WO2001068786A1 - Element hydrophile et son procede de fabrication - Google Patents

Element hydrophile et son procede de fabrication Download PDF

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Publication number
WO2001068786A1
WO2001068786A1 PCT/JP2001/001984 JP0101984W WO0168786A1 WO 2001068786 A1 WO2001068786 A1 WO 2001068786A1 JP 0101984 W JP0101984 W JP 0101984W WO 0168786 A1 WO0168786 A1 WO 0168786A1
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WO
WIPO (PCT)
Prior art keywords
titanium oxide
oxide
tungsten oxide
member according
surface layer
Prior art date
Application number
PCT/JP2001/001984
Other languages
English (en)
Japanese (ja)
Inventor
Masahiro Miyauchi
Mitsuhide Shimohigoshi
Kazuhito Hashimoto
Toshiya Watanabe
Original Assignee
Toto 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 Toto Ltd. filed Critical Toto Ltd.
Priority to JP2001567272A priority Critical patent/JP5130603B2/ja
Priority to AU41124/01A priority patent/AU4112401A/en
Publication of WO2001068786A1 publication Critical patent/WO2001068786A1/fr

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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
    • 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
    • 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
    • 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
    • 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
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/212—TiO2
    • 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
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • 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
    • C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
    • 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 member having a hydrophilic surface, and more specifically, a member such as a mirror, a lens, a sheet glass, a building interior material, a building exterior material, and the like, for which antifogging property and antifouling property are required. And a method for producing the same.
  • WO96 / 293375 discloses that the surface of a photocatalyst-containing layer formed on the surface of a substrate has a high degree of hydrophilicity (for example, in terms of a contact angle with water, depending on the photoexcitation of the photocatalyst). 10 ° or less). Utilizing this property, it is said that it is possible to improve the anti-fog and visibility enhancement of transparent members such as glass, lenses and mirrors, and to improve the water washing property and rainfall washing property of the article surface.
  • Japanese Patent Application Laid-Open No. 11-388867 discloses that the mixed metal oxide has a wavelength of 300 in the presence of a mixed metal oxide of titanium oxide and tungsten oxide, an oxidizable compound and a gas containing oxygen. It discloses a deodorization method using a photocatalyst that irradiates light having a maximum wavelength of not less than 370 nm and a wavelength of not more than 370 nm.
  • Japanese Patent Application Laid-Open No. 10-1141545 discloses a hydrophilic member having a surface layer containing photocatalytic titanium oxide and tungsten oxide formed on the surface of a substrate.
  • WO97 / 235772 discloses a substrate, a layer containing a photocatalyst formed on the surface of the substrate, and water molecules physically adsorbed on the surface of the layer in response to photoexcitation of the photocatalyst.
  • a hydrophilic member comprising a layer, disclose that capable of carrying a T i 0 2 / W0 3 to the photocatalyst-containing layer surface.
  • Japanese Patent Application Laid-Open No. H10-57871 discloses a photocatalyst structure having a photocatalyst layer on a substrate surface, wherein at least a part of the photocatalyst layer surface has a metal compound having a thickness of 0.2 to 10 O nm.
  • a photocatalyst structure having a thin film is disclosed.
  • the present inventors have recently suggested that the combination of photocatalytic titanium oxide and amorphous tungsten oxide can efficiently induce hydrophilicity with a photocatalyst even with a small amount of photocatalyst or a weak amount of ultraviolet light. Obtained knowledge.
  • the present invention quickly develops excellent hydrophilicity in response to sunlight or weak light of the indoor lighting level even with a small amount of photocatalytic titanium oxide, thereby achieving antifogging and antifouling properties. It is an object of the present invention to provide a member capable of obtaining the above and a method for producing the same.
  • the member of the present invention comprises: a base material; and a surface layer bonded to the surface of the base material and containing a photocatalytic titanium oxide and an amorphous tungsten oxide.
  • the titanium oxide and the amorphous tungsten oxide are joined to each other without forming a solid solution;
  • the outermost surface of the surface layer exhibits a hydrophilicity of 10 degrees or less in terms of water contact angle in response to light excitation by light irradiation of 10 ⁇ W / cm 2 or less in terms of ultraviolet illuminance. .
  • FIG. 1 is a diagram illustrating a charge transfer process when both titanium oxide and tungsten oxide are photoexcited.
  • Figure 2 is a diagram explaining the charge transfer process when tungsten oxide is photoexcited.
  • FIG. 3 is a diagram illustrating a charge transfer process when photocatalytic titanium oxide is photoexcited.
  • FIG. 4 is a conceptual diagram showing a cross section of a member according to the first embodiment of the present invention.
  • FIG. 5 is a conceptual diagram showing a cross section of a member according to the second embodiment of the present invention.
  • FIG. 6 is a conceptual diagram showing a cross section of a member according to the third embodiment of the present invention.
  • FIG. 7 is a conceptual diagram showing a cross section of a member according to the fourth embodiment of the present invention.
  • FIG. 8 is a conceptual diagram showing a cross section of a member according to the fifth embodiment of the present invention.
  • FIG. 9 is a conceptual diagram showing a cross section of a member according to the sixth embodiment of the present invention.
  • FIG. 10 is a conceptual diagram showing a cross section of a member according to the seventh embodiment of the present invention.
  • FIG. 11 is a conceptual diagram showing a cross section of a member according to the eighth embodiment of the present invention.
  • FIG. 12 is a diagram showing the relationship between the contact angle with water on the sample surface and the light irradiation time when the UV illuminance is 10 W / cm 2 in Example A1.
  • FIG. 13 is a diagram showing the relationship between the contact angle with water on the sample surface and the light irradiation time when the ultraviolet illuminance is 3 zW / cm 2 in Example A1.
  • FIG. 14 is a diagram showing the relationship between the contact angle of the sample surface with water and the light irradiation time in Example A2.
  • FIG. 15 is a diagram showing the relationship between the contact angle of the sample surface with water and the light irradiation time in Example A3.
  • FIG. 16 is a diagram showing the relationship between the contact angle of the sample surface with water and the light irradiation time in Example A4.
  • FIG. 17 is a diagram showing the relationship between the contact angle of the sample surface with water and the light irradiation time in Example A5.
  • FIG. 18 is a diagram showing the relationship between the contact angle of the sample surface with water and the storage time at a location in Example A6.
  • FIG. 19 is a diagram showing the relationship between the rate of hydrophilicity conversion and the ratio of the tungsten raw material to the solid content in the raw material solution in Example B1.
  • FIG. 20 is a diagram showing the relationship between the rate of hydrophilicity constant and the proportion of the tungsten raw material occupying the solid content in the raw material solution in Example B2.
  • FIG. 21 is a diagram showing the relationship between the rate of hydrophilicity constant and the ratio of the tungsten raw material to the solid content in the raw material solution in Example B3.
  • the member of the present invention has a base material and a surface layer bonded to the surface of the base material.
  • the substrate used in the present invention can be a metal, an inorganic material, an organic material, and a composite thereof. Specific examples include tiles, sanitary ware, tableware, calcium silicate plates, cement extruded plates, ceramic substrates, new ceramics such as semiconductors, insulators, glass, mirrors, wood, and resins.
  • examples of the base material when expressed as the use of the member include building exterior materials, building interior materials, window frames, window glass, structural members, vehicle exteriors, dustproof covers for articles, traffic signs, various display devices , Advertising towers, road noise barriers, railway noise barriers, bridges, guardrails, tunnel interiors and coatings, insulators, solar battery covers, solar water heater collector covers, plastic greenhouses, vehicle lighting covers, housing Equipment, toilets, bathtubs, wash basins, lighting fixtures, lighting covers, kitchen utensils, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods, ventilation fans, protective films, etc.
  • the surface layer contains photocatalytic titanium oxide and amorphous tungsten oxide.
  • the titanium oxide and the amorphous tungsten oxide are bonded to each other without forming a solid solution.
  • a combination of photocatalytic titanium oxide and tungsten oxide has been known.
  • the tungsten oxide is crystallized or forms a solid solution with the titanium oxide and is bonded thereto.
  • the surface layer of the member according to the present invention is excellent in hydrophilization efficiency.
  • the hydrophilicity can be efficiently induced by the photocatalyst even with a small amount of the photocatalyst or a small amount of the ultraviolet light.
  • the amount of titanium oxide as a photocatalyst can be reduced, high transparency can be realized without causing iris or cloudiness on the surface layer.
  • the band gap of amorphous tungsten oxide is 3.2 leV, which is narrower than the band gap of titanium oxide 3.2 eV.
  • the amorphous oxide evening tungsten is, c upper end of the lower end and the valence band of the conduction band is on the positive side of the titanium oxide
  • the electrons generated and the holes generated in the valence band can move between different types of photocatalysts, which may promote charge separation.
  • an impurity level is generated between the titanium oxide and the tungsten oxide. It is thought that the impurity level acts as a recombination center between the photoexcited electron and the hole and hinders the hydrophilization reaction.
  • Figure 1 shows the energy structures of titanium oxide and tungsten oxide.
  • electrons generated in the conduction band of titanium oxide move to the conduction band of the tungsten oxide material, and are generated in the valence band of tungsten oxide.
  • the holes can move to the valence band of titanium oxide.
  • the holes transferred to the titanium oxide react with the lattice oxygen of the titanium oxide itself to generate oxygen vacancies with high affinity for water and become hydrophilic, while the electrons transferred to the tungsten oxide are oxygen in the air. Reacts with to generate superoxodonion and is released to the outside world. It is thought that the holes generated in tungsten oxide act effectively on the surface of the titanium oxide to make it hydrophilic, and assist this.
  • Fig. 2 shows the irradiation of visible light with a wavelength of 400 nm or more, which makes it difficult to excite titanium oxide.
  • FIG. Titanium oxide cannot be excited by visible light with a wavelength of 400 nm or more, but can excite tungsten oxide. The holes generated by the tungsten oxide move to the titanium oxide side. It is considered that the probability of recombination is extremely low due to the separation of the electron-hole pairs, and that the surface of the titanium oxide particles is promoted to be hydrophilic.
  • FIG. 3 shows a case where light for exciting only titanium oxide is irradiated. Even in this case, it is considered that the generated holes are efficiently collected on the titanium oxide without recombination with the electrons, and the hydrophilicity of the titanium oxide is promoted.
  • preferable crystal structures of titanium oxide include an analog type, a rutile type, and a wurtzite type.
  • the amorphous tungsten oxide means not only so-called amorphous tungsten oxide but also tungstic acid or a salt thereof. Further, it may be a mixture of amorphous tungsten oxide and tungstic acid or a salt thereof.
  • Preferred examples of the tungstate include ammonium salt, hydrochloric acid salt, nitrate, nitrate, organic acid salt, alcoholate, chelate, acetate and the like.
  • both or either of the titanium oxide and the amorphous tungsten have a particle shape.
  • the particle size of the titanium oxide particles is preferably about 1 to 5 O nm, more preferably about 5 to 30 nm.
  • the particle size of the tungsten oxide is preferably 50 nm or less, more preferably about 5 to 3 O nm.
  • the titanium oxide is present on the outermost surface of the surface layer in a state where the titanium oxide can come into contact with moisture in the outside air.
  • the tungsten oxide preferably has oxygen vacancies.
  • the ratio of tungsten oxide atoms: titanium atoms on the surface of the surface layer is 0.005 to 0.50 in terms of a value measured by X-ray photoelectron spectroscopy. : 0.995-0.50.
  • the oxidized ring in the surface layer is preferably from 0.1% to 70% by weight, more preferably from 5% to 50%. By being in such a range, hydrophilicity can be induced more efficiently.
  • the surface layer comprises a layer made of the titanium oxide and an amorphous tungsten oxide dispersed and scattered on the surface of the titanium oxide layer. That is, it is preferable that the tungsten oxide is scattered like islands on the layer made of titanium oxide. It should be noted that specific examples of this aspect include the first to fourth aspects of the present invention described below.
  • the surface layer includes the titanium oxide particles and the tungsten oxide particles in a mixed form. Also in this case, it is preferable that the titanium oxide exists on the outermost surface of the surface layer in a state where the titanium oxide can come into contact with moisture in the outside air. Specific examples of this aspect include the fifth to eighth aspects of the present invention described below.
  • the surface layer further includes a metal oxide having at least one bond selected from the group consisting of a siloxane bond, a porosiloxane bond, and an aluminosilicate bond (hereinafter, referred to as a “metal oxide”).
  • a metal oxide having at least one bond selected from the group consisting of a siloxane bond, a porosiloxane bond, and an aluminosilicate bond (hereinafter, referred to as a “metal oxide”).
  • metal oxide simply referring to a metal oxide means the metal oxide).
  • These compounds have the property of being able to adsorb a large amount of chemically adsorbed water, so that the efficiency of inducing hydrophilicity is improved. Is advantageous.
  • Specific examples of such a metal oxide include silica, silicone, alkyl silicate, alkali silicate, and acrylic silicon.
  • the metal oxide may be dispersed and scattered on the surface layer.
  • the metal oxide may be present as a layer on the surface of the surface layer.
  • the hydrophilicity appears at the resurface of this metal oxide layer.
  • the metal oxide layer preferably has a thickness of about 1 nm to about 100 nm from the viewpoint of maintaining hydrophilicity. In some cases, it is preferable that the metal oxide layer has open pores from the viewpoint of developing the hydrophilicity of titanium oxide.
  • Surface layer in the present invention in terms of ultraviolet intensity 1 0 zW / cm 2 or less, rather preferably below 3 ⁇ W / cm z, more preferably corresponding to excitation by light irradiation less than 1 ⁇ W / cm z
  • the outermost surface exhibits a hydrophilicity of 10 degrees or less, preferably 5 degrees or less, more preferably 3 degrees or less in terms of a water contact angle.
  • very advantageous that the surface is capable of highly hydrophilic to less than 5 degrees in terms of water contact angle It is. That is, indoors generally have a small amount of ultraviolet rays. Even in such an environment, as a result of achieving a high degree of hydrophilicity, the effects of anti-fog, drip-proof, and self-purification can be expected indoors.
  • the irradiated light be a light having a wavelength that can excite both titanium oxide and tungsten oxide.
  • light having a wavelength in the range of 30 O nm to 450 nm can be suitably used to excite titanium oxide and tungsten oxide.
  • the light emitted from fluorescent lamps and incandescent lamps to the articles installed on the indoor wall has a wavelength of 300 nm to 450 nm.
  • the integrated illuminance of the area is estimated to be 0.1 to 10 1W / cm 2 .
  • the component according to the invention is advantageous for indoor use. Use of parts
  • the surface of the component according to the invention is highly hydrophilic. As a result, the attached water does not become water droplets but spreads as a thin water film. As a result, the component according to the invention has application as a non-fogging or anti-fog component.
  • the member according to the present invention is a member that is hardly soiled. Furthermore, for example, when the member according to the present invention is installed outdoors, if it adheres, it has an advantageous property that it is easily washed away by rainfall or the like, that is, it is self-cleaning (self-cleaning).
  • the surface layer of the member according to the present invention is substantially transparent and has no interference color, the design property of any article of architectural exterior materials, interior materials and other indoor members may not be impaired. It is also advantageous in that it does not have any.
  • the hydrophilic member of the present invention emits light from a mercury lamp, a xenon lamp, a mercury-xenon lamp, a halogen lamp, a metal halide lamp, etc., which has a high light intensity, and sunlight and sunlight scattered from a window. It is needless to say that even when the photo-excitation is performed, the anti-fogging, anti-fouling, and self-cleaning effects as described above are exhibited. Production method
  • the first manufacturing method according to the present invention is to form a two-layer surface layer composed of a titanium oxide layer and an amorphous tungsten oxide layer on the surface of a base material. That is, the first production method of the present invention comprises:
  • the temperature at which a solid solution is not formed is preferably lower than 500 ° C, more preferably in the range of 20 ° C to 350 ° C.
  • the second production method of the present invention comprises:
  • the temperature at which a solid solution is not formed may be the same as the temperature according to the first production method described above. In both the first and second production methods, photocatalytic titanium oxide or a precursor thereof is used.
  • Preferred examples of the precursor of the photocatalytic titanium oxide include amorphous titania sol, crystalline titania sol, tetramethyltitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetran-propoxytitanium, tetrabutoxytitanium, titanium chelate, a
  • the raw material includes at least one selected from the group consisting of cetylacetone titanium, titanium tetrachloride, titanium sulfate, and titanium hydroxide.
  • the precursors of the amorphous tungsten oxide include ammonium tungstate, tungstic acid, a sol in which amorphous tungsten oxide particles are suspended, penethoxyethoxytungsten, pentamethoxytungsten, pengupropoxytungsten, pen Examples include those containing at least one tungsten compound selected from the group consisting of butoxytungsten, tungsten chelate, acetate tungsten, tungsten sulfate, tungsten chloride, and tungsten hydroxide.
  • subbing coating, flow coating, dip coating, spray coating, roll coating and the like can be suitably used.
  • the thickness of the coating can be controlled by the rotation speed of the base material and the concentration of the raw material solution.
  • any of a titanium oxide layer and an amorphous tungsten oxide layer, or a surface layer containing titanium oxide and tungsten oxide in a mixed form is formed by sputtering, CVD, or the like. , A plasma CVD method, an ion plating method, an MBE method, or the like.
  • a layer 12 containing titanium oxide is formed on a substrate 10, and an island 14 made of tungsten oxide is formed on the layer 12. It is bonded to a layer 12 containing titanium oxide. At least a part of the titanium oxide is exposed to the outside air, and is capable of coming into contact with moisture in the outside air.
  • the member according to the first embodiment can be manufactured as follows. First, a starting material of titanium oxide is applied to a substrate, and then a thin film of titanium oxide is formed by drying or baking. Further, after the starting material of tungsten oxide is applied on the titanium oxide thin film, drying or heating is performed.
  • the member according to the second embodiment of the present invention maintains the surface hydrophilicity in a dark place or strengthens it. 6 may be formed.
  • the member according to the second embodiment can be manufactured, for example, as follows. First, a starting material of titanium oxide is applied to a substrate, and then a thin film of titanium oxide is formed by drying or baking. Further, a coating agent containing a starting material of tungsten oxide and a starting material of metal oxide is applied on the titanium oxide thin film and then dried or baked. Further, after forming the titanium oxide thin film, the starting material of tungsten oxide may be applied, followed by drying or baking, and then the starting material of the metal oxide may be applied, followed by drying or baking. After forming the titanium oxide thin film, the starting material of the metal oxide may be applied, followed by drying or baking, and then the starting material of tungsten oxide may be applied, followed by drying or baking.
  • a layer 32 containing titanium oxide is formed on a base material 30, and an island 34 made of tungsten oxide is bonded thereon. Further, a layer 36 made of a metal oxide is formed thereon.
  • the member according to the fourth aspect can be manufactured, for example, as follows. First, a starting material of titanium oxide is applied to a substrate, and then a thin film of titanium oxide is formed by drying or baking. Further, after the starting material of tungsten oxide is applied on the titanium oxide thin film, drying or baking is performed. After that, the starting material containing a metal oxide is applied thereon, and then drying or baking is performed.
  • a mixed layer 42 containing a metal oxide capable of adsorbing more chemically adsorbed water than tan and titanium oxide is formed, and an island 44 made of tungsten oxide is further joined to the mixed layer 42. .
  • the member according to the fourth embodiment can be manufactured, for example, as follows. First, a coating agent containing a starting material of titanium oxide and a starting material of metal oxide is applied to a substrate, and then a mixed layer containing titanium oxide and a metal oxide is formed by drying or baking. Further, a tungsten oxide starting material is applied on the mixed layer, and then dried or heated and baked.
  • a coating 52 made of titanium oxide particles and tungsten oxide particles is formed on a base material 50. At least a portion of the titanium oxide particles and at least a portion of the tungsten oxide particles are joined without forming a solid solution, and at least a portion of the titanium oxide particles are exposed to the open air.
  • the member according to the fifth embodiment, which is exposed and can come into contact with moisture in the outside air, can be manufactured, for example, as follows. First, a coating agent containing a starting material of titanium oxide and a starting material of tungsten oxide is applied to a substrate. Then, dry or heat bake.
  • a mixed film 62 formed by adding a metal oxide to titanium oxide and tungsten oxide is formed on a base material 60. ing.
  • the member according to the sixth aspect can be manufactured, for example, as follows. First, a coating material containing a starting material of titanium oxide, a starting material of tungsten oxide, and a starting material of metal oxide is applied to a substrate. Then, dry or heat bake.
  • the member according to the seventh embodiment of the present invention includes a bird film made of metal oxide on a film 72 made of titanium oxide and tungsten oxide formed on a base material 70. 7 4 are formed.
  • the member according to the seventh aspect can be manufactured, for example, as follows. First, a coating agent containing a starting material of titanium oxide and a starting material of tungsten oxide is applied to a substrate, and then a mixed film of titanium oxide and tungsten oxide is formed by drying or baking. Further, a starting material containing a metal oxide is applied on the mixed film, and then dried or baked.
  • the member according to the first embodiment of the present invention has a film 82 made of titanium oxide and tungsten oxide formed on a base material 80, and a layer made of a metal oxide formed thereon. 8 4 are formed.
  • the member according to the eighth aspect can be manufactured in the same manner as the member according to the seventh aspect. At this time, the thickness of the layer made of the metal oxide can be controlled by adjusting the concentration of the starting material containing the metal oxide. Antifogging method and antifouling method
  • a method for imparting anti-fog properties to a member surface comprises providing a substrate with a surface layer comprising photocatalytic titanium oxide and amorphous tungsten oxide, wherein the titanium oxide and the amorphous tungsten oxide do not form a solid solution. They are joined together. By irradiating this base material with light of 10 ⁇ W / cm 2 or less in terms of ultraviolet illuminance and photo-excitation, the member exhibits antifogging properties.
  • a method for imparting antifouling property to a member surface comprises providing a surface layer comprising a photocatalytic titanium oxide and an amorphous tungsten oxide on a base material, wherein the titanium oxide and the amorphous tungsten oxide form a solid solution without forming a solid solution. Be joined. By irradiating the substrate with light of 10 W / cm 2 or less in terms of ultraviolet illuminance and photo-excitation, the member exhibits antifouling properties. The surface of this member is easily cleaned only by occasional contact with running water. JP01 / 01984
  • a titanium oxide coating agent (Nippon Soda, NDH510C) having a solid concentration of 10% was applied to silica-coated glass by dip coating. The dip coating was performed at a pulling speed of 15 cm / min. Then, the coated film was baked at 500 ° (:, 30 minutes) in an electric furnace. The above steps were repeated twice to produce a photocatalytic titanium oxide thin film having a thickness of about 20 Onm.
  • a liquid in which tungstic acid was dissolved in 25% aqueous ammonia was further coated on the thin film by spin coating.
  • Spin coating was performed at a rotation speed of 1500 revolutions per minute for 10 seconds. Thereafter, the thin film was fired in an electric furnace at 300 ° C for 30 minutes.
  • concentration of tungstic acid samples with different loading amounts of photocatalytic tungsten oxide on titanium oxide were obtained.
  • Sample # 1 no tungstic acid coating
  • Sample # 2 tungstic acid concentration 0.5% by weight (solid content, same hereafter)
  • Sample # 3 tungstic acid concentration 1.0% by weight
  • Sample # 4 evening stainless acid concentration was 2.0% by weight.
  • the ratio of tungsten atoms: titanium atoms on the surface of the thin film was measured by X-ray photoelectron spectroscopy. as a result,
  • Sample # 1 is 0: 1.00
  • Sample # 3 is 0.20: 0.80
  • Sample # 4 was 0.40: 0.60.
  • X-ray diffraction confirmed the presence of amorphous photocatalytic tungsten oxide on the surface of the thin film.
  • Ultraviolet illuminance on the surface of the thin film was measured with an ultraviolet illuminometer (Shisho Electric, UVR-2), and the distance between the thin film and the fluorescent lamp was changed to 10 W / cm 2 or 3 / W / cii.
  • UVR-2 ultraviolet illuminometer
  • a drop of water was dropped from the microsyringe, and the contact angle with water was measured with a contact angle measuring instrument (Kyowa Interface Science, CA-X150).
  • Example A1 In the same manner as in Example A1, a photocatalytic titanium oxide thin film having a thickness of about 200 nm was produced.
  • a liquid in which tungstic acid was dissolved in 25% aqueous ammonia was further coated on the thin film by spin coating (1,500 rpm for 10 minutes). Thereafter, the thin film was fired in an electric furnace at 100 ° C for 30 minutes.
  • concentration of tungstic acid samples having different amounts of photocatalytic tungsten oxide on titanium oxide were obtained.
  • Sample # 5 no coating of tungstic acid
  • Sample # 6 dungstenic acid concentration 1.0% by weight (solid content, the same applies hereinafter);
  • Sample # 7 tungstic acid concentration 2.0% by weight;
  • Sample # 8 tungstic acid concentration was 5.0% by weight.
  • the ratio of tungsten atoms: titanium atoms on the surface of the thin film was measured by X-ray photoelectron spectroscopy. as a result,
  • Example A 3 The contact angle of the obtained thin film was measured in the same manner as in Example A1. However, the UV illuminance was set to 10 ⁇ W / cm 2 . The results were as shown in FIG. Sample # 5 was hydrophilized to about 10 degrees, and samples # 6 and # 7 were further hydrophilized to 0 degrees. Example A 3
  • Example A1 In the same manner as in Example A1, a photocatalytic titanium oxide thin film having a thickness of about 200 nm was produced.
  • a 25% aqueous ammonia solution having a tungstic acid concentration of 1.0% by weight (solid content) was further coated on the thin film by spin coating (1,500 rotations per minute, 10 seconds). Thereafter, the thin film was baked for 30 minutes in an electric furnace while changing the temperature as follows.
  • the state of tungstic acid present on the surface of the thin film was observed by X-ray diffraction.
  • ammonium tungstate in sample # 10 the presence of amorphous tungsten oxide in sample # 11
  • the presence of a composite phase of amorphous tungsten oxide and crystallized tungsten oxide in sample # 12 the presence of crystallized tungsten oxide in sample # 13 .
  • the ratio of tungsten atoms: titanium atoms on the thin film surface was measured by X-ray photoelectron spectroscopy. As a result, the ratio of sample # 9 was 0: 1.00, and the ratio of samples # 10 to # 13 was 0.20: 0.80.
  • Aqueous titanium oxide sol (Ishihara STS21) was diluted with pure water until the solid content became 8%, and applied to silica-coated glass by spin coating (1500 rpm, 10 seconds). Thereafter, the coating film was fired in a Matsufuru furnace at 500 ° C for 30 minutes.
  • a 25% aqueous ammonia solution having a tungstic acid concentration of 1.0% by weight was further coated on the thin film by spin coating (at a rotation speed of 1500 rpm for 10 seconds). Thereafter, the thin film was baked for 30 minutes in an electric furnace while changing the temperature as follows.
  • the ratio of tungsten atoms: titanium atoms on the thin film surface was measured by X-ray photoelectron spectroscopy. As a result, Sample # 14 had a ratio of 0: 1.00, and Samples # 15 and # 16 had a ratio of 0.20: 0.80. When the structure of the thin film surface was observed with an atomic force microscope, the surfaces of the samples # 15 and # 16 had almost no difference from the sample # 14. The results suggested a structure composed of a layer made of titanium oxide and amorphous tungsten oxide dispersed on the surface of the titanium oxide layer and scattered in stripes.
  • Example A 5 The contact angle of the obtained thin film was measured in the same manner as in Example A1. However, the UV illuminance was 1 / W / cm 2 . The results were as shown in Figure 16. Sample # 14 was hydrophilized to 10 degrees, while samples # 15 and # 16 were further hydrophilized to 1 degree. Example A 5
  • a photocatalytic antifogging film containing photocatalytic titanium oxide and silica was attached to the glass, and on top of this, an evening stainless acid concentration of 1.0% by weight. was coated by spin coating (150 rpm / min, 10 seconds) and dried at 100 ° C. for 30 minutes.
  • X-ray diffraction confirmed the presence of ammonium tungstate on the surface of the thin film.
  • the ratio of tungsten atoms: titanium atoms on the surface of the thin film was 0.20: 0.80.
  • the contact angle of the obtained thin film was measured in the same manner as in Example A1. However, the UV illuminance was set to 10 W / cm 2 . The results were as shown in FIG. Example A 6
  • Example A1 In the same manner as in Example A1, a photocatalytic titanium oxide thin film having a thickness of about 200 nm was produced.
  • a 25% aqueous ammonia solution having a tungstic acid concentration of 1.0% by weight was further coated on the thin film by spin coating (1500 rotations per minute, 10 seconds). Then, the thin film was baked for 30 minutes in an electric furnace while changing the temperature as follows. .
  • X-ray photoelectron spectroscopy was used to measure the ratio of tungsten: silicon: titanium on the surface of the thin film. As a result, it was 0.20: 0.40: 0.40.
  • Example B 1 that remained 5 degrees or less hydrophilic
  • aqueous titanium oxide sol (NTB-21, manufactured by Showa Denko KK) and an aqueous solution of ammonium tungstate were mixed at the following concentrations to obtain a coating solution having a solid concentration of 2% by weight for these components. That is, coating solutions were prepared in which the weight ratio of ammonium tungstate to titanium oxide was 5%, 10%, 20%, 30%, 40%, 50%, 70%, and 90%. This coating solution was applied to silica-coated glass by spin coating (1,500 revolutions per minute, 10 seconds), followed by baking at 300 ° C for 30 minutes in a Matsufur furnace.
  • the obtained glass member having a thin film on the surface was substantially transparent without cloudiness or iris color.
  • X-ray diffraction confirmed the presence of a mixed phase of amorphous tungsten oxide and ananases-type titanium oxide on the surface of the thin film.
  • the contact angle of the obtained thin film was measured in the same manner as in Example A1. However, the UV illuminance was 5 / W / cm 2 . From the obtained value of the contact angle, a hydrophilization rate constant was determined according to the following equation. Empirically, the change in contact angle during light irradiation is expressed by a secondary reaction equation as shown in equation (1). Obey. That is, when the reciprocal of the contact angle 0 is plotted against time, a linear relationship is obtained, and this slope can be defined as a hydrophilization rate constant.
  • a glass member was obtained in the same manner as in Example 2. However, the firing temperature in the Matsufuru furnace was 100 ° C.
  • the obtained glass member having a thin film on the surface was substantially transparent without cloudiness or iris color.
  • X-ray diffraction confirmed the presence of a mixed phase of ammonium tungstate and an anatase-type titanium oxide on the surface of the thin film.
  • the lattice constant of titanium oxide obtained from the results of X-ray diffraction is
  • the contact angle of the obtained thin film was measured in the same manner as in Example A1. However, the UV illuminance was 5 W / cm 2 . From the value of the obtained contact angle, a hydrophilization rate constant was obtained from the equation (1) in the same manner as in Example B1.
  • FIG. 20 shows the relationship between the rate constant of hydrophilization and the ratio of the tungsten raw material to the solid content in the coating solution. From these results, it is most advantageous to promote the hydrophilization when the proportion of the tungsten raw material is in the range of 5 to 50%. It turns out that it is. It should be noted that when the proportion of the tungsten raw material was in the range of 5 to 50%, the material became hydrophilic to 5 degrees or less.
  • a glass member having a thin film on the surface was obtained in the same manner as in Example B1, except that the aqueous titanium oxide sol was changed to A-6, manufactured by Taki Kagaku.
  • X-ray diffraction confirmed the presence of a mixed phase of amorphous tungsten oxide and ana-type titanium oxide on the thin film surface.
  • the lattice constant of titanium oxide obtained from the results of X-ray diffraction showed a value similar to the literature value of anatomical titanium oxide in stoichiometry. This suggested that no solid solution was generated between titanium oxide and tungsten oxide.
  • the contact angle of the obtained thin film was measured in the same manner as in Example A1. However, the UV illuminance was 5 zW / cm 2 . From the value of the obtained contact angle, a hydrophilization rate constant was obtained from the equation (1) in the same manner as in Example B1.
  • Figure 21 shows the relationship between the rate constant of hydrophilization and the ratio of the tungsten raw material to the solid content in the coating solution. From this result, it can be seen that when the proportion of the tungsten raw material is in the range of 5 to 40%, it is most advantageous for promoting the hydrophilization.

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Abstract

On décrit un élément qui comprend un substrat sur la surface duquel est formée et reliée une couche de surface comprenant un oxyde de titane et un oxyde de tungstène amorphe ayant une activité photocatalytique, l'oxyde de titane et un oxyde de tungstène amorphe étant reliés l'un à l'autre sans former pour autant une solution solide et la surface la plus élevée de la couche de surface présentant une hydrophilicité maximale de 10 degrés en termes d'angle de contact avec l'eau en réponse au pompage optique effectué par le rayonnement de la lumière de 10 νW/cm2 ou moins en termes d'éclairement lumineux des rayons ultraviolets. On décrit également un procédé de fabrication de l'élément, ce dernier étant capable de présenter une excellente hydrophilicité en réponse à une faible lumière du niveau d'éclairage interne et à la lumière du soleil, même avec une faible quantité de catalyseur, ceci lui permettant de résister à l'embuage et au maculage.
PCT/JP2001/001984 2000-03-13 2001-03-13 Element hydrophile et son procede de fabrication WO2001068786A1 (fr)

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JP2002211928A (ja) * 2000-12-30 2002-07-31 Altra:Kk 可視光反応型チタン酸化物及びその製造方法並びに汚染物質の除去方法
JP2003135972A (ja) * 2001-10-31 2003-05-13 Ube Nitto Kasei Co Ltd 光触媒含有多孔性薄膜およびコーティング剤
JP2003260134A (ja) * 2002-03-11 2003-09-16 Yukiyasu Okumura 院内感染防止輸液システム
JP2005231935A (ja) * 2004-02-18 2005-09-02 Taki Chem Co Ltd 酸化タングステン含有酸化チタンゾル及びその製造方法並びにコーティング剤及び光機能体
WO2005102952A2 (fr) * 2004-04-13 2005-11-03 Saint-Gobain Glass France Substrat photocatalytique actif sous lumiere visible
JP2006198464A (ja) * 2005-01-18 2006-08-03 Nippon Shokubai Co Ltd 可視光応答型光触媒およびその製造方法
WO2009036284A1 (fr) * 2007-09-14 2009-03-19 Cardinal Cg Company Revêtements à faible entretien et procédés de production de revêtements à faible entretien
JP2012120967A (ja) * 2010-12-07 2012-06-28 Nissan Motor Co Ltd 可視光応答型光触媒およびこれを含む親水性部材ならびにこれらの製造方法
USRE43817E1 (en) 2004-07-12 2012-11-20 Cardinal Cg Company Low-maintenance coatings
JP2014098542A (ja) * 2008-09-16 2014-05-29 Toshiba Corp 冷蔵庫
JP2014194028A (ja) * 2008-03-04 2014-10-09 Toshiba Corp 親水性部材の製造方法
US9738967B2 (en) 2006-07-12 2017-08-22 Cardinal Cg Company Sputtering apparatus including target mounting and control
JP2018122246A (ja) * 2017-02-01 2018-08-09 株式会社オプト 構造物表面の保護層形成方法
US10604442B2 (en) 2016-11-17 2020-03-31 Cardinal Cg Company Static-dissipative coating technology
KR20210113818A (ko) 2020-03-09 2021-09-17 엘지전자 주식회사 저액조, 정수기, 및 가전기기

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JP2002211928A (ja) * 2000-12-30 2002-07-31 Altra:Kk 可視光反応型チタン酸化物及びその製造方法並びに汚染物質の除去方法
JP2003135972A (ja) * 2001-10-31 2003-05-13 Ube Nitto Kasei Co Ltd 光触媒含有多孔性薄膜およびコーティング剤
JP2003260134A (ja) * 2002-03-11 2003-09-16 Yukiyasu Okumura 院内感染防止輸液システム
JP2005231935A (ja) * 2004-02-18 2005-09-02 Taki Chem Co Ltd 酸化タングステン含有酸化チタンゾル及びその製造方法並びにコーティング剤及び光機能体
JP4507066B2 (ja) * 2004-02-18 2010-07-21 多木化学株式会社 酸化タングステン含有酸化チタンゾル及びその製造方法並びにコーティング剤及び光機能体
WO2005102952A2 (fr) * 2004-04-13 2005-11-03 Saint-Gobain Glass France Substrat photocatalytique actif sous lumiere visible
WO2005102952A3 (fr) * 2004-04-13 2006-08-24 Saint Gobain Substrat photocatalytique actif sous lumiere visible
JP2007532462A (ja) * 2004-04-13 2007-11-15 サン−ゴバン グラス フランス 可視光下で活性な光触媒性基材
USRE44155E1 (en) 2004-07-12 2013-04-16 Cardinal Cg Company Low-maintenance coatings
USRE43817E1 (en) 2004-07-12 2012-11-20 Cardinal Cg Company Low-maintenance coatings
JP2006198464A (ja) * 2005-01-18 2006-08-03 Nippon Shokubai Co Ltd 可視光応答型光触媒およびその製造方法
US9738967B2 (en) 2006-07-12 2017-08-22 Cardinal Cg Company Sputtering apparatus including target mounting and control
JP2010538960A (ja) * 2007-09-14 2010-12-16 日本板硝子株式会社 低保守コーティングおよび低保守コーティングの製造方法
EP2261186A3 (fr) * 2007-09-14 2012-07-11 Cardinal CG Company Technologie de revêtement à faible entretien
WO2009036263A3 (fr) * 2007-09-14 2009-06-04 Cardinal Cg Co Technologie de revêtement à faible entretien
WO2009036263A2 (fr) * 2007-09-14 2009-03-19 Cardinal Cg Company Technologie de revêtement à faible entretien
WO2009036284A1 (fr) * 2007-09-14 2009-03-19 Cardinal Cg Company Revêtements à faible entretien et procédés de production de revêtements à faible entretien
JP2014194028A (ja) * 2008-03-04 2014-10-09 Toshiba Corp 親水性部材の製造方法
JP2014098542A (ja) * 2008-09-16 2014-05-29 Toshiba Corp 冷蔵庫
JP2012120967A (ja) * 2010-12-07 2012-06-28 Nissan Motor Co Ltd 可視光応答型光触媒およびこれを含む親水性部材ならびにこれらの製造方法
US10604442B2 (en) 2016-11-17 2020-03-31 Cardinal Cg Company Static-dissipative coating technology
US11325859B2 (en) 2016-11-17 2022-05-10 Cardinal Cg Company Static-dissipative coating technology
JP2018122246A (ja) * 2017-02-01 2018-08-09 株式会社オプト 構造物表面の保護層形成方法
KR20210113818A (ko) 2020-03-09 2021-09-17 엘지전자 주식회사 저액조, 정수기, 및 가전기기
KR20220035061A (ko) 2020-03-09 2022-03-21 엘지전자 주식회사 저액조, 및 정수기

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