WO2009078109A1 - Water-repellent, oil-repellent, soil-resistant glass plate, method of manufacturing the same, and transport equipment, construction and optical equipment using the same - Google Patents

Water-repellent, oil-repellent, soil-resistant glass plate, method of manufacturing the same, and transport equipment, construction and optical equipment using the same Download PDF

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Publication number
WO2009078109A1
WO2009078109A1 PCT/JP2007/074624 JP2007074624W WO2009078109A1 WO 2009078109 A1 WO2009078109 A1 WO 2009078109A1 JP 2007074624 W JP2007074624 W JP 2007074624W WO 2009078109 A1 WO2009078109 A1 WO 2009078109A1
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Prior art keywords
repellent
water
oil
soil
glass plate
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PCT/JP2007/074624
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French (fr)
Inventor
Kazufumi Ogawa
Original Assignee
Kazufumi Ogawa
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Application filed by Kazufumi Ogawa filed Critical Kazufumi Ogawa
Priority to PCT/JP2007/074624 priority Critical patent/WO2009078109A1/en
Publication of WO2009078109A1 publication Critical patent/WO2009078109A1/en

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Classifications

    • 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
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • 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
    • 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
    • C03C2217/76—Hydrophobic and oleophobic 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • 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
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes

Definitions

  • the present invention relates to a glass plate having high durability and a water-repellent, oil-repellent, and soil-resistant coating formed on a surface thereof.
  • the present invention relates to the glass plate for a window of transport equipment, such as an automobile, or construction, such as a building, and for a filter of optical equipment, where water-repellent, oil-repellent, and soil-resistant functions are required. Further, the present invention relates to the transport equipment, the construction, and the optical equipment using the same, as well as a method of manufacturing the same.
  • a film-forming solution comprising a chlorosilane-based adsorbent containing a fluorocarbon group and a non-water-based organic solvent can be used to effect chemisorption in a liquid phase so as to form a water-repellent, oil-repellent, and soil-resistant chemisorption film in the form of a monomolecular film (for example, see Japanese Patent Publication (Kokai) No. 04-132637).
  • a manufacture principle of the chemisorption monomolecular film in such a solution is in forming the monomolecular film by means of dehydrochlorination reaction between active hydrogen, such as a hydroxyl group on a substrate surface, and a chlorosilyl group of the chlorosilane-based adsorbent.
  • the present invention is, in a glass plate for a window of transport equipment, such as an automobile, or construction, such as a building, and for a filter of optical equipment, where water-repellent, oil-repellent, and soil-resistant functions are required, intended to provide a water-repellent, oil-repellent, and soil-resistant glass plate, that can improve the water-repellent, oil-repellent, and soil-resistant properties, the water releasing property (also referred to as water lubricity), as well as the durability, such as the wear resistance and the whether resistance, a method of manufacturing the same, and the transport equipment, the construction, and the optical equipment using the same.
  • a water-repellent, oil-repellent, and soil-resistant glass plate according to a first invention provided as means for solving the foregoing problems is characterized in that a surface thereof is covered with water-repellent, oil-repellent, and soil-resistant transparent particles that have been fixed thereto by sintering.
  • the water-repellent, oil-repellent, and soil-resistant glass plate according to a second invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the first invention, characterized in that a surface of the transparent particle is partially coated with a water-repellent, oil-repellent, and soil-resistant coating.
  • the water-repellent, oil-repellent, and soil-resistant glass plate according to a third invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the second invention, characterized in that the transparent particle is fixed by sintering to a surface of a substrate glass via a transparent metal oxide film.
  • the water-repellent, oil-repellent, and soil-resistant glass plate according to a fourth invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the third invention, characterized in that the metal oxide film is a silica-based glass film.
  • the water-repellent, oil-repellent, and soil-resistant glass plate according to a fifth invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the fourth invention, characterized in that a surface of the silica-based glass film is coated with the water-repellent, oil-repellent, and soil-resistant coating.
  • the water-repellent, oil-repellent, and soil-resistant glass plate according to a sixth invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the fifth invention, characterized in that at least the water-repellent, oil-repellent, and soil-resistant coating is covalently bonded to the surfaces of the transparent particle and silica-based glass film.
  • the water-repellent, oil-repellent, and soil-resistant glass plate according to a seventh invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the first to sixth inventions, characterized in that the transparent particle is translucent silica, alumina, or zirconia.
  • the water-repellent, oil-repellent, and soil-resistant glass plate according to an eighth invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the first to seventh inventions, characterized in that the size of the transparent particle is less than a wavelength of visible light.
  • the water-repellent, oil-repellent, and soil-resistant glass plate according to a ninth invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the first to eighth inventions, characterized in that a contact angle to water is controlled to be not less than 130 degrees.
  • Transport equipment according to a tenth invention is characterized in that the water-repellent, oil-repellent, and soil-resistant glass plate according to the first to ninth inventions is mounted thereto as a windowpane.
  • a construction according to an eleventh invention is characterized in that the water-repellent, oil-repellent, and soil-resistant glass plate according to the first to ninth inventions is mounted thereto as a windowpane.
  • Optical equipment according to a twelfth invention is characterized in that the water-repellent, oil-repellent, and soil-resistant glass plate according to the first to ninth inventions is mounted to a front face of a lens thereof as a filter.
  • a method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to a thirteenth invention is characterized by including: a first step of preparing the transparent particles, the surfaces thereof being covered with a water-repellent or oil-repellent coating; a second step of preparing a dispersion, wherein the transparent particles are dispersed in a solution containing metal alkoxide; a third step of applying and drying the dispersion on the surface of the substrate glass; a fourth step of heat-treating the substrate glass having the dispersion applied thereto in an atmosphere containing oxygen; and a fifth step of forming the water-repellent, oil-repellent, and soil-resistant coating on the surface of the substrate glass that has been heat-treated at the fourth step.
  • the "metal alkoxide” includes tetraalkoxysilane in this description.
  • the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to a fourteenth invention is, in the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to the thirteenth invention, characterized in that the metal alkoxide produces silica-based glass by the heat treatment.
  • the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to a fifteenth invention is, in the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to the thirteenth and fourteenth inventions, characterized in that a temperature of the heat treatment at the fourth step is not less than 250 degrees C, and not higher than a melting point of the substrate glass and the transparent particle.
  • the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to a sixteenth invention is, in the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to the thirteenth to fifteenth inventions, characterized in that a solvent having the metal alkoxide dissolved therein is water-based, and that the coating covering the surface of the transparent particle at the first step is water-repellent.
  • the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to a seventeenth invention is, in the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to the thirteenth to fifteenth inventions, characterized in that the solvent having the metal alkoxide dissolved therein is organic-based, and that the coating covering the surface of the transparent particle at the first step is oil-repellent.
  • the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to an eighteenth invention is, in the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to the thirteenth to seventeenth inventions, characterized in that the formation of the water-repellent, oil-repellent, and soil-resistant coating at the fifth step is carried out by contacting a film-forming solution containing any of: (1 ) a trialkoxysilane derivative containing a fluorocarbon group and a silanol condensation catalyst; (2) a trichlorosilane derivative containing the fluorocarbon group; and (3) an isocyanate derivative containing the fluorocarbon group, as well as an organic solvent, with the substrate glass having the transparent particles fixed by sintering to the surface thereof.
  • the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to a nineteenth invention is, in the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to the eighteenth invention, characterized in that, after contacting the film-forming solution with the substrate glass, the excess film-forming solution is washed off.
  • the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to a twentieth invention is, in the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to the eighteenth and nineteenth inventions, characterized in that the film-forming solution contains the silanol condensation catalyst, and that one or more compounds selected from the group consisting of a ketimine compound, organic acid, metal oxide, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are used as a co-catalyst with the silanol condensation catalyst.
  • the surface of the glass plate is covered with the water-repellent, oil-repellent, and soil-resistant transparent particles fixed thereto by sintering, it becomes possible to improve water-repellent, oil-repellent, and soil-resistant properties, water releasing property (water lubricity), wear resistance, whether resistance, and the like of the glass plate.
  • the transparent particle with the surface thereof being partially covered with the water-repellent, oil-repellent, and soil-resistant coating, because it allows for manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate in a simple manner using a raw material, such as silica and alumina, which is inexpensive and exhibits excellent wear resistance or the like. It is advantageous in order to improve the wear resistance that the transparent particle is fixed by sintering to the surface of the substrate glass via the transparent metal oxide film.
  • the metal oxide film if it is the silica-based glass film, has the same refractive index or coefficient of thermal expansion as that of the substrate glass.
  • the surface of the silica-based glass film is coated with the water-repellent, oil-repellent, and soil-resistant coating. It is advantageous in order to improve the durability that at least the water-repellent, oil-repellent, and soil-resistant coating is covalently bonded to the surfaces of the transparent particle and silica-based glass film.
  • the transparent particle is translucent silica, alumina, or zirconia.
  • the size of the transparent particle is less than the wavelength of the visible light (360-700 nm).
  • the size of the transparent particle is preferably 10-300 nm, and more preferably 50-100 nm. It is advantageous that the contact angle to water is controlled to be not less than 130 degrees for the water-repellent, oil-repellent, and soil-resistant glass plate, because it allows for improving the water releasing property, resulting in improving outside visibility in the rainy weather, as well as soil resistance, when used as the windowpane of the transport equipment or construction. In addition, it is advantageous that the water-repellent, oil-repellent, and soil-resistant glass plate is mounted to the transport equipment, such as the automobile, as the windowpane, because it allows for improving the outside visibility in the rainy weather.
  • the water-repellent, oil-repellent, and soil-resistant glass plate is mounted to the construction as the windowpane, because it allows for improving the outside visibility in the rainy weather. Further, it is advantageous that the water-repellent, oil-repellent, and soil-resistant glass plate is mounted to the front face of the lens as the filter of the optical equipment, such as a surveillance camera, because it allows for maintaining an image to be clear in the rainy weather as well.
  • the invention relating to the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate, including: the first step of preparing the transparent particles, the surfaces thereof being covered with the water-repellent or oil-repellent coating; the second step of preparing the dispersion, wherein the transparent particles are dispersed in the solution containing the metal alkoxide; the third step of applying and drying the dispersion on the surface of the substrate glass; the fourth step of heat-treating the substrate glass having the dispersion applied thereto in the atmosphere containing oxygen; and the fifth step of forming the water-repellent, oil-repellent, and soil-resistant coating on the surface of the substrate glass that has been heat-treated at the fourth step, it becomes possible to manufacture the water-repellent, oil-repellent, and soil-resistant glass plate with the improved water-repellent, oil-repellent, and soil-resistant properties, water releasing property (water lubricity), wear resistance, weather resistance, and the like, in an inexpensive and simple manner.
  • the metal alkoxide produces the silica-based glass by the heat treatment, because it allows for improving the wear resistance and the weather resistance.
  • the temperature of the heat treatment at the fourth step is not less than 250 degrees C, and not higher than the melting point of the substrate glass and transparent particle, because it allows for preventing the substrate glass and the transparent particle from deformation due to melting upon fixing the particles by bonding.
  • the coating covering the surface of the transparent particle is water-repellent in the case that the solvent having the metal alkoxide dissolved therein is water-based, because it allows the particle to be exposed from the solution containing the metal alkoxide upon application, resulting in forming irregularities having a high aspect ratio.
  • the coating covering the surface of the transparent particle is oil-repellent in the case that the solvent having the metal alkoxide dissolved therein is organic-based, because it allows the particle to be exposed from the solution containing the metal alkoxide upon application, resulting in forming the irregularities having the high aspect ratio.
  • the step of forming the water-repellent, oil-repellent, and soil-resistant coating is carried out by contacting the film-forming solution containing any of: (1 ) the trialkoxysilane derivative containing the fluorocarbon group and the silanol condensation catalyst; (2) the trichlorosilane derivative containing the fluorocarbon group; and (3) the isocyanate derivative containing the fluorocarbon group, as well as the organic solvent, with the substrate glass having the transparent particles fixed by sintering to the surface thereof, because it allows for improving water-repellent, oil-repellent, and soil-resistant performance with simple operation.
  • the film-forming solution containing the silanol condensation catalyst is used at the fifth step of forming the water-repellent, oil-repellent, and soil-resistant coating, to use one or more compounds selected from the group consisting of the ketimine compound, organic acid, the metal oxide, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxysilane compound as the co-catalyst with the silanol condensation catalyst, because it allows for reducing manufacturing time.
  • a water-repellent, oil-repellent, and soil-resistant glass plate having excellent water releasing property (also referred to as water lubricity), soil resistance, as well as durability, such as wear resistance and weather resistance, along with transport equipment, construction, and optical equipment using the same.
  • FIG. 1 is a conceptual diagram enlarged to a molecular level for illustrating process of forming a fluorocarbon-based monomolecular film on a surface of a silica particle in a first example of the present invention, wherein FIG. 1 A is a sectional view of the silica particle before reaction and FIG. 1 B is a sectional view thereof after the monomolecular film containing a fluorocarbon group is formed; and
  • FIG. 2 is a conceptual diagram enlarged to a molecular level for illustrating process of forming a water-repellent, oil-repellent, and soil-resistant fluorocarbon-based monomolecular film in the first example of the present invention, wherein FIG 2A is a sectional view showing a state that the silica particle coated with the fluorocarbon-based monomolecular film and a silica-based glass film are applied to a surface of a glass substrate, FIG. 2B is a sectional view showing a state after the fluorocarbon-based monomolecular film on the surface of the silica particle is removed by decomposition by means of sintering in an atmosphere containing oxygen, and FIG. 2C is a sectional view showing a state that the fluorocarbon-based monomolecular film is formed on the exposed surfaces of the silica particle and silica-based glass film.
  • FIG. 2A is a sectional view showing a state that the silica particle coated with the fluorocarbon-
  • the present invention provides a water-repellent, oil-repellent, and soil-resistant glass plate, characterized in that a surface thereof is covered with water-repellent, oil-repellent, and soil-resistant transparent particles that have been sintered, manufactured by a method including: a first step of preparing the transparent particles, the surfaces thereof being covered with a water-repellent or oil-repellent coating; a second step of preparing a dispersion, wherein the transparent particles are dispersed in a solution containing metal alkoxide; a third step of applying and drying the dispersion on a surface of a substrate glass; a fourth step of heat-treating the substrate glass having the dispersion applied thereto in an atmosphere containing oxygen; and a fifth step of forming a water-repellent, oil-repellent, and soil-resistant coating on the surface of the substrate glass that has been heat-treated at the fourth step. Further, the present invention provides transport equipment, construction, and optical equipment having such a water-
  • the present invention has an effect, in the glass plate for a window of the transport equipment or construction, and a filter of the optical equipment, where water-repellent, oil-repellent, and soil-resistant functions are required, that it is possible to provide the water-repellent, oil-repellent, and soil-resistant glass plate or filter having excellent water releasing property (water lubricity), soil resistance, and durability, such as wear resistance and weather resistance, along with the transport equipment, the construction, or the optical equipment using the same.
  • water releasing property water lubricity
  • soil resistance such as wear resistance and weather resistance
  • the water-repellent, oil-repellent, and soil-resistant glass plate according to the present invention can be used as a windowpane of the transport equipment, such as an automobile, or the construction, such as a building, and as the filter of the optical equipment, the case will be described as a representative example where the glass plate is used as the windowpane of the transport equipment, such as an automobile, or the construction, such as a building, and as the filter of the optical equipment, the case will be described as a representative example where the glass plate is used as the windowpane of the transport equipment, such as an automobile, or the construction, such as a building, and as the filter of the optical equipment, the case will be described as a representative example where the glass plate is used as the windowpane of the transport equipment, such as an automobile, or the construction, such as a building, and as the filter of the optical equipment, the case will be described as a representative example where the glass plate is used as the windowpane of the transport equipment, such as an automobile, or the construction, such as a building, and
  • a chemisorption liquid is prepared by weighing 99 weight parts of CF 3 (CF2)7(CH2)2Si(OCH3)3, as an example of a trialkoxysilane derivative containing a fluorocarbon group (-CF 3 ), and 1 weight part of dibutyltin diacetylacetonate, as an example of a silanol condensation catalyst, respectively, and by dissolving them in a hexamethyldisiloxiane solvent, as an example of an organic solvent, so that the trialkoxysilane derivative accounts for approximately 1 weight % (preferable concentration is approximately 0.5 to 3%).
  • a silica particle 1 (it may be a particle of alumina or zirconia, as long as it is transparent), as an example of a transparent particle, having a diameter of approximately 100 nm is sufficiently dried, mixed in the chemisorption liquid, and caused to react for approximately 1 hour while agitating in atmospheric air (relative humidity of 45%)
  • the diameter of the particle is preferably smaller than a wavelength of visible light (360 to 700 nm).
  • the diameter of the particle is preferably 10 to 300 nm, and more preferably 50 to 100 nm).
  • a surface of the silica particle 1 contains many hydroxyl groups 2, a -Si(OCH3)3 group of the trialkoxysilane derivative and the hydroxyl group 2 undergo dealcoholization condensation (in this case, CH 3 OH is removed) under the presence of the silanol condensation catalyst, and a monomolecular film 3 containing the fluorocarbon group, having a film thickness of approximately 1 nm, is formed over the entire surface of the silica particle 1 , as represented in the following Formula C1. [C1]
  • a dispersion is prepared by dispersing approximately 1 wt% of the silica particles 4 coated with the oil-repellent monomolecular film 3 in a solution (it may utilize a commercially available metal alkoxide solution, diluted with alcohol, that can form a transparent coating using the sol-gel method), which has been prepared by weighing tetramethoxysilane (Si(OCH 3 )4), as an example of the metal alkoxide that forms silica-based glass by heat treatment, and dibutyltin diacetylacetonate, as an example of the silanol condensation catalyst, respectively, in the molar ratio of 99:1 , and by dissolving them in the hexamethyldisiloxane solvent, as an example of the organic solvent, with the concentration of approximately 1 wt% in total (preferable concentration is approximately 0.5 to 3%).
  • a solution it may utilize a commercially available metal alkoxide solution, diluted with alcohol, that can form a transparent coating
  • a silanol group resulting from hydrolysis by tetramethoxysilane reacting with moisture in the air, undergoes dealcoholization reaction with an alkoxysilyl group, eventually forming a silica-based glass film (an example of a metal oxide film) 6 having the film thickness of approximately 50 nm.
  • the silica particle 1 is fixed by sintering to the surface of the substrate glass 5 via the silica-based glass film 6, so that the irregular substrate 7 on which the transparent particle are sintered can be manufactured (the baking temperature is not less than 250 degrees C, and not higher than a melting point of the substrate glass 5 or the silica particle 1 , wherein the higher it is, the more robustly the particle can be fixed by sintering to the glass surface).
  • the monomolecular film 3 containing the fluorocarbon group on the surface of the silica particle 4 was completely removed by decomposition by heat-treating it under the presence of oxygen (FIG. 2B).
  • the trialkoxysilane derivative forms the monomolecular film 8 (an example of the water-repellent, oil-repellent, and soil-resistant coating) containing the fluorocarbon group by bonding with the hydroxyl group on the surface of the silica particle 1 and of the silica-based glass film 6 via chemical bonding represented by Formula C1 (FIG. 2C).
  • the silica particle 1 on the surface of the super water-repellent, oil-repellent, and soil-resistant glass plate 10 is fixed by sintering to the surface of the substrate glass 5 via the silica-based glass film 6, and the surface on which the silica particle 1 fixed by sintering is exposed and the surface on which the silica-based glass film 6 is exposed are fully coated (covalently bonded) with the monomolecular film 8 containing the fluorocarbon group.
  • the film thickness of the monomolecular film 8 containing the fluorocarbon group is approximately 1 nm, which is much smaller than the size of the silica particle 1 on the surface of the glass substrate 5.
  • the trialkoxysilane derivative CF 3 (CF 2 )7(CH2)2Si(OCH 3 )3, having the fluorocarbon group is used for forming the monomolecular film 8 containing the fluorocarbon group
  • the trialkoxysilane derivatives represented in the following (1) to (12) can be used.
  • alkyltrialkoxysilane derivative CH 3 (CH 2 ) 9 Si(OCH 3 ) 3
  • the alkyltrialkoxysilane derivatives represented in the following (21) to (32), other than the above example, can be used.
  • the silanol condensation catalyst it is possible, as the silanol condensation catalyst, to use carboxylic acid metal salts, carboxylate ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanates, and titanate chelates.
  • stannous acetates dibutyltin dilaulates, dibutyltin dioctates, dibutyltin diacetates, dioctyltin dilaurates, dioctyltin dioctates, dioctyltin diacetates, stannous dioctates, lead naphthenates, cobalt naphthenates, 2-ethyl hexenic acid irons, dioctyltin-bis-octylthioglycolate salts, dioctyltin maleate salts, dibutyltin maleate polymers, dimethyltin mercaptopropionate polymers, dibutyltin bis-acetyl acetates, dioctyltin bis-acetyllaurates, tetrabutyl titanates, tetranonyl titanates, and bis(acetylace
  • the trichlorosilane derivatives having the fluorocarbon group represented in the following (41 ) to (45) and the triisocyanatesilane derivatives containing the fluorocarbon group represented in (46) to (52) can be used, wherein the silanol condensation catalyst is not required.
  • (41 ) CF 3 CH 2 O(CH 2 ) 15 SiC
  • the solvent of the film-forming solution can include an organochlorine-based solvent having no water content, a hydrocarbon-based solvent, a fluorocarbon-based solvent, a silicone-based solvent, or a mixture thereof. Note herein that if the monomolecular film 8 containing the fluorocarbon group is formed by vaporizing the solvent without washing off, it is preferred that a boiling point of the solvent is approximately 50 to 250 degrees C.
  • the specifically available solvent can include, in the case of the chlorosilane derivative, non-water-based petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, alkyl-modified silicone, polyether silicone, dimethylformamide, or the like. Furthermore, if the monomolecular film 8 containing the fluorocarbon group is formed by only vaporizing the solvent using the alkoxysilane derivative, it is possible to use, in addition to the above-described solvent, an alcohol-based solvent, such as methanol, ethanol, propanol, and the like, or a mixture thereof.
  • an alcohol-based solvent such as methanol, ethanol, propanol, and the like, or a mixture thereof.
  • the available fluorocarbon-based solvent includes a flon-based solvent, Florinate (from 3M, U.S.), Aflude (from Asahi Glass Co., Ltd.), or the like. Note herein that one of them may be singularly used, or two or more of them may be combined as long as they are mixed well.
  • the organochlorine-based solvent such as chloroform, may be added.
  • reaction time can be reduced to about half to two-third under the condition that the concentration thereof is similar to that of the above-described silanol condensation catalysts.
  • the reaction can be further accelerated by several times, so that the time required for film-formation process can be reduced to a few tenths (while the silanol condensation catalyst and the co-catalyst can be used in a range of the molar ratio of 1 :9 to 9:1 , approximately 1 :1 is desired).
  • reaction time can be reduced to approximately 20 minutes.
  • the ketimine compound, the organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxysilane compound have the higher activity than that of the silanol condensation catalyst. Further, it has been proved that using one selected from the group consisting of the ketimine compound, the organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxysilane compound as the co-catalyst with the silanol condensation catalyst further increases the activity.
  • the available ketimine compound includes, but not specifically limited to, for example, 2, 5, 8-triaza-1 , 8-nonadiene, 3, 11 -dimethyl-4, 7, 10-triaza-3, 10-tridecadiene, 2, 10-dimethyl-3, 6, 9-triaza-2, 9-undecadiene, 2, 4, 12, 14-tetramethyl-5, 8, 11-triaza-4, 11 -pentadecadiene, 2, 4, 15, 17-tetramethyl-5, 8, 11 , 14-tetraaza-4, 14-octadecadiene, 2, 4, 20, 22-tetramethyl-5, 12, 19-triaza-4, 19-trieicosadiene, or the like.
  • the available organic acid can include, but not specifically limited to, for example, formic acid, acetic acid, monobasic acids, such as propionic acid, hydroxyl acids, such as butyric acid, dibasic acids, such as malonic acid, wherein any of them exhibits the similar result.
  • the super water-repellent, oil-repellent, and soil-resistant glass plates produced under the same conditions with those of the glass plate produced according to the first example, except that alumina is used as the transparent particle, having the contact angle to water droplets of approximately 150 degrees (in practice, the contact angle to water droplets of not less than 130 degrees can achieve the similar effect), were mounted as a front windowpane (also referred to as a windshield, an inclination angle of approximately 45 degrees), a side windowpane (the inclination angle of approximately 70 degrees), and a read windowpane (the inclination angle of approximately 30 degrees), for carrying out driving experiments in the rainy weather.
  • a front windowpane also referred to as a windshield, an inclination angle of approximately 45 degrees
  • a side windowpane the inclination angle of approximately 70 degrees
  • a read windowpane the inclination angle of approximately 30 degrees
  • the front windowpane fabricated in this example exhibited much higher wear resistance because the alumina particles having high hardness have been fixed by sintering to the surface.

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Abstract

There are provided a water-repellent, oil-repellent, and soil-resistant glass plate having improved water-repellent, oil-repellent, and soil-resistant properties, water releasing property (also referred to as water lubricity), and durability, such as wear resistance or whether resistance, a method of manufacturing the same, as well as transport equipment, construction, and optical equipment using the same. A super water-repellent, oil-repellent, and soil-resistant glass plate 10 is manufactured, a surface thereof being covered with a water-repellent, oil-repellent, and soil-resistant transparent particle 9 fixed thereto by sintering, by preparing transparent particles 1 having a water-repellent or oil-repellent coating 3, dispersing them in a solution containing metal alkoxide, applying and drying the obtained dispersion on a surface of a substrate glass 5, then heat-treating it, and forming a water-repellent, oil-repellent, and soil-resistant coating 8 on the surface of the substrate glass 5, to which the transparent particles are fixed by bonding. This super water-repellent, oil-repellent, and soil-resistant glass plate 10 is used for the transport equipment, the construction, or the optical equipment.

Description

DESCRIPTION
WATER-REPELLENT, OIL-REPELLENT, SOIL-RESISTANT GLASS PLATE, METHOD OF MANUFACTURING THE SAME, AND TRANSPORT EQUIPMENT, CONSTRUCTION AND OPTICAL EQUIPMENT USING THE SAME
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a glass plate having high durability and a water-repellent, oil-repellent, and soil-resistant coating formed on a surface thereof.
In particular, the present invention relates to the glass plate for a window of transport equipment, such as an automobile, or construction, such as a building, and for a filter of optical equipment, where water-repellent, oil-repellent, and soil-resistant functions are required. Further, the present invention relates to the transport equipment, the construction, and the optical equipment using the same, as well as a method of manufacturing the same.
Description of Related Art Generally, it has been already known well that a film-forming solution comprising a chlorosilane-based adsorbent containing a fluorocarbon group and a non-water-based organic solvent can be used to effect chemisorption in a liquid phase so as to form a water-repellent, oil-repellent, and soil-resistant chemisorption film in the form of a monomolecular film (for example, see Japanese Patent Publication (Kokai) No. 04-132637). A manufacture principle of the chemisorption monomolecular film in such a solution is in forming the monomolecular film by means of dehydrochlorination reaction between active hydrogen, such as a hydroxyl group on a substrate surface, and a chlorosilyl group of the chlorosilane-based adsorbent.
SUMMARY OF THE INVENTION However, since a conventional chemisorption film utilizes only chemical bonding between an adsorbent and a planar surface of a substrate, a contact angle to water droplets would be no more than approximately 120 degrees, resulting in a problem that water-repellent, oil-repellent, and soil-resistant properties and water releasing property are insufficient for the water droplets or soil to be removed by itself. Moreover, there has been a problem that durability, such as wear resistance and weather resistance, is insufficient. The present invention is, in a glass plate for a window of transport equipment, such as an automobile, or construction, such as a building, and for a filter of optical equipment, where water-repellent, oil-repellent, and soil-resistant functions are required, intended to provide a water-repellent, oil-repellent, and soil-resistant glass plate, that can improve the water-repellent, oil-repellent, and soil-resistant properties, the water releasing property (also referred to as water lubricity), as well as the durability, such as the wear resistance and the whether resistance, a method of manufacturing the same, and the transport equipment, the construction, and the optical equipment using the same.
A water-repellent, oil-repellent, and soil-resistant glass plate according to a first invention provided as means for solving the foregoing problems is characterized in that a surface thereof is covered with water-repellent, oil-repellent, and soil-resistant transparent particles that have been fixed thereto by sintering.
The water-repellent, oil-repellent, and soil-resistant glass plate according to a second invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the first invention, characterized in that a surface of the transparent particle is partially coated with a water-repellent, oil-repellent, and soil-resistant coating.
The water-repellent, oil-repellent, and soil-resistant glass plate according to a third invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the second invention, characterized in that the transparent particle is fixed by sintering to a surface of a substrate glass via a transparent metal oxide film.
The water-repellent, oil-repellent, and soil-resistant glass plate according to a fourth invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the third invention, characterized in that the metal oxide film is a silica-based glass film.
The water-repellent, oil-repellent, and soil-resistant glass plate according to a fifth invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the fourth invention, characterized in that a surface of the silica-based glass film is coated with the water-repellent, oil-repellent, and soil-resistant coating.
The water-repellent, oil-repellent, and soil-resistant glass plate according to a sixth invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the fifth invention, characterized in that at least the water-repellent, oil-repellent, and soil-resistant coating is covalently bonded to the surfaces of the transparent particle and silica-based glass film.
The water-repellent, oil-repellent, and soil-resistant glass plate according to a seventh invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the first to sixth inventions, characterized in that the transparent particle is translucent silica, alumina, or zirconia.
The water-repellent, oil-repellent, and soil-resistant glass plate according to an eighth invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the first to seventh inventions, characterized in that the size of the transparent particle is less than a wavelength of visible light.
The water-repellent, oil-repellent, and soil-resistant glass plate according to a ninth invention is, in the water-repellent, oil-repellent, and soil-resistant glass plate according to the first to eighth inventions, characterized in that a contact angle to water is controlled to be not less than 130 degrees. Transport equipment according to a tenth invention is characterized in that the water-repellent, oil-repellent, and soil-resistant glass plate according to the first to ninth inventions is mounted thereto as a windowpane.
A construction according to an eleventh invention is characterized in that the water-repellent, oil-repellent, and soil-resistant glass plate according to the first to ninth inventions is mounted thereto as a windowpane.
Optical equipment according to a twelfth invention is characterized in that the water-repellent, oil-repellent, and soil-resistant glass plate according to the first to ninth inventions is mounted to a front face of a lens thereof as a filter.
A method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to a thirteenth invention is characterized by including: a first step of preparing the transparent particles, the surfaces thereof being covered with a water-repellent or oil-repellent coating; a second step of preparing a dispersion, wherein the transparent particles are dispersed in a solution containing metal alkoxide; a third step of applying and drying the dispersion on the surface of the substrate glass; a fourth step of heat-treating the substrate glass having the dispersion applied thereto in an atmosphere containing oxygen; and a fifth step of forming the water-repellent, oil-repellent, and soil-resistant coating on the surface of the substrate glass that has been heat-treated at the fourth step. Note herein that the "metal alkoxide" includes tetraalkoxysilane in this description.
The method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to a fourteenth invention is, in the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to the thirteenth invention, characterized in that the metal alkoxide produces silica-based glass by the heat treatment.
The method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to a fifteenth invention is, in the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to the thirteenth and fourteenth inventions, characterized in that a temperature of the heat treatment at the fourth step is not less than 250 degrees C, and not higher than a melting point of the substrate glass and the transparent particle. The method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to a sixteenth invention is, in the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to the thirteenth to fifteenth inventions, characterized in that a solvent having the metal alkoxide dissolved therein is water-based, and that the coating covering the surface of the transparent particle at the first step is water-repellent.
The method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to a seventeenth invention is, in the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to the thirteenth to fifteenth inventions, characterized in that the solvent having the metal alkoxide dissolved therein is organic-based, and that the coating covering the surface of the transparent particle at the first step is oil-repellent.
The method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to an eighteenth invention is, in the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to the thirteenth to seventeenth inventions, characterized in that the formation of the water-repellent, oil-repellent, and soil-resistant coating at the fifth step is carried out by contacting a film-forming solution containing any of: (1 ) a trialkoxysilane derivative containing a fluorocarbon group and a silanol condensation catalyst; (2) a trichlorosilane derivative containing the fluorocarbon group; and (3) an isocyanate derivative containing the fluorocarbon group, as well as an organic solvent, with the substrate glass having the transparent particles fixed by sintering to the surface thereof.
The method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to a nineteenth invention is, in the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to the eighteenth invention, characterized in that, after contacting the film-forming solution with the substrate glass, the excess film-forming solution is washed off.
The method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to a twentieth invention is, in the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to the eighteenth and nineteenth inventions, characterized in that the film-forming solution contains the silanol condensation catalyst, and that one or more compounds selected from the group consisting of a ketimine compound, organic acid, metal oxide, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are used as a co-catalyst with the silanol condensation catalyst.
Here, since the surface of the glass plate is covered with the water-repellent, oil-repellent, and soil-resistant transparent particles fixed thereto by sintering, it becomes possible to improve water-repellent, oil-repellent, and soil-resistant properties, water releasing property (water lubricity), wear resistance, whether resistance, and the like of the glass plate.
In addition, it is advantageous to use the transparent particle with the surface thereof being partially covered with the water-repellent, oil-repellent, and soil-resistant coating, because it allows for manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate in a simple manner using a raw material, such as silica and alumina, which is inexpensive and exhibits excellent wear resistance or the like. It is advantageous in order to improve the wear resistance that the transparent particle is fixed by sintering to the surface of the substrate glass via the transparent metal oxide film.
Additionally, it is advantageous in order to improve optical property, heat resistance, and the like that the metal oxide film, if it is the silica-based glass film, has the same refractive index or coefficient of thermal expansion as that of the substrate glass.
Moreover, it is advantageous in order to improve the water-repellent, oil-repellent, and soil-resistant properties that the surface of the silica-based glass film is coated with the water-repellent, oil-repellent, and soil-resistant coating. It is advantageous in order to improve the durability that at least the water-repellent, oil-repellent, and soil-resistant coating is covalently bonded to the surfaces of the transparent particle and silica-based glass film.
Further, it is advantageous in order to improve the wear resistance that the transparent particle is translucent silica, alumina, or zirconia. In addition, it is advantageous in order to maintain transparency of the water-repellent, oil-repellent, and soil-resistant glass plate that the size of the transparent particle is less than the wavelength of the visible light (360-700 nm).
Incidentally, the size of the transparent particle is preferably 10-300 nm, and more preferably 50-100 nm. It is advantageous that the contact angle to water is controlled to be not less than 130 degrees for the water-repellent, oil-repellent, and soil-resistant glass plate, because it allows for improving the water releasing property, resulting in improving outside visibility in the rainy weather, as well as soil resistance, when used as the windowpane of the transport equipment or construction. In addition, it is advantageous that the water-repellent, oil-repellent, and soil-resistant glass plate is mounted to the transport equipment, such as the automobile, as the windowpane, because it allows for improving the outside visibility in the rainy weather.
Moreover, it is advantageous that the water-repellent, oil-repellent, and soil-resistant glass plate is mounted to the construction as the windowpane, because it allows for improving the outside visibility in the rainy weather. Further, it is advantageous that the water-repellent, oil-repellent, and soil-resistant glass plate is mounted to the front face of the lens as the filter of the optical equipment, such as a surveillance camera, because it allows for maintaining an image to be clear in the rainy weather as well.
With the invention relating to the method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate, including: the first step of preparing the transparent particles, the surfaces thereof being covered with the water-repellent or oil-repellent coating; the second step of preparing the dispersion, wherein the transparent particles are dispersed in the solution containing the metal alkoxide; the third step of applying and drying the dispersion on the surface of the substrate glass; the fourth step of heat-treating the substrate glass having the dispersion applied thereto in the atmosphere containing oxygen; and the fifth step of forming the water-repellent, oil-repellent, and soil-resistant coating on the surface of the substrate glass that has been heat-treated at the fourth step, it becomes possible to manufacture the water-repellent, oil-repellent, and soil-resistant glass plate with the improved water-repellent, oil-repellent, and soil-resistant properties, water releasing property (water lubricity), wear resistance, weather resistance, and the like, in an inexpensive and simple manner.
Additionally, at this time, it is advantageous that the metal alkoxide produces the silica-based glass by the heat treatment, because it allows for improving the wear resistance and the weather resistance.
Moreover, it is advantageous that the temperature of the heat treatment at the fourth step is not less than 250 degrees C, and not higher than the melting point of the substrate glass and transparent particle, because it allows for preventing the substrate glass and the transparent particle from deformation due to melting upon fixing the particles by bonding.
Furthermore, it is advantageous that the coating covering the surface of the transparent particle is water-repellent in the case that the solvent having the metal alkoxide dissolved therein is water-based, because it allows the particle to be exposed from the solution containing the metal alkoxide upon application, resulting in forming irregularities having a high aspect ratio.
Alternatively, it is advantageous that the coating covering the surface of the transparent particle is oil-repellent in the case that the solvent having the metal alkoxide dissolved therein is organic-based, because it allows the particle to be exposed from the solution containing the metal alkoxide upon application, resulting in forming the irregularities having the high aspect ratio.
In addition, it is advantageous that the step of forming the water-repellent, oil-repellent, and soil-resistant coating is carried out by contacting the film-forming solution containing any of: (1 ) the trialkoxysilane derivative containing the fluorocarbon group and the silanol condensation catalyst; (2) the trichlorosilane derivative containing the fluorocarbon group; and (3) the isocyanate derivative containing the fluorocarbon group, as well as the organic solvent, with the substrate glass having the transparent particles fixed by sintering to the surface thereof, because it allows for improving water-repellent, oil-repellent, and soil-resistant performance with simple operation.
It is advantageous, at the fifth step of forming the water-repellent, oil-repellent, and soil-resistant coating, to include the step of washing off the excess film-forming solution after contacting the film-forming solution with the substrate glass, in order to improve the water-repellent, oil-repellent, and soil-resistant performance.
Further, it is advantageous, if the film-forming solution containing the silanol condensation catalyst is used at the fifth step of forming the water-repellent, oil-repellent, and soil-resistant coating, to use one or more compounds selected from the group consisting of the ketimine compound, organic acid, the metal oxide, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxysilane compound as the co-catalyst with the silanol condensation catalyst, because it allows for reducing manufacturing time.
As has been described, according to the present invention, in a glass plate for a window of an automobile or building, and a filter of optical equipment, where water-repellent, oil-repellent, and soil-resistant functions are required, there is an advantage that it is possible to provide a water-repellent, oil-repellent, and soil-resistant glass plate having excellent water releasing property (also referred to as water lubricity), soil resistance, as well as durability, such as wear resistance and weather resistance, along with transport equipment, construction, and optical equipment using the same.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a conceptual diagram enlarged to a molecular level for illustrating process of forming a fluorocarbon-based monomolecular film on a surface of a silica particle in a first example of the present invention, wherein FIG. 1 A is a sectional view of the silica particle before reaction and FIG. 1 B is a sectional view thereof after the monomolecular film containing a fluorocarbon group is formed; and
FIG. 2 is a conceptual diagram enlarged to a molecular level for illustrating process of forming a water-repellent, oil-repellent, and soil-resistant fluorocarbon-based monomolecular film in the first example of the present invention, wherein FIG 2A is a sectional view showing a state that the silica particle coated with the fluorocarbon-based monomolecular film and a silica-based glass film are applied to a surface of a glass substrate, FIG. 2B is a sectional view showing a state after the fluorocarbon-based monomolecular film on the surface of the silica particle is removed by decomposition by means of sintering in an atmosphere containing oxygen, and FIG. 2C is a sectional view showing a state that the fluorocarbon-based monomolecular film is formed on the exposed surfaces of the silica particle and silica-based glass film.
DETAILED DESCRIPTION The present invention provides a water-repellent, oil-repellent, and soil-resistant glass plate, characterized in that a surface thereof is covered with water-repellent, oil-repellent, and soil-resistant transparent particles that have been sintered, manufactured by a method including: a first step of preparing the transparent particles, the surfaces thereof being covered with a water-repellent or oil-repellent coating; a second step of preparing a dispersion, wherein the transparent particles are dispersed in a solution containing metal alkoxide; a third step of applying and drying the dispersion on a surface of a substrate glass; a fourth step of heat-treating the substrate glass having the dispersion applied thereto in an atmosphere containing oxygen; and a fifth step of forming a water-repellent, oil-repellent, and soil-resistant coating on the surface of the substrate glass that has been heat-treated at the fourth step. Further, the present invention provides transport equipment, construction, and optical equipment having such a water-repellent, oil-repellent, and soil-resistant glass plate mounted thereto.
Hence, the present invention has an effect, in the glass plate for a window of the transport equipment or construction, and a filter of the optical equipment, where water-repellent, oil-repellent, and soil-resistant functions are required, that it is possible to provide the water-repellent, oil-repellent, and soil-resistant glass plate or filter having excellent water releasing property (water lubricity), soil resistance, and durability, such as wear resistance and weather resistance, along with the transport equipment, the construction, or the optical equipment using the same.
Hereinafter, although detailed features and embodiments of the present invention will be described with reference to examples, the invention of the present application is not limited by these examples in any degree.
Incidentally, while the water-repellent, oil-repellent, and soil-resistant glass plate according to the present invention can be used as a windowpane of the transport equipment, such as an automobile, or the construction, such as a building, and as the filter of the optical equipment, the case will be described as a representative example where the glass plate is used as the windowpane of the
• automobile.
[Examples] First Example
(A) Preparation of chemisorption liquid
A chemisorption liquid is prepared by weighing 99 weight parts of CF3(CF2)7(CH2)2Si(OCH3)3, as an example of a trialkoxysilane derivative containing a fluorocarbon group (-CF3), and 1 weight part of dibutyltin diacetylacetonate, as an example of a silanol condensation catalyst, respectively, and by dissolving them in a hexamethyldisiloxiane solvent, as an example of an organic solvent, so that the trialkoxysilane derivative accounts for approximately 1 weight % (preferable concentration is approximately 0.5 to 3%).
(B) Manufacturing of silica particles coated with oil-repellent monomolecular film (an example of coating)
A silica particle 1 (FIG. 1A) (it may be a particle of alumina or zirconia, as long as it is transparent), as an example of a transparent particle, having a diameter of approximately 100 nm is sufficiently dried, mixed in the chemisorption liquid, and caused to react for approximately 1 hour while agitating in atmospheric air (relative humidity of 45%) (In order not to impair transparency, the diameter of the particle is preferably smaller than a wavelength of visible light (360 to 700 nm). In particular, the diameter of the particle is preferably 10 to 300 nm, and more preferably 50 to 100 nm). Since a surface of the silica particle 1 contains many hydroxyl groups 2, a -Si(OCH3)3 group of the trialkoxysilane derivative and the hydroxyl group 2 undergo dealcoholization condensation (in this case, CH3OH is removed) under the presence of the silanol condensation catalyst, and a monomolecular film 3 containing the fluorocarbon group, having a film thickness of approximately 1 nm, is formed over the entire surface of the silica particle 1 , as represented in the following Formula C1. [C1]
I
F 8 C (C F 2) 7 (CH2) a S i - O-
I O -
Then, by washing off the unreacted trialkoxysilane derivative using a chlorine-based solvent, such as chloroform, a silica particle 4 coated with the oil-repellent monomolecular film, which has been coated with the monomolecular film 3 containing the fluorocarbon group over the entire surface thereof, can be manufactured (FIG. 1 B). (C) Preparation of dispersion
A dispersion is prepared by dispersing approximately 1 wt% of the silica particles 4 coated with the oil-repellent monomolecular film 3 in a solution (it may utilize a commercially available metal alkoxide solution, diluted with alcohol, that can form a transparent coating using the sol-gel method), which has been prepared by weighing tetramethoxysilane (Si(OCH3)4), as an example of the metal alkoxide that forms silica-based glass by heat treatment, and dibutyltin diacetylacetonate, as an example of the silanol condensation catalyst, respectively, in the molar ratio of 99:1 , and by dissolving them in the hexamethyldisiloxane solvent, as an example of the organic solvent, with the concentration of approximately 1 wt% in total (preferable concentration is approximately 0.5 to 3%). (D) Manufacturing of irregular substrate 7 on which transparent particle is sintered
By applying the dispersion to a surface of a substrate glass 5 (FIG. 2A) using an arbitrary method, such as the dip-coating method, the spin-coating method, the spraying method, or the like, followed by vaporizing the solvent, a silanol group, resulting from hydrolysis by tetramethoxysilane reacting with moisture in the air, undergoes dealcoholization reaction with an alkoxysilyl group, eventually forming a silica-based glass film (an example of a metal oxide film) 6 having the film thickness of approximately 50 nm. Incidentally, since the silica particle 4 coated with the oil-repellent monomolecular film 3 "sheds" the solvent in this regard, and thus is exposed near the surface of the silica-based glass film 6 without being buried therein as shown in FIG. 2A, irregularities having a high aspect ratio can be formed on the surface of the silica-based glass film 6. Incidentally, in the case where the dispersion is produced using a water-based solvent, formation of a lipophilic and water-repellent coating, as represented by the following Formula C2, on the surface of the silica particle 1 using a less expensive alkyltrialkoxysilane derivative allows for forming the irregularities having the high aspect ratio on the surface of the silica-based glass film 6, in a similar manner to that of the above-described case. [C2] o- I
H 3 C (C H2) g S i — O -
O - Next, by baking (heat-treating) in the atmosphere containing oxygen at 600 degrees C for approximately 30 minutes, the silica particle 1 is fixed by sintering to the surface of the substrate glass 5 via the silica-based glass film 6, so that the irregular substrate 7 on which the transparent particle are sintered can be manufactured (the baking temperature is not less than 250 degrees C, and not higher than a melting point of the substrate glass 5 or the silica particle 1 , wherein the higher it is, the more robustly the particle can be fixed by sintering to the glass surface). At this time, the monomolecular film 3 containing the fluorocarbon group on the surface of the silica particle 4 was completely removed by decomposition by heat-treating it under the presence of oxygen (FIG. 2B). Incidentally, at this time, only the sintering is effected if the baking is carried out at the temperature of 250 to 350 degrees C, but the monomolecular film 3 can be completely removed by decomposition at the temperature of over 350 degrees C. (E) Manufacturing of water-repellent, oil-repellent, and soil-resistant glass plate Finally, by applying the chemisorption liquid prepared at (A), as a film-forming solution, to the surface of the irregular substrate 7 on which the transparent particle 1 has been sintered, effecting the reaction for approximately 2 hours, and then washing off the unreacted trialkoxysilane derivative with the chlorine-based solvent, such as chloroform, a super water-repellent, oil-repellent, and soil-resistant glass plate 10 having a contact angle to water droplets of approximately 150 degrees, with a water-repellent, oil-repellent, and soil-resistant transparent particle 9 being fixed thereto by sintering, can be obtained. The trialkoxysilane derivative forms the monomolecular film 8 (an example of the water-repellent, oil-repellent, and soil-resistant coating) containing the fluorocarbon group by bonding with the hydroxyl group on the surface of the silica particle 1 and of the silica-based glass film 6 via chemical bonding represented by Formula C1 (FIG. 2C).
Here, the silica particle 1 on the surface of the super water-repellent, oil-repellent, and soil-resistant glass plate 10 is fixed by sintering to the surface of the substrate glass 5 via the silica-based glass film 6, and the surface on which the silica particle 1 fixed by sintering is exposed and the surface on which the silica-based glass film 6 is exposed are fully coated (covalently bonded) with the monomolecular film 8 containing the fluorocarbon group. In addition, the film thickness of the monomolecular film 8 containing the fluorocarbon group is approximately 1 nm, which is much smaller than the size of the silica particle 1 on the surface of the glass substrate 5. For that reason, resulting from the water-repellent and oil-repellent properties being imparted to the surface of the irregular substrate 7 on which the transparent particle has been sintered while maintaining the irregularities thereon, super water-repellency with the contact angle to water droplets of approximately 150 degrees can be realized due to the so-called "lotus effect".
Incidentally, in the above-described first example, although the trialkoxysilane derivative, CF3 (CF2)7(CH2)2Si(OCH3)3, having the fluorocarbon group is used for forming the monomolecular film 8 containing the fluorocarbon group, the trialkoxysilane derivatives represented in the following (1) to (12), other than the above example, can be used.
(I ) CF3CH2θ(CH2)i5Si(OCH3)3 (2) CF3(CH2)3Si(CH3)2(CH2)i5Si(OCH3)3 (3) CF3(CF2)5(CH2)2Si(CH3)2(CH2)9Si(OCH3)3
(4) CF3(CF2)7(CH2)2Si(CH3)2(CH2)9Si(OCH3)3
(5) CF3COO(CH2)i5Si(OCH3)3
(6) CF3(CF2)5(CH2)2Si(OCH3)3
(7) CF3CH2O(CH2)I5Si(OC2Hs)3 (8) CF3(CH2)3Si(CH3)2(CH2)i5Si(OC2H5)3
(9) CF3(CF2)5(CH2)2Si(CH3)2(CH2)9Si(OC2H5)3 (10) CF3(CF2)7(CH2)2Si(CH3)2(CH2)9Si(OC2H5)3
(II ) CF3COO(CH2)I5Si(OC2Hs)3 (12) CF3(CF2)5(CH2)2Si(OC2H5)3 In addition, although the alkyltrialkoxysilane derivative, CH3(CH2)9Si(OCH3)3, is used as the lipophilic and water-repellent trialkoxysilane derivative, the alkyltrialkoxysilane derivatives represented in the following (21) to (32), other than the above example, can be used.
(21 ) CH3CH2O(CH2)i5Si(OCH3)3 (22) CH3(CH2)3Si(CH3)2(CH2)15Si(OCH3)3
(23) CH3(CH2)s(CH2)2Si(CH3)2(CH2)9Si(OCH3)3 (24) CH3(CH2)9Si(CH3)2(CH2)9Si(OCH3)3 (25) CH3COO(CH2)i5Si(OCH3)3
(26) CH3(CH2)7Si(OCH3)3
(27) CH3CH2O(CH2)I5Si(OC2Hs)3 (28) CH3(CH2)3Si(CH3)2(CH2)i5Si(OC2H5)3 (29) CH3(CH2)7Si(CH3)2(CH2)9Si(OC2H5)3
(30) CH3(CH2)9Si(CH3)2(CH2)9Si(OC2H5)3
(31 ) CH3COO(CH2)I5Si(OC2Hs)3
(32) CH3(CH2)7Si(OC2H5)3
In the first example, it is possible, as the silanol condensation catalyst, to use carboxylic acid metal salts, carboxylate ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanates, and titanate chelates. More specifically, it is possible to use stannous acetates, dibutyltin dilaulates, dibutyltin dioctates, dibutyltin diacetates, dioctyltin dilaurates, dioctyltin dioctates, dioctyltin diacetates, stannous dioctates, lead naphthenates, cobalt naphthenates, 2-ethyl hexenic acid irons, dioctyltin-bis-octylthioglycolate salts, dioctyltin maleate salts, dibutyltin maleate polymers, dimethyltin mercaptopropionate polymers, dibutyltin bis-acetyl acetates, dioctyltin bis-acetyllaurates, tetrabutyl titanates, tetranonyl titanates, and bis(acetylacetonyl) di-propyltitanates.
Note herein that, in the first example, the trichlorosilane derivatives having the fluorocarbon group represented in the following (41 ) to (45) and the triisocyanatesilane derivatives containing the fluorocarbon group represented in (46) to (52) can be used, wherein the silanol condensation catalyst is not required. (41 ) CF3CH2O(CH2)15SiC|3 (42) CF3(CH2)3Si(CH3)2(CH2)i5SiCI3 (43) CF3(CF2)5(CH2)2Si(CH3)2(CH2)9SiCI3
(44) CF3(CF2)7(CH2)2Si(CH3)2(CH2)9SiCl3
(45) CF3COO(CHs)15SiCI3
(46) CF3(CF2)s(CH2)2Si(NCO)3
(47) CF3CH2O(CH2)15Si(NCO)3 (48) CF3(CH2)3Si(CH3)2(CH2)i5Si(NCO)3
(49) CF3(CF2)5(CH2)2Si(CH3)2(CH2)9Si(NCO)3 (50) CF3(CF2)7(CH2)2Si(CH3)2(CH2)9Si(NCO)3 (51 ) CF3COO(CH2)I5Si(NCO)3
(52) CF3(CF2)5(CH2)2Si(NCO)3
Moreover, in any of the trialkoxysilane derivative, the trichlorosilane derivative, and the triisocyanatesilane derivative being used, the solvent of the film-forming solution can include an organochlorine-based solvent having no water content, a hydrocarbon-based solvent, a fluorocarbon-based solvent, a silicone-based solvent, or a mixture thereof. Note herein that if the monomolecular film 8 containing the fluorocarbon group is formed by vaporizing the solvent without washing off, it is preferred that a boiling point of the solvent is approximately 50 to 250 degrees C. The specifically available solvent can include, in the case of the chlorosilane derivative, non-water-based petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, alkyl-modified silicone, polyether silicone, dimethylformamide, or the like. Furthermore, if the monomolecular film 8 containing the fluorocarbon group is formed by only vaporizing the solvent using the alkoxysilane derivative, it is possible to use, in addition to the above-described solvent, an alcohol-based solvent, such as methanol, ethanol, propanol, and the like, or a mixture thereof.
In addition, the available fluorocarbon-based solvent includes a flon-based solvent, Florinate (from 3M, U.S.), Aflude (from Asahi Glass Co., Ltd.), or the like. Note herein that one of them may be singularly used, or two or more of them may be combined as long as they are mixed well. Furthermore, the organochlorine-based solvent, such as chloroform, may be added.
In the case where, instead of the above-described silanol condensation catalysts, a ketimine compound, organic acid, metal oxide, such as TiO2, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used as the silanol condensation catalyst, reaction time can be reduced to about half to two-third under the condition that the concentration thereof is similar to that of the above-described silanol condensation catalysts.
Furthermore, by using one or more selected from the group consisting of the ketimine compound, the organic acid, the metal oxide, such as TiO2, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxysilane compound, as a co-catalyst, with the above-described silanol condensation catalyst, the reaction can be further accelerated by several times, so that the time required for film-formation process can be reduced to a few tenths (while the silanol condensation catalyst and the co-catalyst can be used in a range of the molar ratio of 1 :9 to 9:1 , approximately 1 :1 is desired).
For example, when the reaction is effected under the same conditions except that dibutyltin oxide as the silanol condensation catalyst is replaced by H3 from Japan Epoxy Resin Co., Ltd. as the ketimine compound, almost similar results can be obtained except that the reaction time can be reduced to approximately 1 hour.
Furthermore, when the reaction is effected under the same conditions, except that the co-catalyst of H3 from Japan Epoxy Resin Co., Ltd. as the ketimine compound is replaced by a dibutyltin bisacetylacetonate mixture (mixing ratio of 1 :1) as the silanol condensation catalyst, the similar result can be obtained except that the reaction time can be reduced to approximately 20 minutes.
Hence, from the above-described results, it has been proved that the ketimine compound, the organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxysilane compound have the higher activity than that of the silanol condensation catalyst. Further, it has been proved that using one selected from the group consisting of the ketimine compound, the organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxysilane compound as the co-catalyst with the silanol condensation catalyst further increases the activity.
Note herein that the available ketimine compound includes, but not specifically limited to, for example, 2, 5, 8-triaza-1 , 8-nonadiene, 3, 11 -dimethyl-4, 7, 10-triaza-3, 10-tridecadiene, 2, 10-dimethyl-3, 6, 9-triaza-2, 9-undecadiene, 2, 4, 12, 14-tetramethyl-5, 8, 11-triaza-4, 11 -pentadecadiene, 2, 4, 15, 17-tetramethyl-5, 8, 11 , 14-tetraaza-4, 14-octadecadiene, 2, 4, 20, 22-tetramethyl-5, 12, 19-triaza-4, 19-trieicosadiene, or the like. In addition, the available organic acid can include, but not specifically limited to, for example, formic acid, acetic acid, monobasic acids, such as propionic acid, hydroxyl acids, such as butyric acid, dibasic acids, such as malonic acid, wherein any of them exhibits the similar result.
Second Example
The super water-repellent, oil-repellent, and soil-resistant glass plates, produced under the same conditions with those of the glass plate produced according to the first example, except that alumina is used as the transparent particle, having the contact angle to water droplets of approximately 150 degrees (in practice, the contact angle to water droplets of not less than 130 degrees can achieve the similar effect), were mounted as a front windowpane (also referred to as a windshield, an inclination angle of approximately 45 degrees), a side windowpane (the inclination angle of approximately 70 degrees), and a read windowpane (the inclination angle of approximately 30 degrees), for carrying out driving experiments in the rainy weather.
First, the adhesion condition of rain droplets to a parked automobile was checked, wherein adhesion of water droplets of approximately 5 mm or more in diameter was not substantially observed for any of the glasses.
Next, the driving experiments at 45 km/h and 60 km/h were carried out. When the adhesion condition of rain droplets while driving at 45 km/h was checked, adhesion of water droplets of approximately 2 mm or more in diameter was not substantially observed for both the side windowpane and rear windowpane. Additionally, as for the front windowpane, a large amount of water droplets was continuously adhered thereto during driving, but water droplets of approximately 2 mm or more in diameter immediately moved upward and then flew away, thus did not remain as much as enough to interfere with a view. While further driving at higher speed of 60 km/h, water droplets of approximately 2 mm or more in diameter instantly flew away, and substantially completely removed.
In addition, the rearward view condition reflected in a side mirror during the driving experiments was checked over the side windowpane, wherein distortion of the view or deterioration of visibility due to rain droplets was not substantially perceived. Moreover, in comparing the difference between influences on the outside visibility due to presence and absence of the water-repellent, oil-repellent, and soil-resistant coating in the clear weather, deterioration of visibility was not perceived at all as compared to that of the automobile without the coating, because the transparency of the coating was not less than 97% for the light having the wavelength of 400 to 700 nm. Furthermore, in comparing the wear resistance to a wiper with the front windowpane, wherein the glass surface thereof not having the almina particles fixed by sintering was directly coated with the water-repellent, oil-repellent, and soil-resistant coating according to the method similar to (E) of the first example, the front windowpane fabricated in this example exhibited much higher wear resistance because the alumina particles having high hardness have been fixed by sintering to the surface.
It has been proved from the above-described experiments that the automobile having the super water-repellent, oil-repellent, and soil-resistant glass plate of the present invention mounted thereto exhibits a particular effect on safe driving in the rainy weather.
Third Example The super water-repellent, oil-repellent, and soil-resistant glass plate having the contact angle to water droplets of approximately 150 degrees, produced under the same conditions with those of the glass plate produced in the first example, was mounted as the windowpane of a building, and adhesion of rain droplets in the rainy weather was checked, wherein rain droplets of not less than 1 mm in diameter did not adhere thereto at all. In addition, soil or dust, which has adhered during the clear weather is washed away by rain droplets, and a residue does not adhere to the glass surface after being dried, so that the glass is maintained to be clean.
Fourth Example The super water-repellent, oil-repellent, and soil-resistant glass plate having the contact angle to water droplets of approximately 150 degrees, produced under the same conditions with those of the glass plate produced in the first example, was mounted to a front face of a lens of the optical equipment, such as a surveillance camera, as the filter, and a taken image in the rainy weather was evaluated. Although the image was blurred due to adhesion of rain droplets to the surface of a filter glass when the above-mentioned filter was not mounted, rain droplets run down and did not adhere in the case where the super water-repellent, oil-repellent, and soil-resistant glass plate fabricated in this example was mounted, so that the clear image was continuously obtained without the need to wipe off.

Claims

1. A water-repellent, oil-repellent, and soil-resistant glass plate, wherein a surface thereof is covered with water-repellent, oil-repellent, and soil-resistant transparent particles that have been fixed thereto by sintering.
2. The water-repellent, oil-repellent, and soil-resistant glass plate according to claim 1 , wherein a surface of the transparent particle is partially coated with a water-repellent, oil-repellent, and soil-resistant coating.
3. The water-repellent, oil-repellent, and soil-resistant glass plate according to claim 2, wherein the transparent particle is fixed by sintering to a surface of a substrate glass via a transparent metal oxide film.
4. The water-repellent, oil-repellent, and soil-resistant glass plate according to claim 3, wherein the metal oxide film is a silica-based glass film.
5. The water-repellent, oil-repellent, and soil-resistant glass plate according to claim 4, wherein a surface of the silica-based glass film is coated with the water-repellent, oil-repellent, and soil-resistant coating.
6. The water-repellent, oil-repellent, and soil-resistant glass plate according to claim 5, wherein at least the water-repellent, oil-repellent, and soil-resistant coating is covalently bonded to the surfaces of the transparent particle and silica-based glass film.
7. The water-repellent, oil-repellent, and soil-resistant glass plate according to any of claims 1 to 6, wherein the transparent particle is translucent silica, alumina, or zirconia.
8. The water-repellent, oil-repellent, and soil-resistant glass plate according to any of claims 1 to 7, wherein the size of the transparent particles is less than a wavelength of visible light.
9. The water-repellent, oil-repellent, and soil-resistant glass plate according to any of claims 1 to 8, wherein a contact angle to water is controlled to be not less than 130 degrees.
10. Transport equipment wherein the water-repellent, oil-repellent, and soil-resistant glass plate according to any of claims 1 to 9 is mounted thereto as a windowpane.
11. Construction wherein the water-repellent, oil-repellent, and soil-resistant glass plate according to any of claims 1 to 9 is mounted thereto as a windowpane.
12. Optical equipment wherein the water-repellent, oil-repellent, and soil-resistant glass plate according to any of claims 1 to 9 is mounted to a front face of a lens thereof as a filter.
13. A method of manufacturing a water-repellent, oil-repellent, and soil-resistant glass plate, comprising: a first step of preparing transparent particles, surfaces thereof being covered with a water-repellent or oil-repellent coating; a second step of preparing a dispersion, wherein the transparent particles are dispersed in a solution containing metal alkoxide; a third step of applying and drying the dispersion on a surface of a substrate glass; a fourth step of heat-treating the substrate glass having the dispersion applied thereto in an atmosphere containing oxygen; and a fifth step of forming a water-repellent, oil-repellent, and soil-resistant coating on the surface of the substrate glass that has been heat-treated at the fourth step.
14. The method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to claim 13, wherein the metal alkoxide produces silica-based glass by the heat treatment.
15. The method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to any of claims 13 and 14, wherein a temperature of the heat treatment at the fourth step is not less than 250 degrees C, and not higher than a melting point of the substrate glass and the transparent particle.
16. The method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to any of claims 13 to 15, wherein a solvent having the metal alkoxide dissolved therein is water-based, and wherein the coating covering the surface of the transparent particle at the first step is water-repellent.
17. The method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to any of claims 13 to 15, wherein the solvent having the metal alkoxide dissolved therein is organic-based, and wherein the coating covering the surface of the transparent particle at the first step is oil-repellent.
18. The method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to any of claims 13 to 17, wherein the formation of the water-repellent, oil-repellent, and soil-resistant coating at the fifth step is carried out by contacting a film-forming solution containing any of: (1 ) a trialkoxysilane derivative containing a fluorocarbon group and a silanol condensation catalyst; (2) a trichlorosilane derivative containing the fluorocarbon group; and (3) an isocyanate derivative containing the fluorocarbon group, as well as an organic solvent, with the substrate glass having the transparent particles fixed by sintering to the surface thereof.
19. The method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to claim 18, wherein, after contacting the film-forming solution with the substrate glass, the excess film-forming solution is washed off.
20. The method of manufacturing the water-repellent, oil-repellent, and soil-resistant glass plate according to any of claims 18 and 19, wherein the film-forming solution contains the silanol condensation catalyst, and wherein one or more compounds selected from the group consisting of a ketimine compound, organic acid, a metal oxide, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are used as a co-catalyst with the silanol condensation catalyst.
PCT/JP2007/074624 2007-12-17 2007-12-17 Water-repellent, oil-repellent, soil-resistant glass plate, method of manufacturing the same, and transport equipment, construction and optical equipment using the same WO2009078109A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014058625A1 (en) * 2012-10-12 2014-04-17 Empire Technology Development Llc Superhydrophobic and lipophobic surfaces

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10203882A (en) * 1997-01-21 1998-08-04 Saga Pref Gov Water-repellent ceramic
JPH1192175A (en) * 1997-09-11 1999-04-06 Matsushita Electric Ind Co Ltd Water-repellent glass coating film and its production

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10203882A (en) * 1997-01-21 1998-08-04 Saga Pref Gov Water-repellent ceramic
JPH1192175A (en) * 1997-09-11 1999-04-06 Matsushita Electric Ind Co Ltd Water-repellent glass coating film and its production

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014058625A1 (en) * 2012-10-12 2014-04-17 Empire Technology Development Llc Superhydrophobic and lipophobic surfaces

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