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WO2009084119A1 - Solar energy utilizing apparatus and method of manufacturing the same - Google Patents

Solar energy utilizing apparatus and method of manufacturing the same Download PDF

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Publication number
WO2009084119A1
WO2009084119A1 PCT/JP2007/075421 JP2007075421W WO2009084119A1 WO 2009084119 A1 WO2009084119 A1 WO 2009084119A1 JP 2007075421 W JP2007075421 W JP 2007075421W WO 2009084119 A1 WO2009084119 A1 WO 2009084119A1
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Prior art keywords
repellent
solar energy
utilizing apparatus
water
energy utilizing
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French (fr)
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Kazufumi Ogawa
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/30—Coatings
    • H10F77/306—Coatings for devices having potential barriers
    • H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
    • H10F77/315—Coatings for devices having potential barriers for photovoltaic cells the coatings being antireflective or having enhancing optical properties
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a solar energy utilizing apparatus, such as a solar battery, a solar water heater, and a greenhouse, having durability, high water releasing property (also referred to as water lubricity), and an effect of reducing surface reflection of incident light, and wherein a water-repellent, oil-repellent, and soil-resistant coating is formed on a surface of a transparent substrate on a light incident side, as well as a method of manufacturing the same.
  • a chemisorpotion liquid 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 Patent Document 1: Japanese Unexamined 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.
  • a conventional chemisorption monomolecular film utilizes chemical bonding between an adsorbent and a substrate surface, and thus has a certain degree of wear resistance or water-repellent, oil-repellent, and soil-resistant functions, there has been a problem that weather resistance, water releasing property, and soil resistance are insufficient when used as a soil-resistant film for a solar battery, a solar water heater, or a greenhouse. In addition, there has also been a problem that a sufficient effect of reducing surface reflection of incident light cannot be expected due to a thinness of the film.
  • the present invention is, in the solar battery, the solar water heater, or the greenhouse, where high durability, high water releasing property, and water-repellent, oil-repellent, and soil-resistant performance are required, intended to provide a solar energy utilizing apparatus that improves power generation efficiency of the solar battery or heat collection efficiency of the solar water heater, the greenhouse, or the like, and that prevents deterioration over time due to soil, by the improvement in the wear resistance, the high water releasing property, and the soil resistance, along with the effect of reducing surface reflection of the incident light, as well as a method of manufacturing the same.
  • a solar energy utilizing apparatus provided as means for solving the foregoing problems is characterized in that a surface of a transparent substrate on a light incident side is covered with water-repellent, oil-repellent, and soil-resistant transparent particles that have been fixed by sintering to the surface of the transparent substrate.
  • the solar energy utilizing apparatus according to a second invention is, in the solar energy utilizing apparatus 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 solar energy utilizing apparatus according to a third invention is, in the solar energy utilizing apparatus according to the second invention, characterized in that the transparent particle is fixed by sintering to the surface of the transparent substrate via a transparent metal oxide film.
  • the solar energy utilizing apparatus according to a fourth invention is, in the solar energy utilizing apparatus according to the third invention, characterized in that the metal oxide film is a silica-based glass film.
  • the solar energy utilizing apparatus according to a fifth invention is, in the solar energy utilizing apparatus 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 solar energy utilizing apparatus is, in the solar energy utilizing apparatus 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 solar energy utilizing apparatus according to a seventh invention is, in the solar energy utilizing apparatus according to the first to sixth inventions, characterized in that the transparent particle is translucent silica, alumina, or zirconia.
  • the solar energy utilizing apparatus according to an eighth invention is, in the solar energy utilizing apparatus 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 solar energy utilizing apparatus according to a ninth invention is, in the solar energy utilizing apparatus according to the eighth inventions, characterized in that the size of the transparent particle is not more than 100 nm.
  • the solar energy utilizing apparatus according to a tenth invention is, in the solar energy utilizing apparatus according to the first to ninth inventions, characterized in that a contact angle to water is controlled to be not less than 130 degrees.
  • a method of manufacturing the solar energy utilizing apparatus 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 transparent substrate; a fourth step of heat-treating the transparent substrate 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 transparent substrate that has been heat-treated at the fourth step.
  • the method of manufacturing the solar energy utilizing apparatus according to a twelfth invention is, in the method of manufacturing the solar energy utilizing apparatus according to the eleventh invention, characterized in that the metal alkoxide produces silica-based glass by the heat treatment.
  • the method of manufacturing the solar energy utilizing apparatus according to a thirteenth invention is, in the method of manufacturing the solar energy utilizing apparatus according to the eleventh and twelfth inventions, characterized in that a temperature of the heat treatment at the fourth step is not less than 250 degrees C, and not more than a melting point of the transparent substrate and the transparent particle.
  • the method of manufacturing the solar energy utilizing apparatus according to a fourteenth invention is, in the method of manufacturing the solar energy utilizing apparatus according to the eleventh to thirteenth 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 solar energy utilizing apparatus according to a fifteenth invention is, in the method of manufacturing the solar energy utilizing apparatus according to the eleventh to fourteenth 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 transparent substrate having the transparent particles fixed by sintering to the surface thereof.
  • the method of manufacturing the solar energy utilizing apparatus according to a sixteenth invention is, in the method of manufacturing the solar energy utilizing apparatus according to the fifteenth invention, characterized in that, after contacting the film-forming solution with the transparent substrate, the excess film-forming solution is washed off.
  • the method of manufacturing the solar energy utilizing apparatus according to a seventeenth invention is, in the method of manufacturing the solar energy utilizing apparatus according to the fifteenth and sixteenth 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 catalyst.
  • the surface of the transparent substrate on the light incident side 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 on the surface of the transparent substrate on the light incident side in the solar energy utilizing apparatus.
  • the transparent particle covered with the water-repellent, oil-repellent, and soil-resistant coating because it allows for manufacturing the water-repellent, oil-repellent, and soil-resistant solar energy utilizing apparatus in a simple manner using a raw material, such as silica and alumina, which is inexpensive and exhibits excellent wear resistance or the like.
  • the transparent particle is fixed by sintering to the surface of the transparent substrate via the transparent metal oxide film, in order to improve the wear resistance.
  • 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 transparent substrate, in order to improve optical property, heat resistance, and the like.
  • the surface of the silica-based glass film is coated with the water-repellent, oil-repellent, and soil-resistant coating, in order to improve the water-repellent, oil-repellent, and soil-resistant properties.
  • water-repellent, oil-repellent, and soil-resistant coating is covalently bonded to the surfaces of the transparent particle and silica-based glass film, in order to improve the durability.
  • the transparent particle is translucent silica, alumina, or zirconia, in order to improve the wear resistance without impairing translucency.
  • the size of the transparent particle is less than the wavelength of the visible light (360-700 nm), in order to ensure the translucency of water-repellent glass.
  • the size of the transparent particle is preferably 5-300 nm, and more preferably 10-100 nm in order not to impair the translucency.
  • the contact angle to water is controlled to be not less than 130 degrees, because it allows for improving the water releasing property and preventing rain droplets from remaining on the surface, resulting in constantly ensuring the translucency.
  • the invention relating to the method of manufacturing the solar energy utilizing apparatus, 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 transparent substrate; the fourth step of heat-treating the transparent substrate 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 transparent substrate that has been heat-treated at the fourth step, it becomes possible to manufacture the solar energy utilizing apparatus 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 if the metal alkoxide produces the silica-based glass by
  • the temperature of the heat treatment at the fourth step is not less than 250 degrees C, and not more than the melting point of the transparent substrate and transparent particle, because it allows for preventing the transparent substrate 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 metal alkoxide upon application, resulting in forming irregularities having a high aspect ratio.
  • the fifth 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 transparent substrate 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 and for reducing surface energy without impairing the irregularities on the surface.
  • the fifth step of forming the water-repellent, oil-repellent, and soil-resistant coating 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 transparent substrate, because it allows for further reducing the surface energy without impairing the irregularities on the surface.
  • the film-forming solution containing the trialkoxysilane derivative having the fluorocarbon group, the silanol condensation catalyst, and the organic solvent 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, metal oxide, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxysilane compound as the co-catalyst with the silanol catalyst, because it allows for reducing manufacturing time.
  • a solar energy utilizing apparatus such as a solar battery, a solar water heater, and a greenhouse
  • high durability, high water releasing property, as well as water-repellent, oil repellent, and soil-resistant performance are required
  • FIG. 1 is a conceptual diagram enlarged to a molecular level for illustrating process of forming a monomolecular film containing an oil-repellent fluorocarbon group on a surface of a silica particle in a first example of the present invention, wherein 1A is a sectional view of the silica particle before reaction and 1B is a sectional view thereof after the monomolecular film containing the fluorocarbon group is formed;
  • Fig. 2 is a conceptual sectional diagram enlarged to a molecular level for illustrating process of manufacturing a transparent glass substrate having nanometer-level irregularities on a surface thereof, using the silica particle having the monomolecular film containing the fluorocarbon group formed on the surface thereof, in the first example of the present invention, wherein 2A is a sectional view showing a state that a coating film containing the silica particle coated with the monomolecular film containing the fluorocarbon group, as well as silica-based glass component, is formed and 2B is a sectional view showing a state that the monomolecular film is removed after baking; and Fig.
  • 3 is a conceptual diagram illustrating process of forming a solar battery layer on a back surface of the glass substrate having the irregularities on the surface thereof in the first example of the present invention, wherein 3A is a sectional view showing a state that the solar battery layer is formed on the back surface and 3B is a sectional view showing a state that the water-repellent, oil-repellent, and soil-resistant monomolecular film is further formed on the surface.
  • the present invention provides a solar energy utilizing apparatus, wherein a surface of a transparent substrate on a light incident side is covered with water-repellent and oil-repellent transparent particles that have been fixed by sintering to the surface of the transparent substrate, 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 the surface of the transparent substrate; a fourth step of heat-treating the transparent substrate 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 transparent substrate that has been heat-treated at the fourth step.
  • the present invention has an effect, in the solar energy utilizing apparatus, such as a solar battery, a solar water heater, and a greenhouse, where high durability, high water releasing property, and water-repellent, oil-repellent, and soil-resistant performance are required, that it is possible to improve power generation efficiency or heat collection efficiency while preventing deterioration due to soil by improvement in wear resistance, the high water releasing property, or soil resistance, along with an effect of reducing surface reflection of incident light.
  • the present invention will be described in detail by reference to examples hereinafter, the present invention is not limited by these examples in any degree.
  • the solar battery, the solar water heater, and the greenhouse apply the similar methods in principle of imparting functions to improve the power generation efficiency or the heat collection efficiency and to prevent the deterioration due to soil, by the improvement in the wear resistance, the high water releasing property, and the soil resistance, along with the effect of reducing surface reflection of the incident light, therefore, the case will be described first as a representative example where the transparent substrate on a light incident side of the solar battery is glass. [Examples]
  • a chemisorption liquid is prepared by weighing 99 weight parts of CF 3 (CF 2 ) 7 (CH2) 2 Si(OCH 3 )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 (Fig. 1A) (it may be a particle of glass, 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 (380 to 700 nm). In particular, the diameter of the particle is preferably 5 to 300 nm, and more preferably 10 to 100 nm).
  • a surface of the silica particle 1 contains many hydroxyl groups 2
  • a -Si(OCH 3 ) 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 (I).
  • O -Si(OCH 3 ) 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 (I).
  • 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 ) ⁇ , 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 hexamethyldisiloxiane 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 coating film 6 cotaining silica-based glass component having the film thickness of approximately 50 nm.
  • the silica particle 1 is fixed by sintering to the surface of the glass substrate 5 via a silica-based glass film (an example of a transparent metal oxide film) 6a, so that a glass substrate 7 having nanometer-level irregularities on the surface thereof can be manufactured (the baking temperature is not less than 250 degrees C, and not more than a melting point of the glass substrate 5 and the silica particle 1 , wherein the higher it is, the more robustly the particle can be fixed by sintering to the glass surface).
  • a silica-based glass film an example of a transparent metal oxide film
  • the monomolecular film 3 containing the fluorocarbon group on the surface of the silica particle 4 is completely removed by decomposition by heat-treating it under the presence of oxygen (Fig. 2B).
  • the sintering is effected if the baking is carried out at the temperature of 250 to 350 degrees C
  • the monomolecular film 3 can be completely removed by decomposition at the temperature of over 350 degrees C.
  • an ITO film is deposited on a back surface of the glass substrate 7 having the nanometer-level irregularities on the surface, using the spatter deposition method, to form an ITO transparent electrode 8.
  • a p-type amorphous silicon layer 9 and an n-type amorphous silicon layer 10 are then formed in that order in a publicly-known manner using the plasma CVD method, and then an aluminum back electrode 11, also serving as a reflection film, is deposited thereon, to fabricate the solar battery layer (Fig. 3A).
  • a film-formation temperature of amorphous silicon and a deposition temperature of the aluminum electrode are generally not more than 450 degrees C (lower than the melting point of the silica particle 1 , the glass substrate 5, and the silica-based glass film 6a), the glass substrate 7 having the particles fixed thereto by sintering is not damaged during fabrication process of the solar battery layer.
  • a solar battery 13 coated with the water-repellent, oil-repellent, and soil-resistant monomolecular film having the irregularities on the surface thereof can be manufactured, wherein a part of the silica particle 1 and the surface of the silica-based glass film 6a are coated with a water-repellent, oil-repellent, and soil-resistant monomolecular film 12 as an example of the water-repellent, oil-repellent, and soil-resistant coating (FIG. 3B).
  • an arrow 14 represents a direction of light incidence.
  • the silica particle 1 on the surface of the glass substrate 5 is fixed by sintering to the surface of the glass plate via the silica-based glass film 6a, and the surface on which the silica particle 1 fixed by sintering is exposed and the surface on which the silica-based glass film 6a is exposed are fully coated (covalently bonded) with the monomolecular film 12 containing the fluorocarbon group.
  • the film thickness of the monomolecular film 12 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 surface of the transparent substrate fabricated according to the method of the present invention has the substantially smaller surface energy (on average, not more than 3 mN/m), so that the surface having extremely high water releasing property and soil resistance can be realized.
  • the silica particle has hardness higher than that of glass, does not substantially contain alkali component, and is fixed by sintering to the surface of the transparent substrate, it has the higher wear resistance and water resistance and can considerably improve weather resistance, as compared to the monomolecular film directly fabricated on the surface of the transparent glass substrate using CF 3 (CF 2 )7(CH 2 ) 2 SiCl3.
  • the thickness of the resulting monomolecular film 12 including the particle 1 is approximately 100 nm in total, transparency is not impaired. Further, since the silica particle 4 coated with the oil-repellent monomolecular film 3 can arbitrarily control surface refractive index in a range between 1.3 and 1.5 by controlling adhesion density of nano particles, surface reflection on the light incident side can be minimized.
  • the trialkoxysilane derivative, CF 3 (CF 2 ) 7 (CH 2 ) 2 Si(OCH 3 ) 3 , having the fluorocarbon group is used for forming the water-repellent, oil-repellent, and soil-resistant monomolecular film 12 in the above-described first example, but the trialkoxysilane derivatives represented in the following (1) to (12), other than the above example, 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.
  • 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.
  • 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. Further, if the monomolecular film containing the fluorocarbon group is formed by only veporizing 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.
  • organochlorine-based solvent such as chloroform
  • 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 1 hour.
  • reaction time can be reduced to approximately 20 minutes.
  • 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.
  • formic acid acetic acid
  • monobasic acids such as propionic acid
  • hydroxyl acids such as butyric acid
  • dibasic acids such as malonic acid
  • alumina, zirconia, or the like is apparently applicable instead of silica as the harder transparent particle than the glass substrate.
  • the present invention is not limited to these applications, but apparently applicable to equipment utilizing the solar energy, such as the greenhouse.

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Abstract

The present invention relates to a solar energy utilizing apparatus, such as a solar battery 13 having irregularities on a surface thereof and covered with a water-repellent monomolecular film, is manufactured by preparing transparent particles having a water-repellent or oil-repellent coating, dispersing them in a solution containing metal alkoxide, applying and drying the obtained dispersion on a surface of a glass substrate 5, then heat-treating it, and forming a water-repellent, oil-repellent, and soil-resistant monomolecular film 12 on the surface of the glass substrate 5, to which the transparent particles are fixed by bonding.

Description

DESCRIPTION
SOLAR ENERGY UTILIZING APPARATUS AND METHOD OF MANUFACTURING
THE SAME
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a solar energy utilizing apparatus, such as a solar battery, a solar water heater, and a greenhouse, having durability, high water releasing property (also referred to as water lubricity), and an effect of reducing surface reflection of incident light, and wherein a water-repellent, oil-repellent, and soil-resistant coating is formed on a surface of a transparent substrate on a light incident side, as well as a method of manufacturing the same.
Description of Related Art
Generally, it is known well that power generation efficiency of a solar battery installed outdoors and heat collection efficiency of a solar water heater, a greenhouse, or the like are reduced over time due to dust in the atmospheric air or soil caused by the rain. Meanwhile, it has been already known well that a chemisorpotion liquid 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 Patent Document 1: Japanese Unexamined 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.
Since a conventional chemisorption monomolecular film utilizes chemical bonding between an adsorbent and a substrate surface, and thus has a certain degree of wear resistance or water-repellent, oil-repellent, and soil-resistant functions, there has been a problem that weather resistance, water releasing property, and soil resistance are insufficient when used as a soil-resistant film for a solar battery, a solar water heater, or a greenhouse. In addition, there has also been a problem that a sufficient effect of reducing surface reflection of incident light cannot be expected due to a thinness of the film.
SUMMARY OF THE INVENTION
The present invention is, in the solar battery, the solar water heater, or the greenhouse, where high durability, high water releasing property, and water-repellent, oil-repellent, and soil-resistant performance are required, intended to provide a solar energy utilizing apparatus that improves power generation efficiency of the solar battery or heat collection efficiency of the solar water heater, the greenhouse, or the like, and that prevents deterioration over time due to soil, by the improvement in the wear resistance, the high water releasing property, and the soil resistance, along with the effect of reducing surface reflection of the incident light, as well as a method of manufacturing the same.
A solar energy utilizing apparatus according to a first invention provided as means for solving the foregoing problems is characterized in that a surface of a transparent substrate on a light incident side is covered with water-repellent, oil-repellent, and soil-resistant transparent particles that have been fixed by sintering to the surface of the transparent substrate.
The solar energy utilizing apparatus according to a second invention is, in the solar energy utilizing apparatus 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 solar energy utilizing apparatus according to a third invention is, in the solar energy utilizing apparatus according to the second invention, characterized in that the transparent particle is fixed by sintering to the surface of the transparent substrate via a transparent metal oxide film.
The solar energy utilizing apparatus according to a fourth invention is, in the solar energy utilizing apparatus according to the third invention, characterized in that the metal oxide film is a silica-based glass film.
The solar energy utilizing apparatus according to a fifth invention is, in the solar energy utilizing apparatus 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 solar energy utilizing apparatus according to a sixth invention is, in the solar energy utilizing apparatus 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 solar energy utilizing apparatus according to a seventh invention is, in the solar energy utilizing apparatus according to the first to sixth inventions, characterized in that the transparent particle is translucent silica, alumina, or zirconia. The solar energy utilizing apparatus according to an eighth invention is, in the solar energy utilizing apparatus 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 solar energy utilizing apparatus according to a ninth invention is, in the solar energy utilizing apparatus according to the eighth inventions, characterized in that the size of the transparent particle is not more than 100 nm.
The solar energy utilizing apparatus according to a tenth invention is, in the solar energy utilizing apparatus according to the first to ninth inventions, characterized in that a contact angle to water is controlled to be not less than 130 degrees.
A method of manufacturing the solar energy utilizing apparatus according to an eleventh 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 transparent substrate; a fourth step of heat-treating the transparent substrate 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 transparent substrate 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 solar energy utilizing apparatus according to a twelfth invention is, in the method of manufacturing the solar energy utilizing apparatus according to the eleventh invention, characterized in that the metal alkoxide produces silica-based glass by the heat treatment. The method of manufacturing the solar energy utilizing apparatus according to a thirteenth invention is, in the method of manufacturing the solar energy utilizing apparatus according to the eleventh and twelfth inventions, characterized in that a temperature of the heat treatment at the fourth step is not less than 250 degrees C, and not more than a melting point of the transparent substrate and the transparent particle.
The method of manufacturing the solar energy utilizing apparatus according to a fourteenth invention is, in the method of manufacturing the solar energy utilizing apparatus according to the eleventh to thirteenth 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 solar energy utilizing apparatus according to a fifteenth invention is, in the method of manufacturing the solar energy utilizing apparatus according to the eleventh to fourteenth 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 transparent substrate having the transparent particles fixed by sintering to the surface thereof.
The method of manufacturing the solar energy utilizing apparatus according to a sixteenth invention is, in the method of manufacturing the solar energy utilizing apparatus according to the fifteenth invention, characterized in that, after contacting the film-forming solution with the transparent substrate, the excess film-forming solution is washed off.
The method of manufacturing the solar energy utilizing apparatus according to a seventeenth invention is, in the method of manufacturing the solar energy utilizing apparatus according to the fifteenth and sixteenth 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 catalyst.
Here, since the surface of the transparent substrate on the light incident side 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 on the surface of the transparent substrate on the light incident side in the solar energy utilizing apparatus.
In addition, it is advantageous to use the transparent particle covered with the water-repellent, oil-repellent, and soil-resistant coating, because it allows for manufacturing the water-repellent, oil-repellent, and soil-resistant solar energy utilizing apparatus 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 if the transparent particle is fixed by sintering to the surface of the transparent substrate via the transparent metal oxide film, in order to improve the wear resistance.
Additionally, it is advantageous 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 transparent substrate, in order to improve optical property, heat resistance, and the like.
Moreover, it is advantageous if the surface of the silica-based glass film is coated with the water-repellent, oil-repellent, and soil-resistant coating, in order to improve the water-repellent, oil-repellent, and soil-resistant properties.
It is advantageous if the water-repellent, oil-repellent, and soil-resistant coating is covalently bonded to the surfaces of the transparent particle and silica-based glass film, in order to improve the durability.
Further, it is advantageous if the transparent particle is translucent silica, alumina, or zirconia, in order to improve the wear resistance without impairing translucency.
Additionally, it is advantageous if the size of the transparent particle is less than the wavelength of the visible light (360-700 nm), in order to ensure the translucency of water-repellent glass. Incidentally, the size of the transparent particle is preferably 5-300 nm, and more preferably 10-100 nm in order not to impair the translucency.
It is advantageous if the contact angle to water is controlled to be not less than 130 degrees, because it allows for improving the water releasing property and preventing rain droplets from remaining on the surface, resulting in constantly ensuring the translucency.
With the invention relating to the method of manufacturing the solar energy utilizing apparatus, 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 transparent substrate; the fourth step of heat-treating the transparent substrate 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 transparent substrate that has been heat-treated at the fourth step, it becomes possible to manufacture the solar energy utilizing apparatus 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 if 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 if the temperature of the heat treatment at the fourth step is not less than 250 degrees C, and not more than the melting point of the transparent substrate and transparent particle, because it allows for preventing the transparent substrate and the transparent particle from deformation due to melting upon fixing the particles by bonding. Meanwhile, it is advantageous if 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 metal alkoxide upon application, resulting in forming irregularities having a high aspect ratio.
Additionally, it is advantageous if the fifth 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 transparent substrate 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 and for reducing surface energy without impairing the irregularities on the surface.
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 transparent substrate, because it allows for further reducing the surface energy without impairing the irregularities on the surface.
Further, it is advantageous, if the film-forming solution containing the trialkoxysilane derivative having the fluorocarbon group, the silanol condensation catalyst, and the organic solvent 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, metal oxide, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxysilane compound as the co-catalyst with the silanol catalyst, because it allows for reducing manufacturing time.
As has been described, according to the present invention, in a solar energy utilizing apparatus, such as a solar battery, a solar water heater, and a greenhouse, where high durability, high water releasing property, as well as water-repellent, oil repellent, and soil-resistant performance, are required, there is an advantage that it is possible to achieve improvement in power generation efficiency of the solar battery or improvement in heat collection efficiency of the solar water heater of the greenhouse, along with prevention of deterioration over time due to soil, by reducing surface reflection of incident light and improving wear resistance, the high water releasing property, or soil resistance, and to provide the solar battery which can maintain the power generation efficiency over the long periods or the solar water heater which can maintain the heat collection efficiency over the long periods.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual diagram enlarged to a molecular level for illustrating process of forming a monomolecular film containing an oil-repellent fluorocarbon group on a surface of a silica particle in a first example of the present invention, wherein 1A is a sectional view of the silica particle before reaction and 1B is a sectional view thereof after the monomolecular film containing the fluorocarbon group is formed;
Fig. 2 is a conceptual sectional diagram enlarged to a molecular level for illustrating process of manufacturing a transparent glass substrate having nanometer-level irregularities on a surface thereof, using the silica particle having the monomolecular film containing the fluorocarbon group formed on the surface thereof, in the first example of the present invention, wherein 2A is a sectional view showing a state that a coating film containing the silica particle coated with the monomolecular film containing the fluorocarbon group, as well as silica-based glass component, is formed and 2B is a sectional view showing a state that the monomolecular film is removed after baking; and Fig. 3 is a conceptual diagram illustrating process of forming a solar battery layer on a back surface of the glass substrate having the irregularities on the surface thereof in the first example of the present invention, wherein 3A is a sectional view showing a state that the solar battery layer is formed on the back surface and 3B is a sectional view showing a state that the water-repellent, oil-repellent, and soil-resistant monomolecular film is further formed on the surface.
DETAILED DESCRIPTION The present invention provides a solar energy utilizing apparatus, wherein a surface of a transparent substrate on a light incident side is covered with water-repellent and oil-repellent transparent particles that have been fixed by sintering to the surface of the transparent substrate, 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 the surface of the transparent substrate; a fourth step of heat-treating the transparent substrate 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 transparent substrate that has been heat-treated at the fourth step.
Hence, the present invention has an effect, in the solar energy utilizing apparatus, such as a solar battery, a solar water heater, and a greenhouse, where high durability, high water releasing property, and water-repellent, oil-repellent, and soil-resistant performance are required, that it is possible to improve power generation efficiency or heat collection efficiency while preventing deterioration due to soil by improvement in wear resistance, the high water releasing property, or soil resistance, along with an effect of reducing surface reflection of incident light. Although the present invention will be described in detail by reference to examples hereinafter, the present invention is not limited by these examples in any degree.
Incidentally, as the solar energy utilizing apparatus according to the present invention, the solar battery, the solar water heater, and the greenhouse apply the similar methods in principle of imparting functions to improve the power generation efficiency or the heat collection efficiency and to prevent the deterioration due to soil, by the improvement in the wear resistance, the high water releasing property, and the soil resistance, along with the effect of reducing surface reflection of the incident light, therefore, the case will be described first as a representative example where the transparent substrate on a light incident side of the solar battery is glass. [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 glass, 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 (380 to 700 nm). In particular, the diameter of the particle is preferably 5 to 300 nm, and more preferably 10 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 (I). O -
F3C (CF2)7 (CH2)2 Si - O-
° - (D Thereafter, by washing off the excess unreacted adsorbent using a chlorine-based solvent, such as chloroform, a silica particle 4 having a oil-repellent surface and the entire surface thereof being coated with a chemisorption monomolecular film containing the fluorocarbon group, which has been chemically bonded to the surface, can be manufactured (Fig. 1B). (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)^, 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 hexamethyldisiloxiane 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 on which transparent particle is sintered
By applying the dispersion to a surface of a glass substrate 5 (Fig. 2A), as an example of the transparent substrate, 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 coating film 6 cotaining silica-based glass component 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 coating film 6 containing the silica-based glass component without being buried therein as shown in Fig. 2A, irregularities having a high aspect ratio can be formed on the surface of the coating film 6 containing the silica-based glass component.
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 (II), 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 coating film 6 containing the silica-based glass component, in a similar manner to that of the above-described case. O -
H3C (CH2)9 Si . O-
0 - (ID
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 glass substrate 5 via a silica-based glass film (an example of a transparent metal oxide film) 6a, so that a glass substrate 7 having nanometer-level irregularities on the surface thereof can be manufactured (the baking temperature is not less than 250 degrees C, and not more than a melting point of the glass substrate 5 and 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 is completely removed by decomposition by heat-treating it under the presence of oxygen (Fig. 2B). Incidentally, although only the sintering is effected if the baking is carried out at the temperature of 250 to 350 degrees C, the monomolecular film 3 can be completely removed by decomposition at the temperature of over 350 degrees C. (E) Fabrication of a solar battery layer
Next, an ITO film is deposited on a back surface of the glass substrate 7 having the nanometer-level irregularities on the surface, using the spatter deposition method, to form an ITO transparent electrode 8. A p-type amorphous silicon layer 9 and an n-type amorphous silicon layer 10 are then formed in that order in a publicly-known manner using the plasma CVD method, and then an aluminum back electrode 11, also serving as a reflection film, is deposited thereon, to fabricate the solar battery layer (Fig. 3A). Here, since a film-formation temperature of amorphous silicon and a deposition temperature of the aluminum electrode are generally not more than 450 degrees C (lower than the melting point of the silica particle 1 , the glass substrate 5, and the silica-based glass film 6a), the glass substrate 7 having the particles fixed thereto by sintering is not damaged during fabrication process of the solar battery layer.
(F) Manufacturing of water-repellent, oil-repellent, and soil-resistant glass plate Finally, by applying a film-forming solution, prepared by dissolving the trichlorosilane derivative having the water-repellent, oil-repellent, and soil-resistant fluorocarbon group (for example, CF3(CF2)7(CH2)2SiCl3) in a non-water-based organic solvent (for example, dehydrated nonane) by the concentration of approximately 1 wt% in a dry atmosphere (preferably, the relative humidity is not more than 30%) to the surface of the glass substrate 7 having the nanometer-level irregularities on the surface thereof on a light incident 14 side surface, and causing reaction, dehydrochlorination reaction is effected between a chlorosylil group (SiCI) of the film-forming solution and the hydroxyl group on the surface of the silica particle 1 , because the silica particle 1 on the surface of the glass substrate 7 having the nanometer-level irregularities on the surface thereof is covered with many hydroxyl groups (-OH), resulting in covalent bonding as represented by Formula (I) above being formed over the entire surface of the silica particle 1. Thereafter, by washing with a flon-based solvent to remove the unreacted trichlorosilane derivative, a solar battery 13 coated with the water-repellent, oil-repellent, and soil-resistant monomolecular film having the irregularities on the surface thereof can be manufactured, wherein a part of the silica particle 1 and the surface of the silica-based glass film 6a are coated with a water-repellent, oil-repellent, and soil-resistant monomolecular film 12 as an example of the water-repellent, oil-repellent, and soil-resistant coating (FIG. 3B). Here, an arrow 14 represents a direction of light incidence.
Here, the silica particle 1 on the surface of the glass substrate 5 is fixed by sintering to the surface of the glass plate via the silica-based glass film 6a, and the surface on which the silica particle 1 fixed by sintering is exposed and the surface on which the silica-based glass film 6a is exposed are fully coated (covalently bonded) with the monomolecular film 12 containing the fluorocarbon group. In addition, the film thickness of the monomolecular film 12 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 a contact angle to water droplets of approximately 160 degrees can be realized due to the so-called "lotus effect".
Incidentally, when the monomolecular film is formed on a planar substrate surface using the trichlorosilane derivative, CF3(CF2)7(CH2)2SiCI3, having the fluorocarbon group, critical surface energy would be 6-7 mN/m and the maximum contact angle to water droplets would be approximately 115 degrees. Namely, the surface of the transparent substrate fabricated according to the method of the present invention has the substantially smaller surface energy (on average, not more than 3 mN/m), so that the surface having extremely high water releasing property and soil resistance can be realized. Further, since the silica particle has hardness higher than that of glass, does not substantially contain alkali component, and is fixed by sintering to the surface of the transparent substrate, it has the higher wear resistance and water resistance and can considerably improve weather resistance, as compared to the monomolecular film directly fabricated on the surface of the transparent glass substrate using CF3(CF2)7(CH2)2SiCl3.
In addition, since the thickness of the resulting monomolecular film 12 including the particle 1 is approximately 100 nm in total, transparency is not impaired. Further, since the silica particle 4 coated with the oil-repellent monomolecular film 3 can arbitrarily control surface refractive index in a range between 1.3 and 1.5 by controlling adhesion density of nano particles, surface reflection on the light incident side can be minimized.
Incidentally, the trialkoxysilane derivative, CF3(CF2)7(CH2)2Si(OCH3)3, having the fluorocarbon group is used for forming the water-repellent, oil-repellent, and soil-resistant monomolecular film 12 in the above-described first example, but the trialkoxysilane derivatives represented in the following (1) to (12), other than the above example, can be used.
(1) CF3CH2O(CH2)15Si(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(OCHs)3
(6) CF3(CF2)5(CH2)2Si(OCH3)3 (7) CF3CH2O(CH2)15Si(OC2H5)3
(8) CF3(CH2)3Si(CH3)2(CH2)15Si(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 (H) 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)15Si(OCH3)3
(22) CH3(CH2)3Si(CH3)2(CH2)i5Si(OCH3)3
(23) CH3(CH2)5(CH2)2Si(CH3)2(CH2)9Si(OCH3)3
(24) CH3(CH2)9Si(CH3)2(CH2)9Si(OCH3)3 (25) CH3COO(CH2)I5Si(OCHs)3
(26) CH3(CH2)7Si(OCH3)3
(27) CH3CH2O(CH2)I5Si(OC2Hs)3 (28) CH3(CH2)3Si(CH3)2(CH2)15Si(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. Incidentally, 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. (4I) CF3CH2O(CH2)I5SiCI3
(42) CF3(CH2)SSi(CHs)2(CH2)I5SiCI3
(43) CF3(CF2)5(CH2)2Si(CH3)2(CH2)9SiCl3
(44) CF3(CF2)7(CH2)2Si(CH3)2(CH2)9SiCI3
(45) CF3COO(CH2)15SiCI3 (46) CF3(CF2)5(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
Meanwhile, 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. Incidentally, when the monomolecular film 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. Further, if the monomolecular film containing the fluorocarbon group is formed by only veporizing 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.
Meanwhile, the available fluorocarbon-based solvent includes a flon-based solvent, Florinate (from 3M, U.S.), Aflude (from Asahi Glass Co., Ltd.), or the like.
Incidentally, one of them may be singularly used, or two or more of them may be combined as long as they are mixed well. Further, 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.
Further, 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 catalyst is replaced by H3 from Japan Epoxy Resin Co., Ltd. as the ketimine compound, the similar result can be obtained except that the reaction time can be reduced to approximately 1 hour.
Further, 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 bis(acetylacetonate) mixture (mixing ratio of 1 :1) as the silanol 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 using one 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, which have the higher activity than that of the silanol condensation catalyst, 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. Moreover, although the above-described example illustrates the silica particle as an example, the present invention is applicable to any transparent particle as long as the surface thereof contains active hydrogen, such as hydroxy-group hydrogen, amino-group hydrogen, or imino-group hydrogen.
Specifically, alumina, zirconia, or the like is apparently applicable instead of silica as the harder transparent particle than the glass substrate. (Second Example)
In practical outdoor experiments carried out using the glass plate produced under the same conditions with those of the transparent substrate produced according to the first example, having the contact angle to water droplets of approximately 160 degrees (in practice, the contact angle to water droplets of not less than 130 degrees can achieve the similar effect), and mounted to the solar water heater, dust in the atmospheric air or soil caused by the rain did not substantially adhere thereto, and the heat collection efficiency was improved by approximately 5% on average as compared to the case where general glass was mounted. In addition, deterioration over time of the heat collection efficiency was reduced to one of tenths as compared to the case where the general glass was mounted.
The above-described experimental results indicate that the solar battery or the solar water heater, as an example of the solar energy utilizing apparatus of the present invention, exhibits the extremely high durability and efficiency.
Incidentally, although the above-described examples disclose applications of the solar battery or the solar water heater, the present invention is not limited to these applications, but apparently applicable to equipment utilizing the solar energy, such as the greenhouse.

Claims

1. A solar energy utilizing apparatus, wherein a surface of a transparent substrate on a light incident side is covered with water-repellent, oil-repellent, and soil-resistant transparent particles that have been fixed by sintering to the surface of the transparent substrate.
2. The solar energy utilizing apparatus 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 solar energy utilizing apparatus according to claim 2, wherein the transparent particle is fixed by sintering to the surface of the transparent substrate via a transparent metal oxide film.
4. The solar energy utilizing apparatus according to claim 3, wherein the metal oxide film is a silica-based glass film.
5. The solar energy utilizing apparatus 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 solar energy utilizing apparatus 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 solar energy utilizing apparatus according to any of claims 1 , wherein the transparent particle is translucent silica, alumina, or zirconia.
8. The solar energy utilizing apparatus according to any of claims 1, wherein the size of the transparent particle is less than a wavelength of visible light.
9. The solar energy utilizing apparatus according to claim 8, wherein the size of the transparent particle is not more than 100 nm.
10. The solar energy utilizing apparatus according to any of claims 1 , wherein a contact angle to water is controlled to be not less than 130 degrees.
11. A method of manufacturing a solar energy utilizing apparatus, 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 transparent substrate; a fourth step of heat-treating the transparent substrate 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 transparent substrate that has been heat-treated at the fourth step.
12. The method of manufacturing the solar energy utilizing apparatus according to claim 11 , wherein the metal alkoxide produces silica-based glass by the heat treatment.
13. The method of manufacturing the solar energy utilizing apparatus according to any of claims 11 , wherein a temperature of the heat treatment at the fourth step is not less than 250 degrees C, and not more than a melting point of the transparent substrate and the transparent particle.
14. The method of manufacturing the solar energy utilizing apparatus according to any of claims 11 , 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.
15. The method of manufacturing the solar energy utilizing apparatus according to any of claims 11 , 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 transparent substrate having the transparent particles fixed by sintering to the surface thereof.
16. The method of manufacturing the solar energy utilizing apparatus according to claim 15, wherein, after contacting the film-forming solution with the transparent substrate, the excess film-forming solution is washed off.
17. The method of manufacturing the solar energy utilizing apparatus according to any of claims 15, 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, metal oxide, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound are used as a co-catalyst with the silanol catalyst.
PCT/JP2007/075421 2007-12-27 2007-12-27 Solar energy utilizing apparatus and method of manufacturing the same Ceased WO2009084119A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07300346A (en) * 1994-05-09 1995-11-14 Nippon Sheet Glass Co Ltd Antifouling low-reflectance glass and its production
JP2001287971A (en) * 2000-03-31 2001-10-16 Matsushita Electric Ind Co Ltd Antifouling coating and method for producing the same, antifouling glass for automobile using the same, method for producing the same, and automobile using the same
JP2005169761A (en) * 2003-12-10 2005-06-30 Nippon Sheet Glass Co Ltd Base material with oxide film and its manufacturing method
JP2007126332A (en) * 2005-11-04 2007-05-24 Kagawa Univ Water-repellent glass plate, method for producing the same, and vehicle or glass window using the same
JP2007137767A (en) * 1991-01-23 2007-06-07 Matsushita Electric Ind Co Ltd Water / oil repellent glass substrate
JP2008007365A (en) * 2006-06-28 2008-01-17 Kagawa Univ Solar energy utilization apparatus and manufacturing method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007137767A (en) * 1991-01-23 2007-06-07 Matsushita Electric Ind Co Ltd Water / oil repellent glass substrate
JPH07300346A (en) * 1994-05-09 1995-11-14 Nippon Sheet Glass Co Ltd Antifouling low-reflectance glass and its production
JP2001287971A (en) * 2000-03-31 2001-10-16 Matsushita Electric Ind Co Ltd Antifouling coating and method for producing the same, antifouling glass for automobile using the same, method for producing the same, and automobile using the same
JP2005169761A (en) * 2003-12-10 2005-06-30 Nippon Sheet Glass Co Ltd Base material with oxide film and its manufacturing method
JP2007126332A (en) * 2005-11-04 2007-05-24 Kagawa Univ Water-repellent glass plate, method for producing the same, and vehicle or glass window using the same
JP2008007365A (en) * 2006-06-28 2008-01-17 Kagawa Univ Solar energy utilization apparatus and manufacturing method thereof

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