WO2007108514A1 - plaque de verre MUNIE D'un film antibactérien, procédé de fabrication d'une telle plaque et article COMPORTant la plaque de verre - Google Patents

plaque de verre MUNIE D'un film antibactérien, procédé de fabrication d'une telle plaque et article COMPORTant la plaque de verre Download PDF

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Publication number
WO2007108514A1
WO2007108514A1 PCT/JP2007/055915 JP2007055915W WO2007108514A1 WO 2007108514 A1 WO2007108514 A1 WO 2007108514A1 JP 2007055915 W JP2007055915 W JP 2007055915W WO 2007108514 A1 WO2007108514 A1 WO 2007108514A1
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Prior art keywords
antibacterial
glass plate
film
antibacterial film
glass
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PCT/JP2007/055915
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English (en)
Japanese (ja)
Inventor
Hidemasa Yoshida
Tsuyoshi Otani
Akira Fujisawa
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Nippon Sheet Glass Company, Limited
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Filing date
Publication date
Application filed by Nippon Sheet Glass Company, Limited filed Critical Nippon Sheet Glass Company, Limited
Publication of WO2007108514A1 publication Critical patent/WO2007108514A1/fr

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    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/225—Nitrides
    • 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
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C03C17/2456—Coating containing 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
    • 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
    • C03C17/3411—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
    • C03C17/3429—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 at least one of the coatings being a non-oxide coating
    • C03C17/3435—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 at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/02—Antibacterial glass, glaze or enamel
    • 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
    • C03C2217/70—Properties of coatings
    • C03C2217/71—Photocatalytic coatings

Definitions

  • the present invention relates to a glass plate with an antibacterial film, a manufacturing method thereof, and an article having the glass plate.
  • the present invention relates to a glass plate with an antibacterial film and a method for producing the same, and further relates to an article having the glass plate.
  • Japanese Patent Application Laid-Open No. 2001-72438 discloses an antibacterial processed plate glass material that can form an antibacterial effect by forming a coating film made of a resin composition containing acid titanium or the like as an antibacterial agent.
  • the antibacterial strength plate glass material is selected from roll coating, dip coating, spray coating, electrostatic coating, electrodeposition coating, wire coating, flow coating, doctor coating, etc. Since the coating film was formed by this method, the thickness of the coating film became 10-50 / ⁇ ⁇ and a micron unit, and a film thinner than these could not be formed uniformly.
  • an antibacterial film a film formed on the surface of a member in order to impart antibacterial properties to the member is referred to as an “antibacterial film”.
  • the antibacterial film metal materials such as silver, zinc and copper and photocatalytic materials such as titanium oxide are used.
  • Titanium oxide is widely used as a photocatalytic material because of its high photocatalytic activity and excellent chemical stability. When titanium oxide is irradiated with ultraviolet rays, electrons and holes are generated.
  • WO94Z11092 pamphlet discloses a technique in which powdered titanium oxide titanium is sintered on a glass plate. Although this technique can be used to obtain a plate-like antibacterial member, when coating particulate glass titanium oxide on a glass plate, the acidity is reduced. Tan particles aggregate to inevitably increase the particle size of titanium oxide. When the particle diameter of the acid titanium is increased, the thickness of the antibacterial film containing the acid titanium is increased. As a result, there was a problem that the reflectance of the antibacterial film increased and the interference color of the reflection became conspicuous.
  • the method of International Publication No. 94Z11092 pamphlet has another problem that the antibacterial film is low in mechanical durability because the antibacterial film is formed using powdered titanium oxide. Furthermore, it is not only difficult to form an antibacterial film uniformly on a large-area glass substrate, but it is also necessary to carry out a baking process and a coating process. It is unsuitable for continuous mass production of large area glass plates.
  • the method for producing a nitrogen-doped titanium oxide film disclosed in WO 01/10552 is an invention relating to a method for producing a glass plate having an antibacterial film formed on the surface thereof, and a sputtering method. After forming the TiO film with the atmosphere containing ammonia and nitrogen
  • the present invention has been completed by paying attention to the above-described problems. Its purpose is to provide a glass plate with an antibacterial film, which has an antibacterial film, which has produced interference colors of reflection. It is another object of the present invention to provide a method for manufacturing a large-sized glass plate with an antibacterial film formed thereon, which is a large area glass plate with improved mechanical durability.
  • the glass plate with an antibacterial film of the present invention is a glass plate with an antibacterial film comprising an antibacterial film directly or via a base film on the glass plate, and the film thickness of the antibacterial film is 2 nm or more and lOOnm or less. is there.
  • the antimicrobial performance of the antimicrobial film is antimicrobial product technology Council irradiation film adhesion method 10 ⁇ WZcm 2 of the ultraviolet light quantity irradiation 24 hours based on the stipulated Antibacterial performance that reduces the number of Staphylococcus aureus or Escherichia coli after irradiation to less than lZio 0 relative to the number of bacteria before irradiation.
  • the antibacterial performance of the antibacterial film is such that the yellow grapes are irradiated with ultraviolet light having a light intensity of 10 ⁇ WZcm 2 for 8 hours based on the light irradiation film adhesion method defined by the Antibacterial Product Technical Council. Antibacterial performance that reduces the number of cocci or E. coli to 1Z100 or less with respect to the number of bacteria before light irradiation.
  • the antibacterial performance of the antibacterial film is based on a light irradiation film adhesion method stipulated by the Antibacterial Product Technical Council, and after irradiating a white fluorescent lamp with an amount of lOOOLx for 24 hours.
  • Antibacterial performance to reduce the number of Staphylococcus aureus or Escherichia coli to 1Z100 or less with respect to the number of bacteria before light irradiation.
  • the antibacterial performance of the antibacterial film is yellow after irradiating a white fluorescent lamp with a light quantity of 500Lx for 24 hours based on the light irradiation film adhesion method defined by the Antibacterial Product Technical Council.
  • Antibacterial performance that reduces the number of Staphylococcus or Escherichia coli to 1Z100 or less compared to the number of bacteria before light irradiation.
  • the antibacterial performance of the antibacterial film is yellow after irradiating a white fluorescent lamp with a light quantity of 250Lx for 24 hours based on the light irradiation film adhesion method defined by the Antibacterial Product Technical Council.
  • Antibacterial performance that reduces the number of Staphylococcus or Escherichia coli to 1Z100 or less compared to the number of bacteria before light irradiation.
  • the antibacterial performance is an antibacterial performance that reduces the number of Staphylococcus aureus or Escherichia coli to 1 Z 10,000 or less.
  • the film thickness of the antibacterial film is 5 nm or more and 80 nm or less, and in a further preferred embodiment, the film thickness of the antibacterial film is more than 25 nm and less than 70 nm.
  • the main component of the antibacterial film is one selected from the group force consisting of titanium oxide, nitrogen-doped titanium oxide, titanium oxynitride, and titanium nitride power.
  • the main component of the antibacterial film is nitrogen-doped titanium oxide.
  • a method for producing a glass plate with an antibacterial film is provided. This For the manufacturing method, the antibacterial film is formed by a thermal decomposition method.
  • the film forming gas is supplied to the surface of the glass plate in which the antibacterial film is maintained at a temperature higher than the temperature at which the film forming gas is decomposed or the glass ribbon surface in the glass plate manufacturing process. To form.
  • the film forming gas contains a titanium-containing compound, a nitrogen-containing compound, and an oxidizing gas.
  • the film-forming gas further includes a reaction inhibitor that suppresses a chemical reaction between the titanium-containing compound and the nitrogen-containing compound.
  • the nitrogen-containing compound is ammonia.
  • the acidic gas is oxygen
  • the molar specific power of the acidic gas such as oxygen to the nitrogen-containing compound such as ammonia in the coating forming gas is 0.05 or more. is there.
  • the reaction inhibitor is salt hydrogen.
  • the thermal decomposition method is a CVD method performed in a nose for forming a molten glass ribbon into a plate shape in a glass manufacturing process by a float method.
  • a glass window for a building has the above glass plate with antibacterial film.
  • living windows or glass windows in medical facilities, indoor glass, etc. are provided.
  • a glass partition in a building has the above glass plate with antibacterial film.
  • furniture has the above-mentioned glass plate with an antibacterial film.
  • glass tables, glass shelves, glass showcases or glass food cases are provided.
  • a glass window for a transport machine has the above glass plate with antibacterial film.
  • vehicle, ship or aircraft glass windows are provided.
  • an information display glass panel is provided. They have the above glass plate with antibacterial film.
  • display panels and touch panels are provided.
  • the thickness of the antibacterial film is set in a range of 2 nm or more and lOOnm or less, generation of reflection interference colors is suppressed even when a titanium compound having a relatively high refractive index is used.
  • An antibacterial film-coated glass plate comprising an antibacterial film is provided.
  • a large area is obtained by performing a pyrolysis method in a bath for forming a molten glass ribbon into a plate shape.
  • a method for producing a glass plate with an antibacterial film in which the mechanical durability of the antibacterial film is enhanced in large quantities at a low cost.
  • an article having an antibacterial film-coated glass is provided.
  • FIG. 1 is a cross-sectional view showing an example of a glass plate with an antibacterial film of the present invention.
  • FIG. 1 (a) shows an example in which the antibacterial film is directly formed on the glass plate. Shows an example in which a base film is interposed between the glass plate and the antibacterial film.
  • FIG. 2 This is a schematic diagram of the equipment used for the on-line CVD method.
  • antibacterial means that the growth of bacteria or microorganisms attached to an object is suppressed, and the viable number of bacteria or microorganisms decreases with the passage of time.
  • main component means a component that occupies 50% by weight or more.
  • light irradiation film adhesion method defined by the Antibacterial Product Technology Council means the light irradiation film adhesion method (2003 version) established by the Antibacterial Product Technology Council. Antibacterial performance is evaluated based on the conditions stipulated in the dressing law. This measurement method was one of the most common measurement methods for assessing the antibacterial properties of products for those skilled in the art until JIS R1702: 2006 was issued after the basic application of this application was filed. .
  • FIG. 1 is a schematic cross-sectional view illustrating two forms of the antibacterial film-coated glass plate 4 according to the present invention. .
  • an antibacterial film 2 is formed on the glass plate 1 as shown in FIG.
  • the base film 3 it is preferable to configure the base film 3 so as to have one or more layers between the glass plate 1 and the antibacterial film 2.
  • This base film preferably has a role such as an alkali barrier function.
  • the glass plate 1 is a glass plate containing an alkali component, for example, when the alkali component moves to the antibacterial membrane 2 during the film formation process of the antibacterial membrane 2, the crystallinity of the antibacterial membrane deteriorates and the antibacterial performance deteriorates. In that case, if the base film is sandwiched, adverse effects due to the movement of the alkali component can be prevented.
  • the thickness of the antibacterial film is preferably in the range of 2 nm to lOOnm and more preferably in the range of 5 nm to 80 nm. Furthermore, the range of more than 20 nm and less than 70 nm is most preferable.
  • the antibacterial performance of the antibacterial film of the present invention is as follows: after the irradiation with ultraviolet light of 10 ⁇ WZcm 2 for 24 hours in the light irradiation film adhesion method (2003 version) established by the Antibacterial Product Technical Council.
  • Antibacterial performance that reduces the number of Staphylococcus aureus or Escherichia coli to 1Z100 or less with respect to the number of bacteria before light irradiation is preferred. More preferably, the antibacterial performance is to reduce the number of Staphylococcus aureus or Escherichia coli after irradiation with ultraviolet light of 10 / z WZcm 2 for 8 hours to 1Z100 or less with respect to the number of bacteria before light irradiation. .
  • the number of Staphylococcus aureus or Escherichia coli after 24 hours of irradiation with a white fluorescent lamp with a light intensity of lOOOLx is measured before light irradiation.
  • Antibacterial performance that reduces the number of bacteria to 1Z100 or less is preferable. More preferably, the antibacterial performance is to reduce the number of Staphylococcus aureus or Escherichia coli after irradiation with a white fluorescent lamp with a light quantity of 500 Lx for 24 hours to 1Z100 or less with respect to the number of bacteria before light irradiation.
  • a staphylococcus aureus or Escherichia coli after being irradiated with a white fluorescent lamp with a light intensity of 25 OLx for 24 hours.
  • Antibacterial performance that reduces the number to less than ⁇ against the number of bacteria before light irradiation. Since antibacterial performance evaluation is a test using microorganisms, the evaluation test error is larger than other physical property evaluations. If the number of bacteria after light irradiation is 1Z100 or less (the sterilization rate is 99% or more), it can be said that there is clearly an advantageous effect on antibacterial performance that is not within the error range.
  • the bacteria survival rate is 1% or less (the number of bacteria is reduced to 1Z100 or less), the difference between antibacterial processed products and unprocessed products Can be judged significantly.
  • the number of bacteria after light irradiation is 1 Ziooo or less.
  • the number of bacteria after light irradiation is 1Z10000 or less.
  • the intensity of the ultraviolet light to be irradiated and the illuminance of the white fluorescent lamp are typified by the following locations.
  • Ultraviolet light WZcm 2 ⁇ ⁇ 'In the daytime room about 1.5m away from the window where sunlight enters.
  • the intensity of the ultraviolet light in the fluorescent lamp lOOOLx is, 4 / z WZcm 2 about.
  • the intensity of ultraviolet light in fluorescent lamp 1000 Lx is about 2 / z WZcm 2 .
  • the bacteria to be reduced by the present invention is not particularly limited, but the present invention can be used for the following fungi.
  • examples include bacteria of Gram-positive bacteria (S. aureus, Bacillus, etc.) or Gram-negative bacteria (E. coli, Salmonella, etc.), fungi such as fungi, mushrooms, yeasts, other viruses, and protists.
  • the main component of the antibacterial film of the present invention is preferably one selected from the group power of titanium oxide, nitrogen-doped titanium oxide, titanium oxynitride, and titanium nitride power. This is because an antibacterial film containing these as main components has high antibacterial performance and excellent chemical stability.
  • the main component is preferably nitrogen-doped acid titanium.
  • nitrogen-doped acid Titanium fluoride is a photocatalytic material that responds to the light of visible light, so it is preferable in that it can use light in the visible light region that is often contained in sunlight and fluorescent lamps.
  • the raw material for the antibacterial membrane of the present invention contains at least one titanium-containing compound, at least one nitrogen-containing compound, and at least one acid gas. is required.
  • the titanium-containing compound is preferably a titanium chloride, a titanium alkoxide or a titanium chelate compound. These titanium-containing compounds are preferably in the form of a gas or liquid at room temperature, and when they are liquid at room temperature, the lower boiling point is preferable. These preferable titanium-containing compounds can be vaporized as they are or by heating a little, and can be used as components of the raw material gas. In addition, a titanium-containing compound that sublimes even if it is solid at room temperature, or a titanium-containing compound that can be dissolved in an organic solvent such as alcohol or toluene can be used.
  • titanium-containing compounds include, for example, tetrasalt-titanium (TiCl), titanium ethoxy
  • Ti Titanium Isoproxide
  • Ti Titanium Normal Butoxide
  • TiCl titanium isoproxide
  • Ti (OC H) titanium isoproxide
  • N-butanol (Ti (OCH)) is preferably used.
  • ammonia NH
  • amines NH
  • hydrazine derivatives are preferable.
  • ammonia easily liquefies by compression and is a gas at room temperature and normal pressure, and is particularly preferable in that it can be obtained in a large amount at a preferred low cost because it can be easily introduced into the raw material gas.
  • Aminyahydrazine derivatives are excellent in that they can easily produce high quality films because of their high reactivity. On the other hand, it is disadvantageous in that it is expensive.
  • the acidic gas it is preferable to use oxygen (O 2). Carbon dioxide (CO 2), acid
  • liquid raw materials such as O
  • esters When liquid raw materials such as O) and esters are used, facilities for vaporizing the liquid raw materials are required. In addition, the amount of vaporization tends to be unstable. It is preferable to use a gas raw material whose supply amount is easy to control. Of these, it is particularly preferable to use oxygen. Air can also be used. When air is used as an acidic gas, nitrogen (N) contained in the air can act as a reaction diluent.
  • N nitrogen
  • the molar ratio of oxygen to ammonia is preferably 0.05 or more.
  • the crystallinity of the film can be improved by setting the molar ratio of oxygen to air to 0.05 or more.
  • the recombination of the generated electrons and holes is thought to occur at the crystal defect site. Therefore, by improving the crystallinity, that is, by reducing the defect sites of the crystal, the rate of successful recombination with electrons can be reduced and antibacterial properties can be enhanced.
  • the raw material of the antibacterial membrane of the present invention preferably further contains a reaction inhibitor that suppresses a chemical reaction between the titanium-containing compound and the nitrogen-containing compound.
  • reaction inhibitor it is preferable to use salt hydrogen.
  • the gas phase reaction may proceed before the raw material gas reaches the glass plate.
  • a solid reaction product is generated in the raw gas piping.
  • This reaction product may block the piping.
  • this reaction product is transported to the surface of the glass plate by the flow of the raw material gas, is taken into the film to be formed, and causes defects such as pinholes.
  • the manufacturing method of the antibacterial film is not particularly limited, but a known thermal decomposition method such as a thermal CVD method or a spray method is used.
  • a fine powder of the antibacterial film is attached to the glass surface, and then the entire glass. Examples thereof include a method of agglomerating the fine powder by heating.
  • the antibacterial film may be crystal-grown by the thermal decomposition method using the agglomerated fine powder as a nucleus.
  • the thermal decomposition method particularly the thermal CVD method, can easily form a film with high mechanical durability.
  • the film formation by the thermal CVD method uses, for example, a glass plate as a substrate and a glass having a predetermined size. This can be done by heating the glass plate and spraying a gaseous raw material on the surface of the heated glass plate.
  • this can be performed as follows.
  • the glass plate is transported on a mesh belt and passed through a tunnel-shaped heating furnace.
  • the glass plate is conveyed into a heating furnace and heated to a temperature at which the film-forming gas decomposes (hereinafter abbreviated as “film-forming gas decomposition temperature”).
  • film-forming gas decomposition temperature a temperature at which the film-forming gas decomposes
  • the source gas is supplied into the heating furnace.
  • the source gas reacts with the heat of the surface of the glass plate, and an antibacterial film having antibacterial action is formed on the glass plate.
  • the film-forming gas decomposition temperature is preferably 500 ° C or higher from the viewpoint of obtaining high crystallinity and high film formation rate. That is, it is preferable to form an antibacterial film on the surface of a glass plate at 500 ° C or higher. TiNCl, TiCl ⁇ ⁇ , etc. when the temperature is below 500 ° C
  • the glass plate in the glass plate manufacturing process, the glass plate is heated at a high temperature in the step of forming the glass melt into the glass plate or in the slow cooling step after the glass plate is formed. It is preferable to utilize that. This is because if a raw material gas is supplied onto a high-temperature glass plate, a thin film can be formed without using a separate heating facility. In addition, in this way, a thin film can be formed at high speed on a glass plate having a large area, and a glass plate with a thin film can be produced for applications that require a large area such as buildings, vehicles, and display panels. it can. As described above, the method of forming a film on a high-temperature glass plate in the middle of the manufacturing process is called an online CVD method.
  • the above-described process of forming the glass melt and the glass plate is performed in a molten tin tank (referred to as a float bath) in the glass plate manufacturing process by the float process.
  • the glass melt melted in the melting furnace (called the float kiln) flows into the float bath.
  • the glass melt is drawn into a long strip without interruption and is called a glass ribbon.
  • a method in which the online CVD method is performed in a float bath is called an in-bus CVD method.
  • the intra-CVD method has the following advantages. First, the atmosphere inside the float bath is controlled so that air does not enter. Therefore, pinhole etc. It is possible to suppress defects.
  • the temperature of the glass ribbon in the float bath is very high. The temperature depends on the strength of the glass ribbon. In the case of ordinary soda lime silicate glass, the temperature is, for example, in the range of 650 to 1150 ° C.
  • the crystallinity of the thin film having antibacterial performance can be improved and the antibacterial performance can be improved.
  • the raw material gas exhibits sufficient reactivity, a thin film having a sufficient thickness of antibacterial performance can be easily formed on the glass ribbon without lowering the conveyance speed of the glass ribbon. As a result, productivity can be expected to increase, and it becomes possible to manufacture a large number of glass plates with antibacterial films at low cost.
  • Fig. 2 shows an embodiment of an apparatus for forming a film on a glass ribbon by the in-bus CVD method in the float method.
  • the surface force of the glass ribbon 10 that flows out from the float kiln 11 into the float bath 12 and moves in a strip shape on the molten tin 15 is also separated by a predetermined distance, and a predetermined number of coaters 16 Is arranged in the float bath.
  • three coaters 16a, 16b and 16c are shown. The number of coaters can be appropriately designed according to the design of the membrane configuration.
  • the on-line CVD method can also be performed in a slow cooling step (called “rare”) after being formed into a glass plate.
  • the raw material gas is introduced at the inlet of the rare (slow cooling kiln) and Z or inside the rare.
  • this method is referred to as a rare-layer CVD method.
  • the glass ribbon near the rare entrance or the rare entrance in the rare is at a lower temperature than in the bath, it has a sufficiently high temperature for the film formation reaction.
  • the rare CVD method has the following features, unlike the chemical CVD method. First of all, it is not suitable for bus CVD method.
  • a raw material whose reaction rate is too high at the glass ribbon temperature of the CVD method in the bath, or a raw material that may have an unfavorable effect on the float bath can be used. It can also be applied to glass plate manufacturing processes that do not have a float bath. For example, it can be applied to a glass plate manufacturing process by a roll-out method, and a plate glass, a netted glass, and a wire glass having an antibacterial film having an antibacterial action can be manufactured.
  • a non-alkali glass plate having a thickness of 0.7 mm was cut into a square having a side of 10 cm, washed, and then dried.
  • a nitrogen-doped titanium oxide film was formed by atmospheric pressure CVD using a transfer furnace of an atmospheric pressure thermal CVD apparatus.
  • the above glass plate was placed on a mesh belt and conveyed in the above furnace to heat the glass plate.
  • a nitrogen-doped titanium oxide film was formed by supplying a source gas to the surface of the glass plate.
  • This source gas includes titanium tetrachloride (TiCl), oxygen (O), ammonia (NH), and hydrogen chloride as a reaction inhibitor.
  • HC1 HC1
  • a gas diluted with nitrogen gas to a predetermined concentration was used.
  • a nitrogen-doped titanium oxide film was formed by adjusting the concentration of the source gas and the conveying speed.
  • a thin film was formed on the surface of the glass ribbon by the CVD method in the bus. Specifically, it is as follows.
  • the first coater (16a in Fig. 2) formed an SiO film with a thickness of 50 nm on the glass ribbon as a base film.
  • the raw material gases include tetrasalt ⁇ titanium (TiCl), ethyl acetate (CHO
  • a titanium oxide film was formed by adjusting the conveyance speed.
  • Example 14 a nitrogen-doped titanium oxide film was formed using the same source gas as in Examples 1 to 12 and the comparative example.
  • the cross section of the glass plate on which the thin film was formed was measured by observing it with a scanning electron microscope (SEM).
  • the antibacterial properties of the obtained films were evaluated by the light irradiation film adhesion method established by the Antibacterial Product Technical Council.
  • the number of Staphylococcus aureus after 24 hours of ultraviolet irradiation is reduced to 1Z100 or less, and has good antibacterial properties.
  • the number of E. coli after 24 hours of ultraviolet irradiation was reduced to 1Z100 or less, and had good antibacterial properties.
  • the UV intensity was adjusted to 10 / z WZcm 2 and the irradiation time of ultraviolet rays was set to 8 hours, as in (Antibacterial performance test 1) above. Test gave.
  • the test strain was evaluated using Staphylococcus aureus NBRC12732.
  • Example 3 For Examples 3, 5, and 8-14, based on the light irradiation film adhesion method defined by the Antibacterial Product Technical Council, using a white fluorescent lamp, adjusting the illuminance to lOOOLx, the white fluorescent lamp The test was conducted in the same manner as the above (Antibacterial performance test 1) except that the irradiation time was 24 hours.
  • the test bacteria were evaluated using Staphylococcus aureus NBRC12732 and Escherichia coli NBRC3972.
  • the white fluorescent lamp was adjusted so that the illuminance was 500 Lx.
  • the test was conducted in the same manner as the above (Antibacterial performance test 1) except that the irradiation time was 24 hours.
  • the test bacteria were evaluated using Staphylococcus aureus NBRC12732.
  • the white fluorescent lamp was adjusted so that the illuminance was 250 Lx, and the white fluorescent lamp was irradiated.
  • the test was conducted in the same manner as (Antibacterial performance test 1) except that the time was 24 hours.
  • the test bacteria were evaluated using Staphylococcus aureus NBRC12732.
  • the thin films of Examples 1 to 14 had a thickness in the range of 5 to 80 nm, and thus had no interference color. On the other hand, an interference color occurred in the comparative thin film having a thickness of 150 nm.
  • the glass plate with an antibacterial film of the present invention is different from conventional ones in the fields of glass windows for buildings, glass windows for transportation machinery, glass panels for information display, etc. It has a great utility value in that it can provide a glass plate with an antibacterial film with improved mechanical durability.

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

Abstract

L'invention concerne une plaque de verre munie d'un film antibactérien qui est équipée d'un film antibactérien montrant à peine une couleur d'interférence due à la réflexion. Elle concerne également un procédé de fabrication dans une grande quantité et à bas prix d'une plaque de verre, qui est une plaque de verre de grande dimension sur laquelle est formé un film antibactérien qui présente une durabilité mécanique améliorée. Cette plaque de verre munie d'un film antibactérien est obtenue par formation d'un film antibactérien ayant une épaisseur de film supérieure ou égal à 2 nm mais ne dépassant pas 100 nm sur une plaque de verre soit directement soit en faisant appel à un film d'apprêt. Le film antibactérien est formé par le procédé de décomposition thermique consistant à appliquer un gaz de formation de film à la surface d'une plaque de verre, qui a été fabriqué à une température permettant la décomposition du gaz de formation de film ou à une température supérieure, ou à la surface d'un ruban de verre pendant la fabrication d'une plaque de verre.
PCT/JP2007/055915 2006-03-22 2007-03-22 plaque de verre MUNIE D'un film antibactérien, procédé de fabrication d'une telle plaque et article COMPORTant la plaque de verre WO2007108514A1 (fr)

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JP2006078818A JP2007254192A (ja) 2006-03-22 2006-03-22 抗菌膜付きガラス板とその製造方法、及びそのガラス板を有する物品
JP2006-078818 2006-03-22

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012246213A (ja) * 2011-05-02 2012-12-13 Hoya Corp 電子機器用カバーガラスのガラス基板及びその製造方法
DE102014013528A1 (de) 2014-09-12 2016-03-17 Schott Ag Beschichtetes Glas-oder Glaskeramiksubstrat mit beständigen multifunktionellen Oberflächeneigenschaften, Verfahren zu dessen Herstellung und dessen Verwendung
GB202011249D0 (en) 2020-07-21 2020-09-02 Pilkington Group Ltd Antimicrobial substrate
WO2022090708A1 (fr) 2020-10-26 2022-05-05 Pilkington Group Limited Utilisation de substrats revêtus

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022048048A (ja) * 2020-09-14 2022-03-25 日本板硝子株式会社 表示装置

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JPH08187604A (ja) * 1994-12-28 1996-07-23 Mitsubishi Materials Corp 硬質被覆層がすぐれた層間密着性を有する表面被覆炭化タングステン基超硬合金製切削工具
JP2000143299A (ja) * 1998-11-10 2000-05-23 Nippon Sheet Glass Co Ltd 光触媒機能を有する窓ガラス
WO2002004376A1 (fr) * 2000-07-12 2002-01-17 Nippon Sheet Glass Co., Ltd. Element photocatalytique
JP2003190809A (ja) * 2001-10-15 2003-07-08 Jfe Steel Kk 光触媒被膜を形成した複合材料の製造方法
JP2004105904A (ja) * 2002-09-20 2004-04-08 Toto Ltd 光触媒による塩基性物質の分解方法および分解に用いる光触媒

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JPH08187604A (ja) * 1994-12-28 1996-07-23 Mitsubishi Materials Corp 硬質被覆層がすぐれた層間密着性を有する表面被覆炭化タングステン基超硬合金製切削工具
JP2000143299A (ja) * 1998-11-10 2000-05-23 Nippon Sheet Glass Co Ltd 光触媒機能を有する窓ガラス
WO2002004376A1 (fr) * 2000-07-12 2002-01-17 Nippon Sheet Glass Co., Ltd. Element photocatalytique
JP2003190809A (ja) * 2001-10-15 2003-07-08 Jfe Steel Kk 光触媒被膜を形成した複合材料の製造方法
JP2004105904A (ja) * 2002-09-20 2004-04-08 Toto Ltd 光触媒による塩基性物質の分解方法および分解に用いる光触媒

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012246213A (ja) * 2011-05-02 2012-12-13 Hoya Corp 電子機器用カバーガラスのガラス基板及びその製造方法
DE102014013528A1 (de) 2014-09-12 2016-03-17 Schott Ag Beschichtetes Glas-oder Glaskeramiksubstrat mit beständigen multifunktionellen Oberflächeneigenschaften, Verfahren zu dessen Herstellung und dessen Verwendung
DE102014013528B4 (de) 2014-09-12 2022-06-23 Schott Ag Beschichtetes Glas-oder Glaskeramiksubstrat mit beständigen multifunktionellen Oberflächeneigenschaften, Verfahren zu dessen Herstellung und dessen Verwendung
WO2021260370A1 (fr) 2020-06-23 2021-12-30 Pilkington Group Limited Substrat antimicrobien
GB202011249D0 (en) 2020-07-21 2020-09-02 Pilkington Group Ltd Antimicrobial substrate
WO2022090708A1 (fr) 2020-10-26 2022-05-05 Pilkington Group Limited Utilisation de substrats revêtus

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