby reducing the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in the indoor space by light irradiation by indoor lighting, Pathogens such as Staphylococcus aureus and Escherichia coli can be killed, and allergens such as mite allergens and cedar pollen allergens can be rendered harmless. Further, the surface of the base material becomes hydrophilic, so that dirt can be easily wiped off, and charging can be prevented.
  • volatile organic substances for example, formaldehyde, acetaldehyde, acetone, toluene, etc.
  • Pathogens such as Staphylococcus aureus and Escherichia coli can be killed, and allergens such as mite allergens and cedar pollen allergens can be rendered harmless.
  • the surface of the base material becomes hydrophilic,

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Abstract

L'invention concerne : un liquide de revêtement photocatalyseur capable de fournir une couche de photocatalyseur qui présente une excellente adhérence sur le substrat lors de la formation de la couche de photocatalyseur sur une surface d'un substrat, la couche de photocatalyseur montrant une haute activité photocatalytique suite à l'irradiation par une source lumineuse pratique telle qu'une lumière fluorescente ; et un produit présentant une fonctionnalité photocatalytique doté d'une couche de photocatalyseur sur sa surface. Le liquide de revêtement photocatalyseur comprend, dans un rapport prédéterminé, (1) des particules de photocatalyseur, (2) des particules de sol d'oxyde de niobium, (3) des particules de silice colloïdale, (4) des alcoxydes de silicium et (5) un solvant, et la teneur en solides obtenue en évaporant les composants volatils du liquide de revêtement photocatalyseur est dans un rapport prédéterminé par rapport au liquide de revêtement photocatalyseur.
PCT/JP2011/064679 2010-07-23 2011-06-27 Liquide de revêtement photocatalyseur et produit présentant une fonctionnalité photocatalytique Ceased WO2012011367A1 (fr)

Applications Claiming Priority (2)

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JP2010165705A JP2012025849A (ja) 2010-07-23 2010-07-23 光触媒体コーティング液、および光触媒機能製品
JP2010-165705 2010-07-23

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WO2012011367A1 true WO2012011367A1 (fr) 2012-01-26

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WO (1) WO2012011367A1 (fr)

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JP6624195B2 (ja) * 2015-03-03 2019-12-25 株式会社スリーボンド 防曇剤組成物
JP7349394B2 (ja) * 2019-05-28 2023-09-22 シャープ株式会社 組成物、コーティング方法及び多層構造体

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WO2000018504A1 (fr) * 1998-09-30 2000-04-06 Nippon Sheet Glass Co., Ltd. Article photocatalyseur, article protege contre l'encrassement et le voilement, et procede de production d'un article protege contre l'encrassement et le voilement
JP2002053772A (ja) * 2000-08-08 2002-02-19 Nippon Soda Co Ltd 光触媒を担持してなる構造体
WO2006025535A1 (fr) * 2004-09-03 2006-03-09 Jsr Corporation Composition de revêtement, composition de sous-couche, corps multicouche ayant un film de revêtement formé d'une telle composition, film de revêtement photocatalyseur et corps moulé
JP2007117999A (ja) * 2005-09-29 2007-05-17 Sumitomo Metal Ind Ltd 酸化チタン系光触媒とその用途
JP2007168137A (ja) * 2005-12-19 2007-07-05 Kubota Matsushitadenko Exterior Works Ltd 塗装体
JP2007185556A (ja) * 2006-01-11 2007-07-26 Mitsubishi Plastics Ind Ltd 光触媒層を形成した基材及び光触媒層形成用組成物
JP2010280859A (ja) * 2009-06-08 2010-12-16 Toto Ltd 高温焼成用光触媒コーティング組成物、および光触媒材の製造方法
JP2011083747A (ja) * 2009-10-19 2011-04-28 Sumitomo Chemical Co Ltd 貴金属担持光触媒体粒子分散液、および光触媒体機能製品
JP2011110542A (ja) * 2009-11-30 2011-06-09 Panasonic Electric Works Co Ltd 空間の浄化方法及び空間の浄化設備

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Publication number Priority date Publication date Assignee Title
WO2000018504A1 (fr) * 1998-09-30 2000-04-06 Nippon Sheet Glass Co., Ltd. Article photocatalyseur, article protege contre l'encrassement et le voilement, et procede de production d'un article protege contre l'encrassement et le voilement
JP2002053772A (ja) * 2000-08-08 2002-02-19 Nippon Soda Co Ltd 光触媒を担持してなる構造体
WO2006025535A1 (fr) * 2004-09-03 2006-03-09 Jsr Corporation Composition de revêtement, composition de sous-couche, corps multicouche ayant un film de revêtement formé d'une telle composition, film de revêtement photocatalyseur et corps moulé
JP2007117999A (ja) * 2005-09-29 2007-05-17 Sumitomo Metal Ind Ltd 酸化チタン系光触媒とその用途
JP2007168137A (ja) * 2005-12-19 2007-07-05 Kubota Matsushitadenko Exterior Works Ltd 塗装体
JP2007185556A (ja) * 2006-01-11 2007-07-26 Mitsubishi Plastics Ind Ltd 光触媒層を形成した基材及び光触媒層形成用組成物
JP2010280859A (ja) * 2009-06-08 2010-12-16 Toto Ltd 高温焼成用光触媒コーティング組成物、および光触媒材の製造方法
JP2011083747A (ja) * 2009-10-19 2011-04-28 Sumitomo Chemical Co Ltd 貴金属担持光触媒体粒子分散液、および光触媒体機能製品
JP2011110542A (ja) * 2009-11-30 2011-06-09 Panasonic Electric Works Co Ltd 空間の浄化方法及び空間の浄化設備

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