WO2004108283A1 - 光触媒部材 - Google Patents

光触媒部材 Download PDF

Info

Publication number
WO2004108283A1
WO2004108283A1 PCT/JP2004/008022 JP2004008022W WO2004108283A1 WO 2004108283 A1 WO2004108283 A1 WO 2004108283A1 JP 2004008022 W JP2004008022 W JP 2004008022W WO 2004108283 A1 WO2004108283 A1 WO 2004108283A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
photocatalyst
member according
heat
photocatalyst member
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2004/008022
Other languages
English (en)
French (fr)
Inventor
Toshiaki Anzaki
Yoshifumi Kijima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Sheet Glass Co Ltd
Original Assignee
Nippon Sheet Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Sheet Glass Co Ltd filed Critical Nippon Sheet Glass Co Ltd
Priority to JP2005506824A priority Critical patent/JP4460537B2/ja
Priority to US10/560,053 priority patent/US20070082205A1/en
Priority to EP04745697A priority patent/EP1637225A4/en
Publication of WO2004108283A1 publication Critical patent/WO2004108283A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B01J21/066—Zirconium or hafnium; 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
    • 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
    • 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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
    • 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
    • B01J37/0228—Coating in several steps
    • 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
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/347—Ionic or cathodic spraying; Electric discharge
    • 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
    • C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
    • 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
    • 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
    • C03C2217/75—Hydrophilic and oleophilic coatings
    • 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
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
    • C03C2217/948—Layers comprising indium tin oxide [ITO]
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/154—Deposition methods from the vapour phase by sputtering
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/365—Coating different sides of a glass substrate

Definitions

  • the present invention relates to architectural glass, automotive glass, display glass, biochips, chemical chips, electronic devices, optical devices, glass fibers, glass flakes, and the like. It relates to the field of application of photocatalysts to clouding, decomposition of organic matter, etc. for these purposes.
  • photocatalysts such as anatase-type titanium oxide exhibit an antifouling effect of decomposing organic substances upon irradiation with ultraviolet rays, and have an antibacterial property and a hydrophilic property. Recently, a photocatalyst that exerts a catalytic function by visible light has attracted attention.
  • a heat treatment is performed at the time of forming the film, or after forming the film, in the air or in a vacuum, so that its crystallinity can be improved. It is disclosed that the photocatalytic activity is improved to make the material worthy of practical use.
  • Patent Document 1 Japanese Patent No. 2517874 (pages 2 to 4).
  • the present invention has been made in view of the above problems, and has been made practical without heat treatment. It is an object to provide a worthy photocatalyst member.
  • a highly active photocatalyst layer without performing heat treatment.
  • a base layer containing a crystalline zirconium compound, especially a monoclinic zirconium compound as a main component is formed on a base material containing elements having low heat resistance without heating, and then an oxide composed of a crystalline phase is formed.
  • a photocatalyst layer containing titanium as a main component is formed without heating.
  • the base material low heat resistance, glass, low heat resistance, a metal, a resin substrate, a resin film, an organic-inorganic composite substrate, or the like, or a non-heat-resistant thin film may be used. May be.
  • the present invention can be applied to a substrate having a heat-resistant temperature of 700 ° C or less. Particularly, the effect of the present invention can be enjoyed at 500 ° C or less. It can be effectively applied to substrates having a heat resistance temperature of 300 ° C or less.
  • the heat-resistant temperature refers to the upper limit temperature at which the optical transmittance, reflectance, and shape do not change by 5% or more after heat treatment in air at this temperature for 30 minutes.
  • the non-heat-resistant thin film may be, for example, a heat ray reflective film using silver, a heat ray reflective film using a laminated film of a dielectric layer / silver layer / dielectric layer, or a dielectric layer / dielectric layer.
  • a heat ray reflective film using a laminated film of a silver layer / dielectric layer / silver layer / dielectric layer is exemplified.
  • a sacrificial layer made of Zn, Ti, Sn, Nb, or the like may be provided immediately after the formation of the silver layer in order to protect the silver layer from plasma generated in a later step.
  • the photocatalyst member according to the present invention can be provided with an oxide containing at least one of silicon and tin, an oxynitride, and a peel prevention layer mainly containing a nitride on the surface of the base material.
  • a photocatalyst layer is formed on the anti-peeling layer via a crystalline underlayer, and a dead layer (an amorphous layer in which no columnar particle structure is observed) is substantially formed between the underlayer and the photocatalyst layer.
  • the configuration does not exist.
  • the thickness of the above-mentioned peeling prevention layer is 2 nm to 200 nm, preferably 5 nm to 50 nm.
  • the thickness of the peel-prevention layer is less than 2 nm, the effect of suppressing film peeling and occurrence of defects is not sufficient, which is not preferable. Further, even if the thickness is larger than 200 nm, the effect of suppressing the film peeling and the occurrence of defects is not significantly improved. From the viewpoint of economy, the upper limit of the thickness of the peeling prevention layer is preferably 200 nm. When the thickness of the anti-peeling layer is more than 5 nm, the effect of blocking water is increased, which is more preferable. On the other hand, when the thickness exceeds 5 Onm, the stress of the amorphous film increases and the film is easily peeled off. Therefore, the more preferable upper limit of the thickness of the peeling prevention layer is 50 nm.
  • a photocatalyst layer is formed on a surface of a base material via a crystalline underlayer, and the base material is a glass substrate manufactured by a float glass method.
  • the underlayer is provided on the surface of the glass substrate including the non-heat-resistant thin film or on the surface opposite to the surface.
  • the crystallinity of the photocatalyst layer can be improved, and the surface of the photocatalyst layer can be made superhydrophilic at high speed. Further, by providing a peeling prevention layer between the base material and the crystalline base layer, the peeling of the base layer of the base material and the generation of defects can be suppressed.
  • the peel prevention layer blocks chlorine ions and moisture from the surface, prevents these ions and molecules from reaching the glass substrate (substrate), and suppresses peeling of the underlayer from the substrate. In addition, it is possible to prevent the carbon dioxide gas or moisture from the outside from reacting with the alkali component of the glass substrate, thereby preventing the occurrence of a missing point.
  • the thickness of the photocatalyst layer is preferably lnm-lOOOnm. If it is thinner than lnm, the continuity of the film is poor and the photocatalytic activity is not sufficient. If it is thicker than lOOOnm, the excitation light (ultraviolet rays) does not reach the depth of the photocatalytic film, and the photocatalytic activity no longer increases even if the film thickness is increased. In particular, the effect of the underlayer is largely observed in the range of lnm-500nm. That is, when compared at the same film thickness, the photocatalytic activity was observed to be larger than that without the underlayer, so that the range of 1 nm to 500 nm is more preferable.
  • the width of the particles constituting the photocatalyst layer in the direction parallel to the substrate is preferably 5 nm or more. This is because if the particle width is smaller than 5 nm, the crystallinity is low and the photocatalytic activity is not sufficient.
  • zirconium oxide to which a small amount of nitrogen is added, zirconium oxynitride, and zirconium oxide to which 0.1 to 10 atm% of niobium (Nb) is added, in addition to the monoclinic dinoleconium oxide, are preferably used.
  • niobium-added target it is possible to prevent the occurrence of arcing, undesired power control for that purpose, and a decrease in the film formation rate due to this.
  • tetragonal titanium oxide is preferably used for the photocatalyst layer.
  • anatase type titanium oxide is preferably used because of its high photocatalytic activity.
  • rutile-type titanium oxide, a composite oxide of titanium and tin, a mixed oxide of titanium and tin, titanium oxide to which a trace amount of nitrogen is added, and titanium oxynitride are preferably used.
  • the thickness of the underlayer is preferably lnm or more and 500nm or less. If the thickness is less than 1 nm, the continuity of the underlayer film is lost, resulting in an island shape and reduced durability. Further, even if the thickness is more than 500 ⁇ m, the influence on the photocatalyst layer does not change much, so that increasing the film thickness is not preferable because it is economically wasteful. More preferably, the thickness of the underlayer is 2 to 50 nm. If the thickness is less than 2 nm, the crystallinity of the underlayer is low and the effect of promoting the crystal growth of the photocatalytic layer is small. If the thickness is more than 5 Onm, the fluctuation of the optical characteristics (color tone and reflectance) with respect to the fluctuation of the film thickness increases, which is not preferable.
  • the non-heat-resistant thin film, the underlayer and the photocatalyst layer may be formed by a liquid phase method (sol gel method, liquid phase deposition method, spray method, neurosol method), a gas phase method (sputtering method, vacuum evaporation method). , CVD, etc.), an excellent effect of improving the crystallinity of the photocatalyst layer by the underlayer is recognized.
  • a liquid phase method sol gel method, liquid phase deposition method, spray method, neurosol method
  • a gas phase method sputtering method, vacuum evaporation method
  • CVD etc.
  • the gas phase method is more suitable.
  • the thin film having hydrophilicity is preferably at least one oxide selected from the group consisting of silicon oxide, dinoconium oxide, germanium oxide, and aluminum oxide. Among them, silicon oxide is more preferably used from the viewpoint of the effect of improving hydrophilicity and durability.
  • the hydrophilic thin film is preferably porous. The porous structure enhances the water retention effect and enhances the hydrophilicity retention performance.
  • Active species such as active oxygen generated on the surface of the photocatalyst layer by the irradiation of ultraviolet light can be applied to the surface of the article through the pores. This is because the photocatalytic activity of the photocatalyst layer is not significantly impaired because it can be reached.
  • a liquid phase method (sol-gel method, liquid-phase deposition method, spray method, sol-gel method) or a gas phase method (sputtering method, vacuum deposition method, CVD method) Is used.
  • sol-gel method liquid phase deposition method
  • sputtering method vacuum deposition method, CVD method
  • CVD method gas phase method
  • a porous film is formed by adjusting a film forming condition so as to increase a dangling bond of an oxide by increasing a gas pressure at the time of sputtering or reducing an amount of oxygen in the gas.
  • the ability to produce thin films is not limited to a gas phase method such as a sputtering method.
  • the thickness of the thin film having hydrophilicity is preferably lnm or more and 30nm or less. If the thickness is less than 1 nm, the hydrophilicity is not sufficiently imparted. If the thickness is more than 30 nm, the photocatalytic activity of the photocatalyst layer is impaired. Further, a more preferable range of the thickness is 1 nm or more and 20 nm or less. Within this range, the performance of maintaining hydrophilicity when light is not applied is high.
  • the zirconium compound underlayer When the zirconium compound underlayer is formed by a vapor deposition method, a sputtering method, or the like, particularly in a reduced-pressure atmosphere, the thin film itself becomes a monoclinic or other crystalline thin film even at a low temperature. . Since this crystalline underlayer plays a role of a seed layer for the growth of titanium oxide and other photocatalytic films formed thereon, it can be formed without heating. A photocatalytic layer having high crystallinity can be easily obtained. When titanium oxide is used as the photocatalyst layer, it often grows into an anatase type crystal, whereby a very highly active photocatalyst layer can be obtained without heating.
  • a photocatalytic layer having high photocatalytic activity can be formed on a base material or a thin film without heating, and can be formed on a base material or a thin film without heating. It is also possible to combine with other members.
  • the present invention can be applied to film formation on a large-sized base material such as glass, which is difficult to uniformly heat and prevent breakage during heating and cooling.
  • a photocatalyst layer is formed on a base material surface via a base layer mainly composed of a crystalline dinoreconium compound, and the base layer reduces the crystallinity of the photocatalyst layer.
  • a base layer mainly composed of a crystalline dinoreconium compound
  • the base layer reduces the crystallinity of the photocatalyst layer.
  • the present invention can also be applied to film formation on a large-sized base material such as glass, which is difficult to uniformly heat and suppress breakage during heating and cooling.
  • FIG. 1 is a cross-sectional view of a specific example of a photocatalyst member according to the present invention.
  • FIG. 2 is a cross-sectional view of a specific example of a photocatalyst member according to the present invention.
  • FIG. 3 is a sectional view of a specific example of a photocatalyst member according to the present invention.
  • FIG. 3 is a cross-sectional view showing a specific example of the photocatalyst member according to the present invention, and in the specific example shown in FIG.
  • a monoclinic Zr ⁇ layer is formed as a formation layer, and a crystalline Ti ⁇ layer is further formed thereon as a photocatalyst layer.
  • an anti-peeling layer may be formed between the substrate and the underlayer, or a porous SiO layer may be formed on the crystalline TiO layer to enhance hydrophilicity.
  • a non-heat-resistant thin film, a monoclinic ZrO layer as an underlayer, and a crystalline TiO layer as a photocatalytic layer are formed in this order on the surface of a glass plate as a substrate. ing.
  • an anti-peeling layer may be formed between the substrate and the underlayer, or a porous SiO layer may be formed on the crystalline TiO layer to enhance hydrophilicity. Good.
  • a monoclinic ZrO layer is formed as an underlayer on the surface of a substrate that is a non-heat-resistant base material, and a crystalline layer is further formed on the monoclinic ZrO layer as a photocatalytic layer.
  • an anti-peeling layer may be formed between the substrate and the underlayer, or a porous SiO layer may be formed on the crystalline TiO layer to enhance hydrophilicity.
  • the non-heat-resistant thin film, ZrO layer, TiO layer and SiO layer are formed by a sputtering method.
  • non-heat-resistant thin film examples include a multilayer film such as a dielectric layer / silver layer / dielectric layer / silver layer / dielectric layer.
  • Tables 1 and 2 below summarize the evaluation results of the non-heat-resistant thin films of Examples 14 to 14, the configurations of the underlayer, the photocatalyst layer, and the anti-peeling layer, and the photocatalytic and optical properties.
  • the heat treatment step of Comparative Example 16 and the method for forming the photocatalytic layer and the peel-prevention layer, and the evaluation results of the photocatalytic properties and the optical properties are also shown.
  • a zinc oxide layer and a silver layer are alternately laminated on a soda-lime glass substrate with a length of Im x width lm and a thickness of 3 mm.
  • a multilayer film having a structure of 40 nm / silver layer 1 Onm / zinc oxide layer 80 nm / silver layer 1 Onm / zinc oxide layer 40 nm was formed.
  • the zinc oxide layer was formed using a zinc oxide target to which aluminum was added, and the silver layer was formed using a silver target.
  • Each of the layers was formed in a reduced-pressure argon atmosphere without heating.
  • This multilayer film of zinc oxide and silver has a heat ray reflection function, but has low heat resistance.
  • the heat resistance temperature as defined above is 150 ° C. would.
  • a photocatalytic glass having a non-heat-resistant function in which a heat ray reflecting film composed of a multilayer film of zinc oxide and silver was formed on one surface of a soda lime glass substrate and a photocatalyst layer was formed on the other surface.
  • a heat ray reflecting film composed of a multilayer film of zinc oxide and silver was formed on one surface of a soda lime glass substrate and a photocatalyst layer was formed on the other surface.
  • silver aggregation did not occur, and an article having high visible light transmittance was obtained.
  • Table 1 shows the measurement results of the visible light transmittance.
  • the visible light transmittance was measured using a D65 light source according to JIS R3106 “Test method for transmittance of sheet glass 'reflectance' emissivity and solar heat gain”.
  • the photocatalytic activity of the photocatalyst layer was evaluated using an index of hydrophilicity-imparting performance. After the formation of the photocatalyst layer, the multilayer film article was left in a place where no light was irradiated for 14 days, and carbon in the atmosphere was deposited on the surface to reduce the hydrophilicity of the surface. Thereafter, the surface of the titanium oxide layer was irradiated with ultraviolet light having an intensity of lmWZcm 2 for 1 hour using a black light, and the following evaluation was performed based on the contact angle of water droplets after irradiation. Water contact angle (°) Photocatalytic activity evaluation
  • soda-lime glass substrate having the heat ray reflective film formed on the inner side With the soda-lime glass substrate having the heat ray reflective film formed on the inner side, another soda lime glass and this glass are subjected to a multi-layer glass processing treatment, and the heat ray reflective film is formed on the inner surface of the outdoor glass.
  • a heat-reflective double-glazed glass having an antifouling function in which a photocatalyst antifouling film was formed on the outer surface of the outdoor glass was obtained.
  • a monoclinic dinoreconium oxide layer lOnmZ anatase-type titanium oxide layer of 20 nm was formed on an acrylic resin substrate having a length of lm x a width of lm and a thickness of 3 mm.
  • Each film was formed by a non-heated reactive sputtering method using a zirconium target and a titanium target in an atmosphere (0.93 Pa) of an equal mixture of argon and oxygen.
  • the acrylic resin has low heat resistance, and the heat resistance temperature as defined above is 230 ° C. Exposure to temperatures higher than this temperature will result in a yellow coloration. Since no heating step was used in the photocatalytic layer film forming step, the acrylic resin substrate did not turn yellow, and the optical characteristics of the acrylic resin before and after the film formation did not change at all.
  • This non-heat-resistant photocatalytic glass substrate can be used as a display substrate.
  • an indium tin oxide (IT ⁇ ) layer and a silver layer are alternately laminated on a polyethylene terephthalate (PET) film substrate with a length of lm x a width of lm and a thickness of 3 mm.
  • a multilayer film having a structure of: ⁇ layer 45 nm / silver layer 1 OnmZlTO layer 40 nm was obtained.
  • the ITO layer was formed by using an ITO target, and the silver layer was formed by using a silver target without heating in a reduced-pressure argon atmosphere.
  • the multilayer film of IT ⁇ and silver has a heat ray reflection function, but has low heat resistance, and the heat resistance temperature defined above is 150 ° C. When exposed to temperatures exceeding this heat resistance temperature, silver aggregates and blacks out. It will be.
  • the PET film itself is also heat-resistant The temperature is 180 ° C. Above this temperature, softening deformation is remarkable.
  • the PET film substrate and the silver layer contain elements having low heat resistance, but since no heating step was used in the film forming step, no deterioration was observed, and the article had good optical characteristics. was gotten.
  • This photocatalyst substrate can be used as an antifouling film having an electromagnetic shielding function.
  • a silicon oxide layer lOnm / monoclinic dinoreconium oxide layer 1 Onm / niobium-doped anatase-type titanium oxide layer 1 on a thin soda lime glass substrate with a length of lm x a width of lm and a thickness of lmm Onm formed.
  • the silicon oxide layer and the monoclinic dinoreconium oxide layer were formed by a non-heating reactive sputtering method using a silicon target and a zirconium target, respectively, in a mixed atmosphere of argon and oxygen (0.93 Pa). Formed.
  • the Nb-doped anatase-type titanium oxide layer was formed by a non-heating sputtering method in an argon atmosphere (0.93 Pa) using a titanium-niobium oxide target.
  • the niobium titanium oxide layer of the obtained article had good photocatalytic activity.
  • a thin soda-lime glass substrate having a thickness of lmm is easily deformed when exposed to a high temperature, and the heat-resistant temperature as defined above is 500 ° C. Since no heating step was performed in the film formation, no deformation of the substrate was observed before and after the film formation.
  • This photocatalyst substrate can be used as a biochemical chip.
  • Example 2 Each film was formed under the same conditions as in Example 1 except that the dinoreconium oxide layer was not formed.
  • the resulting article had a high visible light transmittance of 73%, which was excellent.
  • the evaluation of the photocatalytic activity of the titanium oxide layer was "X".
  • the article of Comparative Example 1 was heated in the air at 400 ° C. for 30 minutes to perform a heat treatment on the titanium oxide film. After this heat treatment, the evaluation of the photocatalytic activity was “ ⁇ ”, but the visible light transmittance was reduced due to aggregation of the silver in the heat ray reflective film (from 73% before heating to 54% after heating).
  • Example 2 Each film was formed under the same conditions as in Example 2 except that the dinoreconium oxide layer was not formed. As a result of evaluating the photocatalytic activity of the titanium oxide layer of the obtained article, the evaluation was "X".
  • the article of Comparative Example 3 was heated in the air at 350 ° C. for 30 minutes to perform a heat treatment on the titanium oxide film. After this heat treatment, the evaluation of the photocatalytic activity was “ ⁇ ”, but the acrylic resin on the substrate turned yellow and the visible light transmittance was reduced (from 92% before heating to 75% after heating).
  • Example 4 Each film was formed under the same conditions as in Example 4 except that the dinoleconium oxide layer was not formed. As a result of evaluating the photocatalytic activity of the titanium oxide layer of the obtained article, the evaluation was “X”.
  • the article of Comparative Example 5 was heated in the air at 600 ° C. for 30 minutes to perform a heat treatment on the titanium oxide film. After this heat treatment, the evaluation of the photocatalytic activity was “ ⁇ ”, but it was clear that the substrate was significantly deformed and could not be used as a commercial product.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Catalysts (AREA)
  • Surface Treatment Of Glass (AREA)
  • Physical Vapour Deposition (AREA)

Description

明 細 書
光触媒部材
技術分野
[0001] 本発明は、建築用ガラス， 自動車用ガラス，ディスプレイ用ガラス，バイオチップ，ケ ミカルチップ，電子デバイス，光デバイス，ガラス繊維，ガラスフレークなどに関するも のであり、特に、防汚，親水，防曇，有機物分解などの目的でこれらに光触媒を適用 する応用分野に関する。
背景技術
[0002] アナターゼ型の酸化チタンなどの光触媒は紫外線の照射によって有機物を分解す る防汚効果、抗菌性および親水性を発揮することが知られている。また最近では可 視光によって触媒機能を発揮する光触媒も注目されている。
[0003] 酸化チタンの膜を形成し、その触媒活性を向上させる手段として、膜を形成する際 、あるいは膜を形成した後に、大気中あるいは真空中などで熱処理を施すことにより 、その結晶性などを向上させ光触媒活性を高めて実用に値する物とすることが開示 されている。
[0004] 特許文献 1：特許第 2517874号公報 (第 2頁一第 4頁)。
発明の開示
発明が解決しょうとする課題
[0005] し力しながら、このような熱処理を実施すると、光触媒の性能は向上するものの、そ の基材となっている材料や、その基材に既に形成されている別の機能性膜などが、こ の熱により変形や酸化、コロイドィ匕などを起こし、その形状や光学特性などが劣化し てしまうという問題がある。
[0006] 特に樹脂基板や樹脂フィルム、耐熱性の低いガラスやその他の材料、また一般的 に耐熱性の低い、銀などの材料を用いた熱線反射膜 (いわゆる Low-E膜)などは熱 処理の影響を受けやすぐこれらを具備した基材に実用的な光触媒層を形成する場 合に特に問題があった。
[0007] 本発明は、上記の問題に鑑みてなされたものであり、熱処理を行わなくても実用に 値する光触媒部材を提供することを目的とする。
課題を解決するための手段
[0008] 上記課題を解決するため、本発明者らは熱処理を施さなくても高活性な光触媒層 を得る手段を鋭意検討した。その結果、ある特定の下地層上に光触媒層を形成する ことで、一貫して低温のプロセスであっても、高活性な光触媒層が得られることを発見 した。具体的には耐熱性の低い要素を含む基材に結晶性ジルコニウム化合物、とり わけ単斜晶系ジルコニウム化合物を主成分とする下地層を非加熱で成膜し、その後 結晶相から構成される酸化チタンを主成分とする光触媒層が非加熱で形成される。
[0009] 上記基材は、耐熱性の低レ、ガラス、耐熱性の低レ、金属、樹脂基体、樹脂フィルム、 有機無機複合体基体などを用いてもいいし、非耐熱性薄膜を有するものでもよい。 本発明は 700°C以下の耐熱温度の基材に適用できる力 特に、本発明の効果が享 受できる 500°C以下、さらには、従来技術では高活性な光触媒層の形成が困難とな る 300°C以下の耐熱温度の基材に有効に適用できる。なお耐熱温度とは、この温度 で 30分間大気中にて熱処理し、光学透過率，反射率，形状に 5%以上の変化がな い上限温度をさす。
[0010] また、上記非耐熱性薄膜としては、例えば、銀を使用した熱線反射膜、若しくは誘 電体層/銀層/誘電体層の積層膜を使用した熱線反射膜、若しくは誘電体層/銀 層/誘電体層/銀層/誘電体層の積層膜を使用した熱線反射膜等が挙げられる。 上記積層膜を形成するに当たり、後の工程で生じるプラズマから銀層を保護するた めに、銀層の成膜直後に Zn， Ti, Sn， Nbなどからなる犠牲層を設けてもよい。
[0011] また、本発明に係る光触媒部材は、基材表面に珪素、錫の少なくとも一方を含む酸 化物、酸窒化物、及び窒化物を主成分とする剥離防止層を設けることができる。この 剥離防止層の上に結晶性の下地層を介して光触媒層が形成され、更に上記下地層 と光触媒層との間にはデッドレイヤー（柱状粒子構造が認められないアモルファス層 )が実質的に存在しない構成である。なお、上記の剥離防止層の厚みは 2nm— 200 nmであり、好ましくは 5nm— 50nmである。剥離防止層の厚みが 2nmより薄いと、膜 剥離や欠点の発生の抑制効果が充分ではなく好ましくなレ、。またこれが 200nmより 厚くなつても、前記膜剥離や欠点の発生の抑制効果が大きく向上することはないの で、経済的観点から、剥離防止層の厚みの上限は 200nmが好ましい。剥離防止層 の厚みが 5nmより厚いと、水に対する遮断効果がより大きくなり、より好ましい。また 5 Onmを超えると、非晶質膜の応力が大きくなり、剥離しやすいので、剥離防止層の厚 みのさらに好ましい上限は 50nmである。
[0012] また、本発明に係る光触媒部材の一形態は、基材表面に結晶性の下地層を介して 光触媒層が形成され、また、基材はフロートガラス法で作製したガラス基板であり、か つこのガラス基板の非耐熱性薄膜を含む面または、その面とは反対側の面の上に前 記下地層が設けられる。
[0013] 結晶性の下地層を設けることによって、光触媒層の結晶性を向上させることができ、 光触媒層表面を高速に超親水化することができる。さらに、基材と結晶性下地層との 間に剥離防止層を設けることによって、基材カ の下地層の剥離や欠点の発生を抑 制すること力 Sできる。
[0014] 上記剥離防止層は、表面からの塩素イオンや水分を遮断し、これらイオンや分子が ガラス基板 (基材)まで到達するのを防ぎ、基板からの下地層の剥離を抑制できる。ま た、外界からの炭酸ガスや水分とガラス基板のアルカリ成分とが反応して、ャケゃ欠 点となるのを防ぐことができる。
[0015] 上記光触媒層の厚みは lnm— lOOOnmが好ましい。 lnmより薄いと膜の連続性が 悪く光触媒活性が十分でなぐ lOOOnmより厚いと光触媒膜の奥まで励起光 (紫外 線）が届かず、膜厚を大きくしてももはや光触媒活性は大きくならない。特に、 lnm— 500nmの範囲では下地層の効果が大きく観測される。即ち、同じ膜厚で比較した場 合、下地層がない場合よりも光触媒活性が大きく観察されたので、 lnm— 500nmの 範囲が更に好ましい。
[0016] 光触媒層の厚みを lnm lOOOnmと薄くしても、光触媒層を構成する粒子が下地 層との界面から光触媒層表面まで連続的に形成されていれば、結晶成長が進んで おり、光触媒活性を十分に発揮できる。
[0017] 光触媒層を構成する粒子の基板と平行な方向の幅は 5nm以上であることが好まし レ、。これは粒子幅が 5nmより小さいと結晶性が低ぐ光触媒活性が十分でないことに よる。 [0018] 下地層としては、前記単斜晶系酸化ジノレコニゥムの他、窒素が微量添加された酸 化ジルコニウム、酸窒化ジルコニウム、ニオブ（Nb)を 0. 1— 10atm%添加した酸化 ジルコニウムが好ましく用いられる。特にニオブを添加したターゲットを用いてスパッタ する場合には、アーキングの発生とそのための不本意なパワー制御及びそれによる 成膜レートの低下を防止できる。
[0019] また、光触媒層としては正方晶系酸化チタンが好ましく用いられるが、特にアナター ゼ型酸化チタンは光触媒活性が高いので好ましく用いられる。アナターゼ型酸化チ タンの他、ルチル型酸化チタン、チタンと錫の複合酸化物、及びチタンと錫の混合酸 化物、窒素が微量添加された酸化チタンや、酸窒化チタンが好ましく用いられる。
[0020] 下地層の厚みは、 lnm以上 500nm以下が好ましレ、。 lnmより薄いと下地層の膜と しての連続性がなくなり、島状になり耐久性が低下するので好ましくない。更に 500η mより厚くても、光触媒層への影響はあまり変わらないので、膜厚を大きくすることが、 経済的な無駄となり好ましくない。さらに好ましい下地層の厚みは 2— 50nmである。 2nmより薄いと、下地層の結晶性が低ぐ光触媒層の結晶成長促進効果が小さい。 5 Onmより厚いと、膜厚変動に対する光学的特性 (色調、反射率）の変動が大きくなる ので、好ましくない。
[0021] 上記非耐熱性薄膜、下地層および光触媒層の形成方法としては、液相法 (ゾルゲ ル法、液相析出法、スプレー法、ノイロゾル法）、気相法 (スパッタリング法、真空蒸着 法、 CVD法）など、何れの方法でも良ぐ下地層による光触媒層の結晶性向上効果 が認められるが、結晶成長を伴うので、本発明において特に大きな効果が認められ るスパッタリング法や蒸着法などの気相法がさらに適当である。
[0022] また、上記光触媒層の表面に親水性を有する薄膜を形成することで親水効果を高 めること力できる。親水性を有する薄膜は、酸化珪素、酸化ジノレコニゥム、酸化ゲル マニウム、酸化アルミニウムからなる群より選ばれる少なくとも一種の酸化物が好まし レ、。これらのうち酸化珪素が、親水性向上効果と耐久性の観点から、さらに好ましく用 レ、られる。親水性を有する薄膜は、多孔質状であることが好ましい。多孔質状である ことで、保水効果が高まり、親水性の維持性能が高まるば力 でなぐ紫外線照射に よって光触媒層表面で発生した活性酸素等の活性種が孔を通って物品の表面まで 到達できるので、光触媒層の光触媒活性を大きく損なうことがないからである。
[0023] 多孔質状の親水性薄膜を形成する方法としては、液相法（ゾルゲル法、液相析出 法、スプレー法、ゾルゲル法)や気相法 (スパッタリング法、真空蒸着法、 CVD法）が 用いられる。一般に知られているゾルゲル法を適用すれば、多孔質状の薄膜が簡単 に作製できる力 ゾルゲル法の原料液中に有機高分子や高級アルコールを添加す ることで、さらに容易に多孔質の薄膜を得ることができる。スパッタリング法などの気相 法では、スパッタ時のガス圧を上げる、ガス中の酸素の量を減らす等、酸化物のダン グリングボンドを増やすように成膜条件を調整することで、多孔質状の薄膜を作製す ること力 Sできる。
[0024] 上記親水性を有する薄膜の厚みは、 lnm以上 30nm以下が好ましレ、。 lnmより薄 いと、親水性の付与が十分でなぐ 30nmより厚いと光触媒層の光触媒活性を損なう ので、好ましくない。また、この厚みのさらに好ましい範囲は、 lnm以上 20nm以下で ある。この範囲で、光が当らない時の親水性維持性能が高い。
[0025] ジルコニウム化合物下地層を、特に減圧雰囲気中で蒸着法やスパッタリング法など にて成膜する場合、低温であってもそれ自体が単斜晶系をはじめとする結晶性の薄 膜となる。この結晶性の下地層がその上に形成される酸化チタンをはじめとする光触 媒の膜の成長に対し、 1種のシード (種)層の役割を果たすため、加熱しなくても、結 晶性の高い光触媒層が容易に得られる。光触媒層として酸化チタンを用いた場合、 アナターゼ型結晶に成長する場合が多ぐこの方法により非常に高活性な光触媒層 を非加熱で得ることができる。
[0026] このように、本発明によれば、非加熱で、高い光触媒活性を有する光触媒層を耐熱 性の低レ、基材上ゃ薄膜上にも形成することができ、耐熱性の低レ、部材との組み合わ せも可能となる。また、均一加熱や、加熱冷却時の破損抑制が難しいガラスをはじめ とする大きなサイズの基材への成膜にも適用できる。
発明の効果
[0027] 以上に説明したように本発明によれば、基材表面に結晶性ジノレコニゥム化合物を 主成分とした下地層を介して光触媒層が形成され、前記下地層が前記光触媒層の 結晶性を高め、光触媒活性を向上させるので、光触媒層形成後の熱処理が不要とな る。よって建築用の窓ガラス，ディスプレイ用ガラス板， DNA分析用のガラス基板，情 報携帯機器，衛生設備， 医療設備，電子機器，生体 ·医療用の検査チップ，水素 *酸 素発生装置用材料などのあらゆる部材に対して、特に耐熱性が低レ、部材に高レ、光 触媒活性及び防汚性を付与することができ、これまで容易に得ることができなかった 非耐熱性部材と高い光触媒活性を有する光触媒層の組み合わせも可能となる。
[0028] また、均一加熱や、加熱冷却時の破損抑制が難しいガラスをはじめとする大きなサ ィズの基材への製膜にも適用できる。
図面の簡単な説明
[0029] [図 1]本発明に係る光触媒部材の具体例の断面図
[図 2]本発明に係る光触媒部材の具体例の断面図
[図 3]本発明に係る光触媒部材の具体例の断面図
発明を実施するための最良の形態
[0030] 以下に本発明の実施の形態を添付図面に基づいて説明する。ここで、図 1乃至図
3は本発明に係る光触媒部材の具体例を示す断面図であり、図 1に示す具体例では 、基材であるガラス板表面に形成された非耐熱性薄膜とは反対の面の表面に下地層 として単斜晶系 Zr〇層を形成し、更にその上に光触媒層として結晶性の Ti〇層を
2 2 形成している。なお、図示しないが、基板と下地層との間に剥離防止層を形成しても よいし、結晶性の TiO層の上に親水性を高めるために多孔質状の SiO層を形成し
2 2 てもよい。
[0031] 図 2に示す具体例では、基材であるガラス板表面に、非耐熱性薄膜、下地層として の単斜晶系 ZrO層、光触媒層として結晶性の TiO層をこの順番で形成している。な
2 2
お、図示しないが、基板と下地層との間に剥離防止層を形成してもよいし、結晶性の TiO層の上に親水性を高めるために多孔質状の SiO層を形成してもよい。
2 2
[0032] 図 3に示す具体例では、非耐熱性の基材である基板表面に下地層として単斜晶系 ZrO層を形成し、この単斜晶 ZrO層の上に更に光触媒層として結晶性の TiO層を
2 2 2 形成している。なお、図示しないが、基板と下地層との間に剥離防止層を形成しても よいし、結晶性の TiO層の上に親水性を高めるために多孔質状の SiO層を形成し
2 2 てもよい。 [0033] 上記非耐熱性薄膜、 ZrO層、 TiO層及び SiO層はスパッタリング法で形成される
2 2 2
。非耐熱性薄膜としては、誘電体層/銀層/誘電体層/銀層/誘電体層のような多 層膜が例示される。
[0034] 以下の表 1及び表 2には、実施例 1一 4の非耐熱性薄膜と、下地層、光触媒層及び 剥離防止層の構成、光触媒特性および光学特性の評価結果をまとめた。なお、比較 として、比較例 1一 6の熱処理工程と、光触媒層及び剥離防止層の形成方法、光触 媒特性及び光学特性の評価結果も示してレ、る。
[0035] [表 1]
Figure imgf000009_0001
[表 2]
Figure imgf000010_0001
(実施例 1)
インライン型マグネトロンスパッタリング装置を用いて、縦 Im X横 lm、厚さ 3mmの ソーダライムガラス基板上に、酸化亜鉛層と銀層を交互に積層し、基板/酸化亜鉛 層 40nm/銀層 1 Onm/酸化亜鉛層 80nm/銀層 1 Onm/酸化亜鉛層 40nmの構 成の多層膜を形成した。酸化亜鉛層は、アルミニウムを添加した酸化亜鉛ターゲット を用い、また銀層は銀ターゲットを用レ、、それぞれ、減圧アルゴン雰囲気中、非加熱 にて形成した。この酸化亜鉛と銀の多層膜は熱線反射機能を有するが耐熱性は低く 、前記定義の耐熱温度は 150°Cであり、この耐熱温度を越える温度に曝されると銀が 凝集して黒化してしまう。
[0037] 次に上記工程と連続して同じインライン型マグネトロンスパッタリング装置内の後段 のチャンバ一内（アルゴンと酸素の等量混合雰囲気、 0. 93Pa)で、このソーダライム ガラス基板の上記酸化亜鉛と銀の多層膜 (非耐熱性薄膜)とは反対側の面に、酸化 珪素層 5nmZ単斜晶系酸化ジルコニウム層 5nm/アナターゼ型酸化チタン層 5nm をこの順で形成した。それぞれの膜は、珪素ターゲット、ジノレコニゥムターゲット、チタ ンターゲットを用いて、非加熱の反応性スパッタリング法により形成した。
[0038] これによりソーダライムガラス基板の片面に酸化亜鉛と銀の多層膜からなる熱線反 射膜が、その反対面に光触媒層が形成された非耐熱性機能を有する光触媒ガラス を得た。この際、加熱工程を一切経なかったので、銀の凝集は起こらず、可視光透過 率の高い物品が得られた。可視光透過率の測定結果を表 1に示す。可視光透過率 は、 D65光源を使用して、 JIS R3106記載の「板ガラス類の透過率 '反射率'放射 率 ·日射熱取得率の試験方法」に準じて測定した。
[0039] また、光触媒層の光触媒活性を、親水性化性能の指標で評価した。光触媒層の成 膜後、光の当らない喑所に多層膜物品を 14日間放置し、大気中のハイド口カーボン を表面に堆積させ、表面の親水性を低下させた。その後、ブラックライトを用いて、酸 化チタン層表面に lmWZcm2強度の紫外線を 1時間照射し、照射後の水滴接触角 にて、以下の評価を行なった。 水滴接触角（° ) 光触媒活性評価
◎ (優)
〇（良) 20— 29 △ (劣）
30以上 X (悪）
[0040] 上記物品の酸化チタン層の光触媒活性を評価した結果、良好な性能を示した。
[0041] このソーダライムガラス基板の熱線反射膜が形成された側を内側として、別のソー ダライムガラスとこのガラスとにより、複層ガラス加工処理を施し、屋外側ガラスの内面 に熱線反射膜が、屋外側ガラスの外面に光触媒防汚膜が形成された防汚機能つき 熱線反射型複層ガラスを得た。
[0042] (実施例 2)
インライン型マグネトロンスパッタリング装置を用いて、縦 lm X横 lm、厚さ 3mmの アクリル樹脂基板上に、単斜晶系酸化ジノレコニゥム層 lOnmZアナターゼ型酸化チ タン層 20nmを形成した。それぞれの膜は、ジルコニウムターゲット、チタンターゲット を用いて、アルゴンと酸素の等量混合雰囲気（0. 93Pa)中、非加熱の反応性スパッ タリング法により形成した。
[0043] アクリル樹脂は、耐熱性が低く前記定義の耐熱温度は 230°Cである。この温度より 高い温度に曝されると黄色に着色する。上記光触媒層成膜工程では、加熱工程を 一切使用しなかったので、アクリル樹脂基板は黄変せず、成膜前後のアクリル樹脂の 光学特性は全く変化しなかった。
[0044] この非耐熱性の光触媒ガラス基板は、ディスプレイ用基板として用いることができる
[0045] (実施例 3)
インライン型マグネトロンスパッタリング装置を用いて、縦 lm X横 lm、厚さ 3mmの ポリエチレンテレフタレート（PET)フィルム基板上に、インジウム錫酸ィ匕物（IT〇）層と 銀層を交互に積層し、基板/ ΙΤΟ層 45nm/銀層 1 OnmZlTO層 40nmの構成の 多層膜を得た。 ITO層は ITOターゲットを用レ、、また銀層は銀ターゲットを用レ、、減圧 アルゴン雰囲気中、非加熱にて形成した。この IT〇と銀の多層膜は熱線反射機能を 有するが耐熱性は低ぐ前記定義の耐熱温度は 150°Cであり、この耐熱温度を越え る温度に曝されると銀が凝集して黒化してしまう。また、 PETフィルム自体も、耐熱温 度は 180°Cであり、この温度を越えると軟化変形が著しい。
[0046] 次に上記工程と連続して同じインライン型マグネトロンスパッタリング装置内の後段 のチャンバ一内（アルゴンと酸素の等量混合雰囲気、 0. 93Pa)で、この ITOと銀の 多層膜の上に、単斜晶系酸化ジノレコニゥム層 10nm/アナターゼ型酸化チタン層 1 Onmをこの順で形成した。それぞれの膜は、ジルコニウムターゲット、チタンターゲッ トを用いて、非加熱の反応性スパッタリング法により形成した。得られた物品の酸化チ タン層は非常に高い光触媒活性を有していた。
[0047] PETフィルム基板及び銀層は、耐熱性の低い要素を含むが、前記成膜工程では、 加熱工程を一切使用しなかったので、これらの劣化は認められず、光学特性が良好 な物品が得られた。
この光触媒基板は、電磁遮蔽機能を有する防汚フィルムとして用いることができる。
[0048] (実施例 4)
インライン型マグネトロンスパッタリング装置を用いて、縦 lm X横 lm、厚さ lmmの 薄板ソーダライムガラス基板上に、酸化珪素層 lOnm/単斜晶系酸化ジノレコニゥム 層 1 Onm/ニオブドープアナターゼ型酸化チタン層 1 Onmを形成した。酸化珪素層 及び単斜晶系酸化ジノレコニゥム層は、それぞれ珪素ターゲット、ジルコニウムターゲ ットを用いて、アルゴンと酸素の等量混合雰囲気（0. 93Pa)中で、非加熱の反応性 スパッタリング法にて形成した。また、 Nbドープアナターゼ型酸化チタン層は、チタン 一ニオブ酸化物ターゲットを用いて、アルゴン雰囲気（0· 93Pa)中で、非加熱のスパ ッタリング法にて形成した。得られた物品のニオブ酸化チタン層は良好な光触媒活性 を有していた。
[0049] 厚さ lmmの薄板ソーダライムガラス基板は、高温に曝されると変形し易ぐ前記定 義での耐熱温度は 500°Cである。前記成膜では、加熱工程を経ることがないので、 成膜前後で基板の変形は全く認められなかった。
この光触媒基板は、バイオケミカルチップとして用いることができる。
[0050] (比較例 1)
酸化ジノレコニゥム層を形成しなかった以外は、実施例 1と同じ条件にて各膜の成膜 を行なった。得られた物品は、可視光透過率が 73%と高く優れていた力 一方で酸 化チタン層の光触媒活性の評価は「 X」となった。
[0051] (比較例 2)
比較例 1の物品を、大気中にて 400°Cで 30分間加熱し、酸化チタン膜の熱処理を 行なった。この熱処理後、光触媒活性の評価は「〇」となったが、熱線反射膜の銀が 凝集して可視光透過率が低下した (加熱前 73%から、加熱後 54%に低下）。
[0052] (比較例 3)
酸化ジノレコニゥム層を形成しなかった以外は、実施例 2と同じ条件にて各膜の成膜 を行なった。得られた物品の酸化チタン層の光触媒活性を評価した結果、評価は「 X」であった。
[0053] (比較例 4)
比較例 3の物品を、大気中にて 350°Cで 30分間加熱し、酸化チタン膜の熱処理を 行なった。この熱処理後、光触媒活性の評価は「〇」となったが、基板のアクリル樹脂 が黄変して可視光透過率が低下した (加熱前 92%から、加熱後 75%に低下)。
[0054] (比較例 5)
酸化ジノレコニゥム層を形成しなかった以外は、実施例 4と同じ条件にて各膜の成膜 を行なった。得られた物品の酸化チタン層の光触媒活性を評価した結果、評価は「 X」となった。
[0055] (比較例 6)
比較例 5の物品を、大気中にて 600°Cで 30分間加熱し、酸化チタン膜の熱処理を 行なった。この熱処理後、光触媒活性の評価は「〇」となったが、基板が大きく変形し てしまい商品として使用できないことがわ力 た。

Claims

請求の範囲
[I] 基材表面に下地層を介して光触媒層が形成され、前記下地層は結晶性ジノレコニゥ ム化合物を主成分とし、前記光触媒層は結晶相から構成され、且つ前記基材は耐熱 性の低レ、要素を含むことを特徴とする光触媒部材。
[2] 前記結晶性ジノレコニゥム化合物は単斜晶系酸化ジルコニウム結晶を含むことを特徴 とする請求項 1に記載の光触媒部材。
[3] 前記基材は、耐熱性の低いガラスであることを特徴とする請求項 1又は 2に記載の光 触媒部材。
[4] 前記基材は、樹脂基体であることを特徴とする請求項 1又は 2に記載の光触媒部材。
[5] 前記基材は、樹脂フィルムであることを特徴とする請求項 1又は 2に記載の光触媒部 材。
[6] 前記基材は、有機無機複合体基体であることを特徴とする請求項 1又は 2に記載の 光触媒部材。
[7] 前記基材は、耐熱性の低い金属であることを特徴とする請求項 1又は 2に記載の光 触媒部材。
[8] 前記基材は非耐熱性薄膜を含むことを特徴とする請求項 1乃至 7のいずれか 1項に 記載の光触媒部材。
[9] 前記非耐熱性薄膜は、銀を使用した熱線反射膜であることを特徴とする請求項 8に 記載の光触媒部材。
[10] 前記非耐熱性薄膜は、誘電体層 Z銀層 Z誘電体層の積層膜を使用した熱線反射 膜であることを特徴とする請求項 9に記載の光触媒部材。
[II] 前記非耐熱性薄膜は、誘電体層 Z銀層 Z誘電体層 Z銀層 Z誘電体の積層膜を使 用した熱線反射膜であることを特徴とする請求項 9に記載の光触媒部材。
[12] 前記基材は、耐熱温度が 700°C以下であることを特徴とする請求項 1乃至 11のいず れか 1項に記載の光触媒部材。
[13] 前記基材は、耐熱温度が 500°C以下であることを特徴とする請求項 1乃至 11のいず れか 1項に記載の光触媒部材。
[14] 前記光触媒層はチタン化合物を主成分とすることを特徴とする請求項 1乃至 13のい ずれ力 1項に記載の光触媒部材。
[15] 前記チタンィ匕合物は正方晶系酸化チタンであることを特徴とする請求項 14に記載の 光触媒部材。
[16] 前記チタンィ匕合物はアナターゼ型酸化チタンであることを特徴とする請求項 14又は
15に記載の光触媒部材。
[17] 前記非耐熱性薄膜と下地層と光触媒層とが気相法にて形成されることを特徴とする 請求項 1乃至 16のいずれ力 4項に記載の光触媒部材。
[18] 前記気相法はスパッタリング法であることを特徴とする請求項 17に記載の光触媒部 材。
PCT/JP2004/008022 2003-06-09 2004-06-09 光触媒部材 Ceased WO2004108283A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2005506824A JP4460537B2 (ja) 2003-06-09 2004-06-09 光触媒部材
US10/560,053 US20070082205A1 (en) 2003-06-09 2004-06-09 Photocatalytic member
EP04745697A EP1637225A4 (en) 2003-06-09 2004-06-09 PHOTOCATALYST ELEMENT

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003164129 2003-06-09
JP2003-164129 2003-06-09

Publications (1)

Publication Number Publication Date
WO2004108283A1 true WO2004108283A1 (ja) 2004-12-16

Family

ID=33508776

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/008022 Ceased WO2004108283A1 (ja) 2003-06-09 2004-06-09 光触媒部材

Country Status (5)

Country Link
US (1) US20070082205A1 (ja)
EP (1) EP1637225A4 (ja)
JP (1) JP4460537B2 (ja)
CN (1) CN100482346C (ja)
WO (1) WO2004108283A1 (ja)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006307623A (ja) * 2005-03-31 2006-11-09 Mitsubishi Materials Corp 環境機能建材及びその製造方法
WO2007092511A3 (en) * 2006-02-08 2008-03-06 Ppg Ind Ohio Inc Coated substrates having undercoating layers that exhibit improved photocatalytic activity
WO2008047810A1 (fr) * 2006-10-16 2008-04-24 Nippon Sheet Glass Company, Limited Substrat antibactérien et son procédé de production
JP2008516878A (ja) * 2004-10-18 2008-05-22 ピルキントン グループ リミテッド 日照調整ガラス
US20090117371A1 (en) * 2006-04-07 2009-05-07 Interpane Entwicklungs-Und Beratungsgesellschaft Mbh & Co. Kg Weather-resistant layer system
JP2012124302A (ja) * 2010-12-08 2012-06-28 Ricoh Co Ltd 電気−機械変換膜とその作製方法、電気−機械変換素子、液体吐出ヘッドおよび液体吐出装置
JP2014071292A (ja) * 2012-09-28 2014-04-21 Dainippon Printing Co Ltd 反射防止物品
JP2015112524A (ja) * 2013-12-10 2015-06-22 大日本印刷株式会社 光触媒機能材料の製造方法、及び光触媒膜形成用スパッタリングターゲットの製造方法
JP2016527078A (ja) * 2013-07-05 2016-09-08 日東電工株式会社 透明光触媒コーティングおよびそれを製造する方法
WO2018190408A1 (ja) * 2017-04-14 2018-10-18 Hoya株式会社 光学素子及び光学薄膜

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100956214B1 (ko) * 2001-12-21 2010-05-04 니혼 이타가라스 가부시키가이샤 광촉매 기능을 갖는 부재 및 그 제조방법
JP4362476B2 (ja) * 2003-06-20 2009-11-11 日本板硝子株式会社 光触媒機能を有する部材および複層ガラス
FR2861386B1 (fr) * 2003-10-23 2006-02-17 Saint Gobain Substrat, notamment substrat verrier, portant une couche a propriete photocatalytique revetue d'une couche mince protectrice.
EP1852402A1 (en) * 2004-12-06 2007-11-07 Nippon Sheet Glass Company Limited Glass member having photocatalytic function and heat ray reflective function, and double layer glass employing it
US7846492B2 (en) * 2006-04-27 2010-12-07 Guardian Industries Corp. Photocatalytic window and method of making same
US7892662B2 (en) 2006-04-27 2011-02-22 Guardian Industries Corp. Window with anti-bacterial and/or anti-fungal feature and method of making same
US7632761B2 (en) * 2006-06-01 2009-12-15 Wayne State University Method of making thin film anatase titanium dioxide
CN104279025A (zh) 2008-05-29 2015-01-14 三井金属矿业株式会社 颗粒燃烧催化剂、颗粒过滤器和废气净化设备
CN102471144B (zh) * 2009-08-17 2014-11-05 日本板硝子株式会社 具备光催化剂膜的玻璃制品
US8946112B2 (en) 2009-10-30 2015-02-03 Empire Technology Development Llc Photocatalytic material for splitting oxides of carbon
FR2963343B1 (fr) * 2010-07-28 2012-07-27 Saint Gobain Vitrage pourvu d'un revetement contre la condensation
KR102099726B1 (ko) * 2012-12-04 2020-04-13 인고 스토르크 게난트 베르스보르그 열처리 모니터링 시스템
US10611679B2 (en) 2017-10-26 2020-04-07 Guardian Glass, LLC Coated article including noble metal and polymeric hydrogenated diamond like carbon composite material having antibacterial and photocatalytic properties, and/or methods of making the same
JP7422450B2 (ja) * 2018-03-20 2024-01-26 キヤノン株式会社 透明部材、撮像装置、透明部材の製造方法および部材
US20190295391A1 (en) * 2018-03-20 2019-09-26 Canon Kabushiki Kaisha Transparent member, imaging apparatus, and method of producing transparent member
US10759693B2 (en) * 2018-07-16 2020-09-01 Guardian Glass, LLC Low-E matchable coated articles having absorber film and corresponding methods
US10752541B2 (en) 2018-07-16 2020-08-25 Guardian Glass, LLC Low-E matchable coated articles having doped seed layer under silver, and corresponding methods
US10301215B1 (en) 2018-07-16 2019-05-28 Guardian Glass, LLC Low-E matchable coated articles having doped seed layer under silver, and corresponding methods
US10787385B2 (en) * 2018-07-16 2020-09-29 Guardian Glass, LLC Low-E matchable coated articles having absorber film and corresponding methods
KR102692564B1 (ko) * 2018-09-21 2024-08-06 삼성전자주식회사 다층 박막 구조물 및 이를 이용한 위상 변환 소자
JP2023148631A (ja) 2022-03-30 2023-10-13 デクセリアルズ株式会社 光触媒部材
TW202513154A (zh) 2023-09-01 2025-04-01 日商迪睿合股份有限公司 光觸媒構件及光觸媒構件之製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10278165A (ja) * 1997-04-08 1998-10-20 Asahi Glass Co Ltd 積層体の製造方法
JP2002030417A (ja) * 2000-07-14 2002-01-31 Japan Atom Energy Res Inst アナターゼ型結晶構造の酸化チタン単結晶薄膜の作製法
WO2002040417A2 (en) * 2000-08-31 2002-05-23 Ppg Industries Ohio, Inc. Methods of obtaining photoactive coatings and/or anatase crystalline phase of titanium oxides and articles made thereby

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0844985A1 (en) * 1995-08-18 1998-06-03 Adam Heller Self-cleaning glass and method of making thereof
FR2738813B1 (fr) * 1995-09-15 1997-10-17 Saint Gobain Vitrage Substrat a revetement photo-catalytique
KR100554451B1 (ko) * 1997-12-02 2006-03-03 쇼와 덴코 가부시키가이샤 광촉매성 산화물 함유 조성물, 박막 및 복합체
JP4174862B2 (ja) * 1998-08-04 2008-11-05 ソニー株式会社 薄膜トランジスタの製造方法および半導体装置の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10278165A (ja) * 1997-04-08 1998-10-20 Asahi Glass Co Ltd 積層体の製造方法
JP2002030417A (ja) * 2000-07-14 2002-01-31 Japan Atom Energy Res Inst アナターゼ型結晶構造の酸化チタン単結晶薄膜の作製法
WO2002040417A2 (en) * 2000-08-31 2002-05-23 Ppg Industries Ohio, Inc. Methods of obtaining photoactive coatings and/or anatase crystalline phase of titanium oxides and articles made thereby

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1637225A4 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008516878A (ja) * 2004-10-18 2008-05-22 ピルキントン グループ リミテッド 日照調整ガラス
JP2006307623A (ja) * 2005-03-31 2006-11-09 Mitsubishi Materials Corp 環境機能建材及びその製造方法
WO2007092511A3 (en) * 2006-02-08 2008-03-06 Ppg Ind Ohio Inc Coated substrates having undercoating layers that exhibit improved photocatalytic activity
US20090117371A1 (en) * 2006-04-07 2009-05-07 Interpane Entwicklungs-Und Beratungsgesellschaft Mbh & Co. Kg Weather-resistant layer system
WO2008047810A1 (fr) * 2006-10-16 2008-04-24 Nippon Sheet Glass Company, Limited Substrat antibactérien et son procédé de production
JP2012124302A (ja) * 2010-12-08 2012-06-28 Ricoh Co Ltd 電気−機械変換膜とその作製方法、電気−機械変換素子、液体吐出ヘッドおよび液体吐出装置
JP2014071292A (ja) * 2012-09-28 2014-04-21 Dainippon Printing Co Ltd 反射防止物品
JP2016527078A (ja) * 2013-07-05 2016-09-08 日東電工株式会社 透明光触媒コーティングおよびそれを製造する方法
US10391482B2 (en) 2013-07-05 2019-08-27 Nitto Denko Corporation Transparent photocatalyst coating and methods of manufacturing the same
US10710063B2 (en) 2013-07-05 2020-07-14 Nitto Denko Corporation Transparent photocatalyst coating and methods of manufacturing the same
JP2015112524A (ja) * 2013-12-10 2015-06-22 大日本印刷株式会社 光触媒機能材料の製造方法、及び光触媒膜形成用スパッタリングターゲットの製造方法
WO2018190408A1 (ja) * 2017-04-14 2018-10-18 Hoya株式会社 光学素子及び光学薄膜
JPWO2018190408A1 (ja) * 2017-04-14 2020-03-05 Hoya株式会社 光学素子及び光学薄膜
JP7091315B2 (ja) 2017-04-14 2022-06-27 Hoya株式会社 光学素子及びその製造方法

Also Published As

Publication number Publication date
EP1637225A1 (en) 2006-03-22
CN100482346C (zh) 2009-04-29
US20070082205A1 (en) 2007-04-12
JPWO2004108283A1 (ja) 2006-07-20
EP1637225A4 (en) 2007-12-19
JP4460537B2 (ja) 2010-05-12
CN1832804A (zh) 2006-09-13

Similar Documents

Publication Publication Date Title
JP4460537B2 (ja) 光触媒部材
EP1466665B1 (en) Member having photocatalytic function and method for manufacture thereof
EP1315682B1 (en) Methods of obtaining photoactive coatings and/or anatase crystalline phase of titanium oxides and articles made thereby
JP4362476B2 (ja) 光触媒機能を有する部材および複層ガラス
KR101131157B1 (ko) 보호용 박층으로 코팅되어 있는 광촉매 층을 지지하는기판, 특히 유리 기판
CA2543075C (fr) Substrat, notamment substrat verrier, portant au moins un empilement couche a propriete photocatalytique / sous-couche de croissance heteroepitaxiale de ladite couche
EP1068899A1 (en) Multilayer structure and process for producing the same
US20080124460A1 (en) Methods of obtaining photoactive coatings and/or anatase crystalline phase of titanium oxides and articles made thereby
JP2007512154A5 (ja)
CN1747907A (zh) 载有涂层叠层的玻璃板
RU2481364C2 (ru) Промежуточные слои, обеспечивающие улучшенную функциональность верхнего слоя
CN100465118C (zh) 涂层的玻璃
JP2000239047A (ja) 親水性光触媒部材
CN101072735A (zh) 具有光催化剂功能和红外线反射功能的玻璃构件以及使用该玻璃构件的多层玻璃
US20250196104A1 (en) Photocatalyst member
JP3925179B2 (ja) 防曇防汚物品とその製造方法
WO2025047938A1 (ja) 光触媒部材及び光触媒部材の製造方法
JP2025036359A (ja) 光触媒部材及び光触媒部材の製造方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200480022592.1

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2005506824

Country of ref document: JP

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

WWE Wipo information: entry into national phase

Ref document number: 2004745697

Country of ref document: EP

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWP Wipo information: published in national office

Ref document number: 2004745697

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2007082205

Country of ref document: US

Ref document number: 10560053

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 10560053

Country of ref document: US