WO2012023347A1 - Miroir à film, procédé pour sa production, et miroir pour la réflexion de la lumière solaire utilisant un miroir à film - Google Patents

Miroir à film, procédé pour sa production, et miroir pour la réflexion de la lumière solaire utilisant un miroir à film Download PDF

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Publication number
WO2012023347A1
WO2012023347A1 PCT/JP2011/064879 JP2011064879W WO2012023347A1 WO 2012023347 A1 WO2012023347 A1 WO 2012023347A1 JP 2011064879 W JP2011064879 W JP 2011064879W WO 2012023347 A1 WO2012023347 A1 WO 2012023347A1
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WIPO (PCT)
Prior art keywords
film
silver
layer
mirror
glass
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PCT/JP2011/064879
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English (en)
Japanese (ja)
Inventor
仁 安達
Original Assignee
コニカミノルタオプト株式会社
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Publication of WO2012023347A1 publication Critical patent/WO2012023347A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0808—Mirrors having a single reflecting layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C03C17/10—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
    • C03C17/3663—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties specially adapted for use as mirrors
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S23/00—Arrangements for concentrating solar-rays for solar heat collectors
    • F24S23/70—Arrangements for concentrating solar-rays for solar heat collectors with reflectors
    • F24S23/82—Arrangements for concentrating solar-rays for solar heat collectors with reflectors characterised by the material or the construction of the reflector
    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/251—Al, Cu, Mg or noble metals
    • C03C2217/254—Noble metals
    • C03C2217/256—Ag
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S23/00—Arrangements for concentrating solar-rays for solar heat collectors
    • F24S23/70—Arrangements for concentrating solar-rays for solar heat collectors with reflectors
    • F24S2023/86—Arrangements for concentrating solar-rays for solar heat collectors with reflectors in the form of reflective coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/0547—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising light concentrating means of the reflecting type, e.g. parabolic mirrors, concentrators using total internal reflection
    • 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
    • Y02E10/40—Solar thermal energy, e.g. solar towers
    • 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
    • Y02E10/52—PV systems with concentrators

Definitions

  • the present invention relates to a film mirror, a manufacturing method thereof, and a solar reflective mirror using the film mirror.
  • Plate-shaped glass mirrors are highly durable against UV rays, temperature, and humidity, but they are damaged by external pressure during transportation and after installation, and are heavy in mass. There was a problem that the construction cost was expensive.
  • the resin-made reflective sheet has been put into practical use as a reflective sheet for a backlight unit of a liquid crystal display (see, for example, Patent Document 1). Can solve problems such as damage and weight.
  • Such a resin mirror has high suitability for continuous production with respect to a plate-like glass mirror, and can increase productivity.
  • a silver complex ink that is soluble in an organic solvent an inexpensive film mirror can be manufactured in Roll to Roll (see, for example, Patent Document 3).
  • the present invention has been made in view of the above-mentioned problems and situations, and the problem to be solved is that the regular reflection rate of the silver reflection layer is high, and the light reflection and weather resistance are excellent. It is an object to provide a film mirror and a method for manufacturing the film mirror that are almost free, lightweight and flexible, can reduce the manufacturing cost, and can be enlarged and mass-produced. Moreover, it is providing the sunlight reflective mirror using a film mirror.
  • the present inventors have a high specular reflectance, weather resistance, and productivity by using a thin glass film that can be wound into a roll, and a film mirror.
  • the present inventors have found that a film mirror satisfying the characteristics of light weight and flexibility as described above can be provided, and have completed the present invention.
  • a film mirror having a silver reflective layer on a support wherein the support is a glass film having a thickness in the range of 1.0 to 200 ⁇ m, and the silver reflective layer is vaporized by a ligand.
  • the silver complex ink After applying the silver complex ink, in order to obtain a highly reflective and stable silver reflecting layer, it is necessary to heat and bak at least at 80 ° C. or more, and the resin film is deteriorated by heat.
  • the use of the glass film can prevent the silver complex ink from being deteriorated during heating and baking. Therefore, the problem of remaining ligand that could not be volatilized in the silver reflecting layer due to the lowering of the firing temperature can be solved.
  • the present invention provides a coating film containing a silver complex compound, so that the coating film itself acts as a cushion due to its elasticity, and prevents the glass film from cracking or cracking. Even if a crack or a crack occurs, the expansion of the crack or the crack can be prevented by the cushioning property of the coating film.
  • the present invention not only solves the problem of applying a silver complex ink to a silver reflective layer in a film mirror having a resin film, but also provides a silver reflective layer by vapor deposition in a film mirror having a thin glass film. It is an invention that can solve the problem at the time.
  • the silver complex compound is a silver complex compound obtained by reacting an ammonium carbamate compound or an ammonium carbonate compound with a silver compound.
  • the glass film has a gas barrier layer positioned on the light incident surface side with respect to the silver reflective layer and has a gas barrier layer on the opposite side of the light incident surface with respect to the silver reflective layer.
  • the film mirror according to any one of the items.
  • the glass film is located on the light incident surface side with respect to the silver reflective layer, and has a layer containing a corrosion inhibitor in an adjacent layer opposite to the light incident surface with respect to the silver reflective layer.
  • the film mirror as described in any one of the first to fourth items.
  • a method for producing a film mirror having a silver reflective layer on a support wherein a glass film having a thickness in the range of 1.0 to 200 ⁇ m is used as a support, and a ligand is vaporized on the support.
  • a method for producing a film mirror comprising: forming a coating film containing a detachable silver complex compound, and then heating and baking the coating film to form the silver reflective layer.
  • a mirror for solar light reflection wherein the film mirror according to any one of items 1 to 5 is provided on a self-supporting base material.
  • the solar reflective mirror according to item 7, wherein the self-supporting base material has one of the following configurations A and B.
  • the regular reflection rate of the silver reflection layer is high, light resistance and weather resistance are excellent, there is almost no decline in regular reflection rate over time, and it is lightweight and flexible, thus suppressing the production cost. It is possible to provide a film mirror that can be increased in area and mass-produced, and a manufacturing method thereof. Moreover, the sunlight reflection mirror using the same can be provided.
  • the film mirror of the present invention is a film mirror having a silver reflective layer on a support, the support being a glass film having a thickness in the range of 1.0 to 200 ⁇ m, and the silver reflective layer Is formed by heating and baking a coating film containing a silver complex compound from which a ligand can be vaporized and eliminated.
  • This feature is a technical feature common to the inventions according to claims 1 to 8.
  • the silver complex compound is a silver complex compound obtained by reacting an ammonium carbamate compound or an ammonium carbonate compound with a silver compound from the viewpoint of manifesting the effects of the present invention.
  • the said glass film is a glass film obtained from the glass roll shape
  • the glass film is located on the light incident surface side with respect to the silver reflective layer, and has a gas barrier layer on the opposite side of the light incident surface with respect to the silver reflective layer. Further, the glass film is located on the light incident surface side with respect to the silver reflecting layer, and has a layer containing a corrosion inhibitor in an adjacent layer opposite to the light incident surface with respect to the silver reflecting layer. preferable.
  • a glass film having a thickness in the range of 1.0 to 200 ⁇ m is used as a support, and a silver complex compound capable of vaporizing and desorbing a ligand is formed on the support.
  • a silver complex compound capable of vaporizing and desorbing a ligand is formed on the support.
  • the film mirror of this invention can be used suitably for the mirror for sunlight reflection, it is preferable to set it as the mirror for sunlight reflection by which the film mirror of this invention is comprised by the self-supporting base material.
  • the self-supporting base material has one of the following configurations A and B.
  • A It has a pair of metal flat plates and an intermediate layer provided between the metal flat plates, and the intermediate layer is a layer having a hollow structure or a layer made of a resin material.
  • B A resin material layer having a hollow structure.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the film mirror of the present invention is a film mirror having a silver reflective layer on a support, and the support is a glass film having a thickness in the range of 1.0 to 200 ⁇ m.
  • the glass film is preferably a glass film obtained from a glass roll formed by a downdraw method. That is, a glass obtained from a glass roll formed by a downdraw method, such as disclosed in JP 2010-132347 A, having a glass film with exposed front and back surfaces, wound on a protective sheet in a roll shape. A film is preferred.
  • the glass film formed by the down draw method with the front and back surfaces exposed is wound as it is together with the protective sheet into a roll to form a glass roll. Therefore, it is not necessary to perform a film forming process for forming a protective film such as a polymer layer on both the front and back surfaces of the glass film in the process before packing, and the polymer layer and the like from the surface of the glass film in the process after unpacking. It is not necessary to perform a removal process for removing the protective film.
  • the pre-packing process can be shortened by an amount that does not require the process of forming the protective film, so the percentage of foreign matter adhering to the front and back surfaces of the glass film can be reduced as much as possible, and the protective film is derived after unpacking The situation that the foreign material to remain cannot also arise.
  • the cleanliness of the front and back surfaces of the glass film derived from the downdraw method can be favorably maintained.
  • the advantage is that cleanliness can be ensured in the state of the unpolished surface without performing subsequent surface polishing of the glass film as in the case of molding by the float method. There is also.
  • the exposed front and back surfaces of the glass film are protected by a protective sheet in a glass roll state.
  • the front and back of a glass film are the glass surfaces in which protective films, such as a polymer layer, are not formed, the situation where a glass film and a protective sheet adhere firmly at the stage which wound up. Therefore, the damage of the glass film in the state of the glass roll can be surely reduced, and the separability between the glass film and the protective sheet can be maintained well, so the damage of the glass film during unpacking is reduced as much as possible. can do.
  • the glass film is kept wound for a long time, it is not warped and can be easily fed to the next process. Furthermore, since it can be made into a long glass film by winding it, it can be cut with a free length after that, and it becomes possible to deal with substrates of various sizes, and waste of the glass film is achieved. Can be prevented.
  • the glass film needs to have a thickness in the range of 1.0 to 200 ⁇ m.
  • the thickness of the glass film is preferably 30 ⁇ m or more and 150 ⁇ m or less, more preferably in the range of 50 to 120 ⁇ m. If the thickness is less than 1 ⁇ m, it cannot withstand the tension at the time of winding in a roll shape and breaks. If it is thicker than 200 ⁇ m, it is difficult to wind as a roll.
  • the arithmetic average roughness Ra of both end surfaces in the width direction of the glass film is 0.1 ⁇ m or less.
  • “arithmetic mean roughness Ra” is a value measured in accordance with JIS B0601: 2001.
  • both end surfaces in the width direction of the glass film are configured by cut surfaces cut by laser cutting.
  • laser cutting here also includes laser cleaving in addition to laser fusing.
  • the film mirror of the present invention is a film mirror having a silver reflective layer on a support, and the silver reflective layer heat-fires a coating film containing a silver complex compound from which a ligand can be vaporized and desorbed. It is formed by these.
  • a silver complex compound from which a ligand can be vaporized / desorbed has a ligand for stably dissolving silver in a solution, but is removed by removing the solvent and heating and firing.
  • the silver complex compound according to the present invention is contained in a silver coating solution composition, and by coating this, a coating film containing the complex according to the present invention is formed on a support. That is, it is preferable to form a silver reflective layer by forming a coating film on a glass film using a silver complex compound and then baking the coating film at a temperature in the range of 80 to 250 ° C. More preferably, it is in the range of 100 to 220, particularly preferably in the range of 120 to 200 ° C. There is no restriction
  • X represents oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetylacetonate
  • a substituent selected from carboxylate and derivatives thereof n is an integer of 1 to 4, and R 1 to R 6 are independently of each other hydrogen, C1 to C30 aliphatic or aliphatic
  • Specific examples of the general formula (1) include, for example, silver oxide, silver thiocyanate, silver sulfide, silver chloride, silver cyanide, silver cyanate, silver carbonate, silver nitrate, silver nitrite, silver sulfate, silver phosphate, perchlorine.
  • Examples include, but are not limited to, acid silver, silver tetrafluoroborate, silver acetylacetonate, silver acetate, silver lactate, silver oxalate and derivatives thereof.
  • R 1 to R 6 are specifically, for example, hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, ethylhexyl, heptyl, octyl, isooctyl , Nonyl, decyl, dodecyl, hexadecyl, octadecyl, docodecyl, cyclopropyl, cyclopentyl, cyclohexyl, aryl, hydroxy, methoxy, hydroxyethyl, methoxyethyl, 2-hydroxypropyl, methoxypropyl, cyanoethyl, ethoxy, butoxy, hexyloxy, methoxy Ethoxyethyl, methoxyethoxyethoxyethyl, hexamethyleneimine, morpholine
  • Examples of compounds of the general formulas (2) to (4) include, for example, ammonium carbamate, ammonium carbonate, ammonium bicarbonate, ethylammonium ethylcarbamate, isopropylammonium isopropylcarbamate, n- Butyl ammonium n-butyl carbamate, isobutyl ammonium isobutyl carbamate, t-butyl ammonium t-butyl carbamate, 2-ethylhexyl ammonium 2-ethylhexyl carbamate, octadecyl ammonium octadecyl carbamate, 2-methoxyethyl ammonium 2-methoxyethyl carbamate 2-cyanoethylammonium 2-cyanoethylcarbamate, dibutylammonium dibutylcarbamate, dioctadecylammonium dioctadecy
  • ammonium carbamate or ammonium carbonate compound are not particularly limited.
  • US Pat. No. 4,542,214 describes that ammonium carbamate compounds can be prepared from carbon dioxide and primary amines, secondary amines, tertiary amines, or at least one of these mixtures. When 0.5 mol of water is further added per 1 mol of the amine, an ammonium carbonate compound is obtained. When 1 mol or more of water is added, an ammonium bicarbonate compound can be obtained.
  • alcohols such as water, methanol, ethanol, isopropanol, butanol, ethylene glycol, glycerin, etc.
  • Glycols ethyl acetate, butyl acetate, acetates such as carbitol acetate, ethers such as diethyl ether, tetrahydrofuran, dioxane, ketones such as methyl ethyl ketone, acetone, hydrocarbons such as hexane, heptane, Examples include aromatics such as benzene and toluene, and halogen-substituted solvents such as chloroform, methylene chloride, and carbon tetrachloride, or mixed solvents thereof. Is carbon dioxide bubbled in the gas phase?
  • the solid phase dry ice it can be reacted in supercritical (supercritical) state.
  • any known method other than the above method may be used as long as the structure of the final substance is the same. That is, it is not necessary to specifically limit the solvent, reaction temperature, concentration or catalyst for production, and the production yield is not affected.
  • An organic silver complex compound can be produced by reacting the ammonium carbamate or ammonium carbonate compound thus produced with a silver compound.
  • a silver compound for example, at least one silver compound represented by the general formula (1), at least one ammonium carbamate or ammonium carbonate derivative represented by the general formulas (2) to (4), and a mixture thereof.
  • alcohols such as water, methanol, ethanol, isopropanol, butanol, ethylene glycol, glycerin Glycols such as ethyl acetate, butyl acetate, acetates such as carbitol acetate, ethers such as diethyl ether, tetrahydrofuran and dioxane, ketones such as methyl ethyl ketone and acetone, hydrocarbons such as hexane and heptane Of benzene, toluene Aromatic UNA, and chloroform and methylene chloride, and halogen-substituted solvents or a mixed solvent such as carbon tetrachloride can be used.
  • glycerin Glycols such as ethyl acetate, butyl acetate, acetates such as carbitol acetate
  • ethers such as diethyl ether, tetrahydrofur
  • a silver complex compound can also be produced by reaction.
  • the reaction can be performed directly without using a solvent in a normal pressure or pressurized state of a nitrogen atmosphere, or can be performed using a solvent.
  • any known method may be used as long as the structure of the final material is the same. That is, it is not necessary to specifically limit the solvent for the production, the reaction temperature, the concentration, the presence or absence of the catalyst, and the production yield is not affected.
  • the silver complex compound used in the present invention has a production method described in JP-T-2008-530001, and is recognized by the structure of the following general formula (5).
  • the silver coating liquid composition used for forming the highly reflective and highly glossy reflecting surface of the present invention contains the above-mentioned silver complex compound, and optionally includes a solvent, a stabilizer, and a leveling agent (Leveling agent). ), A thin film auxiliary, a reducing agent, and an additive for a thermal decomposition reaction accelerator can be contained in the silver coating composition of the present invention.
  • An additive such as an auxiliary agent, a reducing agent, and a thermal decomposition reaction accelerator can be contained in the silver coating composition of the present invention.
  • examples of the stabilizer include amine compounds such as primary amines, secondary amines, and tertiary amines, ammonium carbamates, ammonium carbonates, ammonium bicarbonate compounds, phosphines, and phosphites. And a phosphorus compound such as phosphate, a sulfur compound such as thiol and sulfide, and at least one mixture thereof.
  • amine compounds include, for example, methyl Amine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, isoamylamine, n-hexylamine, 2-ethylhexylamine, n-heptylamine, n-o Tylamine, isooctylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, docodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, arylamine, hydroxyamine, ammonium hydroxide, methoxyamine, 2-ethanol Amine, methoxyethylamine, 2-hydroxypropylamine, 2-hydroxy-2-methylpropylamine, methoxypropylamine, cyanoethylamine, ethoxyamine, n-
  • ammonium carbamate, carbonate, and bicarbonate compounds include ammonium carbamate, ammonium carbonate, ammonium bicarbonate, ethylammonium ethylcarbamate, isopropylammonium isopropylcarbamate, and n-butyl.
  • R 3 P examples include a phosphorus compound represented by (RO) 3 P or (RO) 3 PO.
  • R represents an alkyl or aryl group having 1 to 20 carbon atoms, and specific examples thereof include tributylphosphine, triphenylphosphine, triethyl phosphite, triphenyl phosphite, dibenzyl phosphate, triethyl phosphate and the like.
  • sulfur compound examples include butanethiol, n-hexanethiol, diethyl sulfide, tetrahydrothiophene, aryl disulfide, 2-mercaptobenzoazole, tetrahydrothiophene, octylthioglycolate, and the like.
  • the amount of such a stabilizer used is not particularly limited as long as it matches the ink characteristics of the present invention.
  • the content is preferably 0.1% to 90% in terms of molar ratio with respect to the silver compound.
  • examples of the thin film auxiliary agent include organic acids and organic acid derivatives, or at least one mixture thereof. Specifically, for example, acetic acid, butyric acid (valeric acid), valeric acid (pivalic acid), hexanoic acid, octanoic acid, 2-ethyl-hexanoic acid, neodecanoic acid, lauric acid ( Lauric acid), stearic acid, naphthalic acid, and the like.
  • organic acid derivatives include ammonium acetate, ammonium citrate, ammonium laurate, ammonium lactate, and ammonium maleate.
  • Organic acid ammonium salts such as ammonium oxalate and ammonium molybdate, Au, Cu, Zn, Ni, Co, Pd, Pt, Ti, V, Mn, Fe, Cr, Zr, Nb, Mo, W, Ru, Cd, Ta, Re, O
  • organic acid metal salts such as silver, silver octoate, silver neodecanoate, cobalt stearate, nickel naphthalate and cobalt naphthalate.
  • the amount of the thin film auxiliary used is not particularly limited, but is preferably 0.1 to 25% in terms of molar ratio with respect to the silver complex compound.
  • Examples of the reducing agent include Lewis acid or weak Bronsted acid, and specific examples include hydrazine, hydrazine monohydrate, acetohydrazide, sodium borohydride or potassium borohydride, dimethylamine borane, Amine compounds such as butylamine borane, metal salts such as ferrous chloride and iron lactate, hydrogen, hydrogen iodide, carbon monoxide, aldehyde compounds such as formaldehyde, acetaldehyde and glyoxal, methyl formate, butyl formate, triethyl Mention may be made of formic acid compounds such as o-formic acid and mixtures thereof containing at least one reducing organic compound such as glucose, ascorbic acid and hydroquinone.
  • formic acid compounds such as o-formic acid and mixtures thereof containing at least one reducing organic compound such as glucose, ascorbic acid and hydroquinone.
  • thermal decomposition reaction accelerator examples include ethanolamine, methyldiethanolamine, triethanolamine, propanolamine, butanolamine, hexanolamine, hydroxyalkylamines such as dimethylethanolamine, piperidine, and N-methylpiperidine.
  • a solvent is required for adjusting the viscosity of the silver coating liquid composition and for forming a smooth thin film.
  • the solvent that can be used in this case include water, methanol, ethanol, isopropanol, 1-methoxypropanol, butanol, Ethyl hexyl alcohol, alcohols such as terpineol, ethylene glycol, glycols such as glycerin, ethyl acetate, butyl acetate, methoxypropyl acetate, carbitol acetate, acetates such as ethyl carbitol acetate, methyl cellosolve, butyl cellosolve, diethyl Ethers such as ether, tetrahydrofuran, dioxane, methyl ethyl ketone, acetone, dimethylformamide, ketones such as 1-methyl-2-pyrrolidone, hexane, Hydrocarbons such as pent
  • the heating and baking proceeds quickly on the coating film surface (the side far from the glass film). However, it can happen that the heating and baking does not progress so much in the coating film on the side close to the glass film. That is, depending on the conditions of the manufacturing process, a silver reflective layer with high reflection efficiency is formed on the side far from the glass film, but a silver reflection layer with low reflection efficiency may be formed on the side near the glass film. is there.
  • the glass film side it is preferable to set the glass film side to the side opposite to the light incident side and the silver reflective layer side to the light incident side so that the performance does not vary depending on the conditions of the manufacturing process. In that case, it is preferable to provide a protective layer of resin or glass on the light incident side of the silver reflective layer.
  • the film mirror of the present invention preferably has a gas barrier layer.
  • the gas barrier layer according to the present invention is for preventing deterioration of humidity, particularly deterioration of various functional elements protected by the resin base material and the resin base material due to high humidity, but has a special function and application. As long as the above characteristics are maintained, various types of gas barrier layers can be provided.
  • the glass film is located on the light incident surface side with respect to the silver reflective layer and has a gas barrier layer on the opposite side of the light incident surface with respect to the silver reflective layer.
  • the moisture barrier property of the gas barrier layer is that the water vapor permeability at 40 ° C. and 90% RH is 100 g / m 2 ⁇ day / ⁇ m or less, preferably 50 g / m 2 ⁇ day / ⁇ m or less, more preferably 20 g / m 2. It is preferable to adjust the moisture resistance of the gas barrier layer so as to be not more than day / ⁇ m. Also.
  • the oxygen permeability is preferably 0.6 ml / m 2 / day / atm or less under the conditions of a measurement temperature of 23 ° C. and a humidity of 90% RH.
  • the gas barrier layer according to the present invention is not particularly limited in its formation method, but after applying the ceramic precursor of the inorganic oxide film, the inorganic oxide film is formed by heating and / or ultraviolet irradiation of the coating film.
  • the method is preferably used.
  • the gas barrier layer according to the present invention can be formed by applying a general heating method after applying a ceramic precursor that forms an inorganic oxide film by heating, but is preferably formed by local heating.
  • the ceramic precursor is preferably a sol-like organometallic compound or polysilazane.
  • the organometallic compound according to the present invention includes silicon (Si), aluminum (Al), lithium (Li), zirconium (Zr), titanium (Ti), tantalum (Ta), zinc (Zn), barium (Ba), and indium. It is preferable to contain at least one element of (In), tin (Sn), lanthanum (La), yttrium (Y), and niobium (Nb).
  • the organometallic compound is at least one element of silicon (Si), aluminum (Al), lithium (Li), zirconium (Zr), titanium (Ti), zinc (Zn), and barium (Ba). It is preferable to contain. Furthermore, it is preferable to contain at least one element of silicon (Si), aluminum (Al), and lithium (Li).
  • the organometallic compound is not particularly limited as long as it can be hydrolyzed, and preferred organometallic compounds include metal alkoxides.
  • the metal alkoxide is represented by the following general formula (I).
  • M represents a metal having an oxidation number n.
  • R 1 and R 2 each independently represents an alkyl group.
  • m represents an integer of 0 to (n ⁇ 1).
  • R 1 and R 2 may be the same or different.
  • an alkyl group having 4 or less carbon atoms is preferable.
  • a methyl group CH 3 (hereinafter represented by Me), an ethyl group C 2 H 5 (hereinafter represented by Et), a propyl group C 3 H 7 (hereinafter represented by Pr), isopropyl group i-C 3 H 7 (hereinafter represented by i-Pr), butyl group C 4 H 9 (hereinafter represented by Bu), isobutyl group i- A lower alkyl group such as C 4 H 9 (hereinafter referred to as i-Bu) is more preferred.
  • Examples of the metal alkoxide represented by the general formula (I) include lithium ethoxide LiOEt, niobium ethoxide Nb (OEt) 5 , magnesium isopropoxide Mg (OPr-i) 2 , aluminum isopropoxide Al (OPr -I) 3 , zinc propoxide Zn (OPr) 2 , tetraethoxysilane Si (OEt) 4 , titanium isopropoxide Ti (OPr-i) 4 , barium ethoxide Ba (OEt) 2 , barium isopropoxide Ba ( OPr-i) 2 , triethoxyborane B (OEt) 3 , zirconium propoxide Zn (OPr) 4 , lanthanum propoxide La (OPr) 3 , yttrium propoxide Y (OPr) 3 , lead isopropoxide Pb (OPr- i) 2 etc. are mentioned suitably. All of these metal alkoxide
  • the inorganic oxide according to the present invention is characterized in that it is formed by local heating from a sol using the organometallic compound as a raw material. Therefore, silicon (Si), aluminum (Al), zirconium (Zr), titanium (Ti), tantalum (Ta), zinc (Zn), barium (Ba), indium (In) contained in the organometallic compound, It is an oxide of an element such as tin (Sn) or niobium (Nb).
  • silicon oxide aluminum oxide, zirconium oxide and the like. Of these, silicon oxide is preferable.
  • a method for forming an inorganic oxide from an organometallic compound it is preferable to use a so-called sol-gel method and a method of applying polysilazane.
  • the “sol-gel method” is to obtain a hydroxide sol by hydrolyzing an organometallic compound, etc., dehydrate it into a gel, and further heat-treat the gel. It refers to a method for preparing a metal oxide glass having a certain shape (film, particle, fiber, etc.).
  • a multi-component metal oxide glass can be obtained by a method of mixing a plurality of different sol solutions, a method of adding other metal ions, or the like.
  • an inorganic oxide by a sol-gel method having the following steps.
  • the organometallic compound in a reaction solution containing at least water and an organic solvent, is hydrolyzed and dehydrated and condensed while adjusting the pH to 4.5 to 5.0 using a halogen ion as a catalyst in the presence of boron ion.
  • Generation of fine pores due to high-temperature heat treatment is produced by a sol-gel method having a step of obtaining a reaction product by heating and vitrifying the reaction product at a temperature of 200 ° C. or less. And is particularly preferable from the viewpoint that no deterioration of the film occurs.
  • the organometallic compound used as a raw material is not particularly limited as long as it can be hydrolyzed, and preferred organometallic compounds include the metal alkoxides. .
  • the organometallic compound may be used for the reaction as it is, but it is preferably diluted with a solvent for easy control of the reaction.
  • the solvent for dilution is not particularly limited as long as it can dissolve the organometallic compound and can be uniformly mixed with water.
  • Preferred examples of such a solvent for dilution include aliphatic lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, and mixtures thereof.
  • a mixed solvent of butanol, cellosolve, and butyl cellosolve or a mixed solvent of xylol, cellosolve acetate, methyl isobutyl ketone, and cyclohexane may be used.
  • the metal when the metal is Ca, Mg, Al or the like, it reacts with water in the reaction solution to form a hydroxide, or when carbonate ion CO 3 2- is present, a carbonate is formed. Therefore, it is preferable to add an alcohol solution of triethanolamine as a masking agent to the reaction solution.
  • the concentration of the organometallic compound when mixed and dissolved in a solvent is preferably 70% by mass or less, and more preferably diluted to a range of 5 to 70% by mass.
  • the reaction solution used in the sol-gel method contains at least water and an organic solvent.
  • the organic solvent is not particularly limited as long as it can form a uniform solution with water, acid, and alkali, and usually the same aliphatic lower alcohols used for diluting the organometallic compound are preferably used.
  • the aliphatic lower alcohols propanol, isopropanol, butanol, and isobutanol having a larger number of carbon atoms are preferable to methanol and ethanol. This is because the growth of the metal oxide glass film to be generated is stable.
  • the water ratio is preferably in the range of 0.2 to 50 mol / L as the concentration of water.
  • an organometallic compound is hydrolyzed in the reaction solution in the presence of boron ions using a halogen ion as a catalyst.
  • Preferred examples of the compound that gives the boron ion B 3+ include trialkoxyborane B (OR) 3 . Among these, triethoxyborane B (OEt) 3 is more preferable.
  • the B 3+ ion concentration in the reaction solution is preferably in the range of 1.0 to 10.0 mol / L.
  • halogen ion a fluorine ion and / or a chlorine ion are mentioned suitably. That is, fluorine ions alone, chlorine ions alone or a mixture thereof may be used.
  • the compound to be used may be any compound that generates fluorine ions and / or chlorine ions in the reaction solution.
  • the fluorine ion source ammonium hydrogen fluoride NH 4 HF ⁇ HF, sodium fluoride NaF, or the like is preferable.
  • Preferred examples of the chlorine ion source include ammonium chloride NH 4 Cl.
  • the concentration of the halogen ion in the reaction solution varies depending on the film thickness of an inorganic composition having an inorganic matrix to be produced and other conditions, but generally the reaction containing a catalyst.
  • a range of 0.001 to 2 mol / kg, particularly 0.002 to 0.3 mol / kg is preferable with respect to the total mass of the liquid. If the halogen ion concentration is lower than 0.001 mol / kg, hydrolysis of the organometallic compound does not proceed sufficiently, and film formation becomes difficult. If the halogen ion concentration exceeds 2 mol / kg, the resulting inorganic matrix (metal oxide glass) tends to be non-uniform, which is not preferable.
  • boron used during the reaction, if to be contained as a B 2 O 3 component in the design the composition of the resulting inorganic matrix, by leaving product was added calculated amount of organic boron compound in accordance with the content of
  • boron can be removed by evaporation as boron methyl ester by heating after film formation in the presence of methanol as a solvent or by immersing in methanol.
  • a main agent solution in which a predetermined amount of the organometallic compound is usually mixed and dissolved in a mixed solvent containing a predetermined amount of water and an organic solvent,
  • a predetermined amount of the reaction solution containing a predetermined amount of the above-mentioned halogen ions is mixed at a predetermined ratio and sufficiently stirred to obtain a uniform reaction solution, and then the pH of the reaction solution is adjusted to a desired value with acid or alkali
  • the reaction product is obtained by aging for several hours.
  • a predetermined amount of the boron compound is mixed and dissolved in advance in the main agent solution or reaction solution. Further, when alkoxyborane is used, it is advantageous to dissolve it in the main agent solution together with other organometallic compounds.
  • the pH of the reaction solution is selected depending on the purpose, and for the purpose of forming a film (film) made of an inorganic composition having an inorganic matrix (metal oxide glass), for example, the pH is adjusted using an acid such as hydrochloric acid. It is preferable to ripen the mixture by adjusting it to the range of 4.5 to 5. In this case, for example, it is convenient to use a mixture of methyl red and bromocresol green as an indicator.
  • the main component solution of the same concentration and the reaction solution (containing B 3+ and halogen ions) of the same component are added successively in the same ratio while adjusting to a predetermined pH.
  • the reaction product can also be produced simply and continuously.
  • the concentration of the reaction solution is in the range of ⁇ 50% by mass
  • the concentration of water (containing acid or alkali) is in the range of ⁇ 30% by mass
  • the concentration of halogen ions is in the range of ⁇ 30% by mass. Can be changed.
  • reaction product reaction solution after aging
  • reaction solution after aging reaction solution after aging
  • the temperature is raised gradually while paying particular attention to a temperature range of 50 to 70 ° C., followed by a preliminary drying (solvent volatilization) step and further raising the temperature.
  • This drying is important for forming a non-porous film in the case of film formation.
  • the temperature for heating and drying after the preliminary drying step is preferably 70 to 150 ° C, more preferably 80 to 130 ° C.
  • the gas barrier layer according to the present invention contains an inorganic oxide formed by local heating of a coating film after applying a ceramic precursor that forms an inorganic oxide film by heating.
  • the resin substrate is coated with a solution containing a catalyst in the polysilazane represented by the following formula (I) and an organic solvent as necessary, and the solvent is evaporated. Leaving a polysilazane layer having a layer thickness of 0.05-3.0 ⁇ m on the resin substrate and the presence of oxygen, active oxygen, and in some cases, nitrogen in an atmosphere containing water vapor Below, it is preferable to employ
  • R 1 , R 2 and R 3 are the same or different and independently of each other hydrogen, or an optionally substituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group, preferably Is selected from the group consisting of hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, phenyl, vinyl or 3- (triethoxysilyl) propyl, 3- (trimethoxysilylpropyl)
  • n is an integer and n is determined such that the polysilazane has a number average molecular weight of 150 to 150,000 g / mol.
  • catalysts preferably basic catalysts, in particular N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine or N-heterocyclic compounds are used.
  • the catalyst concentration is usually in the range of 0.1 to 10 mol%, preferably 0.5 to 7 mol%, based on polysilazane.
  • a solution containing perhydropolysilazane in which all of R 1 , R 2 and R 3 are hydrogen atoms is used.
  • the coating according to the invention contains at least one polysilazane of the following formula (II):
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other hydrogen, or optionally substituted alkyl, aryl, vinyl, or (trialkoxysilyl) Represents an alkyl group, where n and p are integers, and n is determined such that the polysilazane has a number average molecular weight of 150 to 150,000 g / mol.
  • R 1 , R 3 and R 6 represent hydrogen and R 2 , R 4 and R 5 represent methyl, R 1 , R 3 and R 6 represent hydrogen and R 2 , A compound in which R 4 represents methyl and R 5 represents vinyl, R 1 , R 3 , R 4 and R 6 represent hydrogen and R 2 and R 5 represent methyl.
  • a solution containing at least one polysilazane represented by the following formula (III) is also preferable.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are independently of each other hydrogen, an optionally substituted alkyl group, or an aryl group.
  • R 1 , R 3 and R 6 represent hydrogen and R 2 , R 4 , R 5 and R 8 represent methyl, R 9 represents (triethoxysilyl) propyl and R 7 Is a compound in which represents alkyl or hydrogen.
  • the proportion of polysilazane in the solvent is generally 1 to 80% by mass, preferably 5 to 50% by mass, and particularly preferably 10 to 40% by mass.
  • an aprotic solvent which does not contain water and a reactive group (for example, hydroxyl group or amine group) and is inert to polysilazane, preferably an aprotic solvent is suitable.
  • aprotic solvent which includes, for example, aliphatic or aromatic hydrocarbons, halogen hydrocarbons, esters such as ethyl acetate or butyl acetate, ketones such as acetone or methyl ethyl ketone, ethers such as tetrahydrofuran or dibutyl ether, and mono- and polyalkylene glycol dialkyl ethers (Diglymes) or a mixture of these solvents.
  • An additional component of the polysilazane solution can be a further binder such as those conventionally used in the manufacture of paints.
  • cellulose ethers and cellulose esters such as ethyl cellulose, nitrocellulose, cellulose acetate or cellulose acetobutyrate, natural resins such as rubber or rosin resins, or synthetic resins such as polymerized resins or condensed resins such as aminoplasts, in particular Urea resins and melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, or polysiloxanes.
  • Further components of the polysilazane formulation include, for example, additives that affect the viscosity of the formulation, substrate wetting, film formability, lubrication or exhaust properties, or inorganic nanoparticles such as SiO 2 , TiO 2 , ZnO , ZrO 2 or Al 2 O 3 .
  • the thickness of the coating film to be formed is preferably in the range of 100 nm to 2 ⁇ m.
  • the corrosion inhibitor for the silver reflective layer used in the film mirror of the present invention is roughly classified into a corrosion inhibitor and an antioxidant having an adsorptive group for silver.
  • corrosion refers to a phenomenon in which metal (silver) is chemically or electrochemically eroded or deteriorated by the environmental material surrounding it (see JIS Z0103-2004).
  • the film mirror of the present invention is preferably an embodiment in which the adhesive layer contains an antioxidant and the upper adjacent layer contains a corrosion inhibitor having an adsorptive group for silver.
  • the glass film is positioned on the light incident surface side with respect to the silver reflective layer, and a layer containing a corrosion inhibitor is disposed on the adjacent layer opposite to the light incident surface with respect to the silver reflective layer. It is preferable to have.
  • the optimum amount of the corrosion inhibitor varies depending on the compound to be used, but generally it is preferably in the range of 0.1 to 1.0 / m 2 .
  • Corrosion inhibitor having an adsorptive group for silver include amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring, compounds having a pyrazole ring, compounds having a thiazole ring, compounds having an imidazole ring, indazole Desirably, the compound is selected from a compound having a ring, copper chelate compounds, thioureas, a compound having a mercapto group, at least one naphthalene-based compound, or a mixture thereof.
  • amines and derivatives thereof include ethylamine, laurylamine, tri-n-butylamine, O-toluidine, diphenylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, monoethanolamine, diethanolamine, triethanolamine, 2N- Dimethylethanolamine, 2-amino-2-methyl-1,3-propanediol, acetamide, acrylamide, benzamide, p-ethoxychrysoidine, dicyclohexylammonium nitrite, dicyclohexylammonium salicylate, monoethanolamine benzoate, dicyclohexylammonium benzoate, diisopropyl Ammonium benzoate, diisopropylammonium nitrite Cyclohexylamine carbamate, nitronaphthalene nitrite, cyclohexylamine benzoate, dicyclohexylammonium
  • Examples of compounds having a pyrrole ring include N-butyl-2,5-dimethylpyrrole, N-phenyl-2,5-dimethylpyrrole, N-phenyl-3-formyl-2,5-dimethylpyrrole, and N-phenyl-3. , 4-diformyl-2,5-dimethylpyrrole, etc., or a mixture thereof.
  • Examples of the compound having a triazole ring include 1,2,3-triazole, 1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-hydroxy-1,2,4-triazole, 3- Methyl-1,2,4-triazole, 1-methyl-1,2,4-triazole, 1-methyl-3-mercapto-1,2,4-triazole, 4-methyl-1,2,3-triazole, Benzotriazole, tolyltriazole, 1-hydroxybenzotriazole, 4,5,6,7-tetrahydrotriazole, 3-amino-1,2,4-triazole, 3-amino-5-methyl-1,2,4- Triazole, carboxybenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy) -5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole
  • Examples of the compound having a pyrazole ring include pyrazole, pyrazoline, pyrazolone, pyrazolidine, pyrazolidone, 3,5-dimethylpyrazole, 3-methyl-5-hydroxypyrazole, 4-aminopyrazole, and a mixture thereof.
  • Examples of the compound having a thiazole ring include thiazole, thiazoline, thiazolone, thiazolidine, thiazolidone, isothiazole, benzothiazole, 2-N, N-diethylthiobenzothiazole, P-dimethylaminobenzallodanine, 2-mercaptobenzothiazole, etc. Or a mixture thereof.
  • Examples of the compound having an imidazole ring include imidazole, histidine, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methyl Imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl Imidazole, 2-phenyl-4-methyl-5-hydromethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 4-formylimidazole, 2-methyl-4-formylimidazole, 2-phenyl-4 Formylimidazole, 4-methyl-5-formylimidazole, 2-ethy
  • Examples of the compound having an indazole ring include 4-chloroindazole, 4-nitroindazole, 5-nitroindazole, 4-chloro-5-nitroindazole, and a mixture thereof.
  • copper chelate compounds include acetylacetone copper, ethylenediamine copper, phthalocyanine copper, ethylenediaminetetraacetate copper, hydroxyquinoline copper, and the like, or a mixture thereof.
  • thioureas examples include thiourea, guanylthiourea, and the like, or a mixture thereof.
  • mercaptoacetic acid thiophenol, 1,2-ethanediol, 3-mercapto-1,2,4-triazole, 1-methyl-3-mercapto
  • naphthalene-based compounds examples include thionalide.
  • an anchor layer may be provided between the silver reflective layer and the glass film.
  • the anchor layer is preferably 0.1 ⁇ m or more and 5 ⁇ m or less. More preferably, it is 0.5 ⁇ m or more and 5 ⁇ m or less.
  • the anchor layer can have a cushioning property, and it is possible to prevent cracks from occurring in the glass film. Further, even if cracks occur, the cracks are prevented from spreading and glass is prevented. It is preferable because scattering of pieces can be prevented.
  • the holding member holding the above-mentioned reflector in the state which can track the sun is further provided.
  • the holding member has a configuration for holding the reflector in a state in which the sun can be tracked.
  • the holding member may be driven manually, or a separate drive device may be provided to automatically track the sun.
  • the solar power generation reflector of the present invention since the reflector is reduced in weight, it is possible to suppress power consumption during solar tracking, so a configuration for automatically tracking by providing a drive device Is preferred.
  • the total thickness of the film mirror according to the present invention is preferably 75 to 250 ⁇ m, more preferably 90 to 230 ⁇ m, and still more preferably 100 to 220 ⁇ m, from the viewpoints of prevention of deflection of the mirror, regular reflectance, handling properties, and the like.
  • the film mirror of the present invention can be preferably used for the purpose of collecting sunlight. Although it can also be used as a solar reflective mirror by itself as a film mirror, more preferably, through a pressure-sensitive adhesive layer coated on the side of the resin base opposite to the side having the silver reflective layer across the resin base
  • the film mirror is affixed on another base material, particularly on a metal base material, and used as a reflection device for solar thermal power generation.
  • the reflecting device When used as a solar power generation reflecting device, the reflecting device is shaped like a bowl (semi-cylindrical), and a cylindrical member having fluid inside is provided at the center of the semicircle, and sunlight is condensed on the cylindrical member.
  • the form which heats an internal fluid by this, converts the heat energy, and generates electric power is mentioned as one form.
  • flat reflectors were installed at multiple locations, and the sunlight reflected by each reflector was collected on one reflector (central reflector) and reflected by the reflector.
  • the film mirror of the present invention is particularly preferably used because a high regular reflectance is required for the reflection device used.
  • the adhesive layer is not particularly limited, and for example, any of a dry laminating agent, a wet laminating agent, an adhesive, a heat seal agent, a hot melt agent, and the like is used.
  • polyester resin urethane resin, polyvinyl acetate resin, acrylic resin, nitrile rubber and the like are used.
  • the laminating method is not particularly limited, and for example, it is preferable to carry out the roll method continuously from the viewpoint of economy and productivity.
  • the thickness of the pressure-sensitive adhesive layer is usually preferably in the range of about 1 to 50 ⁇ m from the viewpoint of the pressure-sensitive adhesive effect, the drying speed and the like.
  • the other substrate to be bonded to the film mirror of the present invention may be any material that can impart the protective property of the silver reflective layer, for example, an acrylic film or sheet, a polycarbonate film or sheet, Polyarylate film or sheet, polyethylene naphthalate film or sheet, polyethylene terephthalate film or sheet, plastic film or sheet such as fluorine film, or resin film or sheet kneaded with titanium oxide, silica, aluminum powder, copper powder, etc.
  • a resin film or sheet coated with a resin kneaded with a resin or subjected to surface processing such as metal deposition is used.
  • the thickness of the laminated film or sheet is not particularly limited but is preferably in the range of 12 to 250 ⁇ m.
  • these other base materials may be bonded after providing a concave portion or a convex portion before being bonded to the film mirror of the present invention, or may be formed to have a concave portion or a convex portion after being bonded.
  • the bonding and the molding so as to have a concave portion or a convex portion may be performed at the same time.
  • the film mirror of the present invention When the film mirror of the present invention is used for a sunlight reflecting mirror, various types of base materials can be used as the base material for supporting the film mirror, but a self-supporting base material is preferably used. That is, it is preferable to be a solar reflective mirror in which the film mirror of the present invention is provided on a self-supporting base material.
  • the self-supporting base material used in the solar reflective mirror according to the present invention preferably has one of the following configurations A and B.
  • A It has a pair of metal flat plates and an intermediate layer provided between the metal flat plates, and the intermediate layer is a layer having a hollow structure or a layer made of a resin material.
  • a resin material layer having a hollow structure A resin material layer having a hollow structure.
  • the term “self-supporting substrate” refers to “self-supporting” means supporting the opposite edge portions when cut to a size used as a substrate for a reflector. This means that the substrate has rigidity enough to support the substrate. Since the base material of the reflecting plate has self-supporting properties, it is easy to handle when installing the reflecting plate, and the holding member for holding the reflecting plate can have a simple configuration. It is possible to reduce the weight of the device, and it is possible to suppress power consumption during solar tracking.
  • the self-supporting base material is composed of a pair of metal flat plates and an intermediate layer provided between the metal flat plates, and the intermediate layer is formed of a layer having a hollow structure or a resin material.
  • the base material is configured only by a metal flat plate.
  • the weight of the substrate can be greatly reduced, and the rigidity can be increased by the relatively lightweight intermediate layer, so that it can be a lightweight and self-supporting support. Become. Even in the case where a layer made of a resin material is used as the intermediate layer, it is possible to further reduce the weight by using a resin material layer having a hollow structure.
  • the intermediate layer when the intermediate layer has a hollow structure, the intermediate layer functions as a heat insulating material, so that the temperature change of the metal flat plate on the back side is prevented from being transmitted to the film mirror, preventing condensation and deterioration due to heat. Can be suppressed.
  • metal flat plate forming the surface layer of the configuration A
  • steel plate copper plate, aluminum plate, aluminum plated steel plate, aluminum alloy plated steel plate, copper plated steel plate, tin plated steel plate, chrome plated steel plate, stainless steel plate, etc.
  • a high metal material can be preferably used.
  • the intermediate layer of the configuration A has a hollow structure
  • a material such as a metal, an inorganic material (glass or the like), or a resin
  • a cellular structure made of a foamed resin, a three-dimensional structure having a wall surface made of a metal, an inorganic material, or a resin material (such as a honeycomb structure), a resin material to which hollow fine particles are added, or the like
  • the cellular structure of the foamed resin refers to a material in which a gas is finely dispersed in a resin material and formed into a foamed or porous shape, and a known foamed resin material can be used as the material.
  • the honeycomb structure represents a general three-dimensional structure composed of a plurality of small spaces surrounded by side walls.
  • the resin material constituting the wall surface is a homopolymer or copolymer of olefins such as ethylene, propylene, butene, isoprene pentene, and methylpentene.
  • Acrylic derivatives such as polyolefin (for example, polypropylene, high-density polyethylene), polyamide, polystyrene, polyvinyl chloride, polyacrylonitrile, ethylene-ethyl acrylate copolymer, vinyl acetate copolymers such as polycarbonate, ethylene-vinyl acetate copolymer Terpolymers such as ionomers and ethylene-propylene-dienes, and thermoplastic resins such as ABS resins, polyolefin oxides and polyacetals are preferably used. In addition, these may be used individually by 1 type, or may mix and use 2 or more types.
  • polyolefin for example, polypropylene, high-density polyethylene
  • polyamide for example, polypropylene, high-density polyethylene
  • polystyrene polyvinyl chloride
  • polyacrylonitrile ethylene-ethyl acrylate copolymer
  • vinyl acetate copolymers such as polycarbon
  • thermoplastic resins olefin-based resins or resins mainly composed of olefin-based resins
  • polypropylene-based resins or resins based mainly on polypropylene-based resins are preferable because of excellent balance between mechanical strength and moldability.
  • the resin material may contain an additive.
  • the additive include silica, mica, talc, calcium carbonate, glass fiber, carbon fiber, and other inorganic fillers, plasticizers, stabilizers, colorants, charging agents.
  • An inhibitor, a flame retardant, a foaming agent, etc. are mentioned.
  • the intermediate layer can be a layer made of a resin plate.
  • the resin material constituting the intermediate layer is preferably the same as the material constituting the support for the film mirror described above. Can do.
  • the intermediate layer does not have to be provided in all regions of the base material, and may be provided in a part of the region as long as the flatness of the metal flat plate and the self-supporting property as the base material can be ensured.
  • the intermediate layer has the above-described three-dimensional structure, it is preferable to provide the three-dimensional structure in a region of about 90 to 95% with respect to the area of the metal flat plate. It is preferable to provide it.
  • the self-supporting base material can be a layer made of a resin material having a hollow structure.
  • the base material is made of a resin-only layer, the thickness required to obtain rigidity sufficient to provide self-supporting properties increases, and as a result, the weight of the base material increases, but the resin base material has a hollow structure.
  • a resin sheet having a smooth surface is provided as a surface layer, and the resin material having a hollow structure is used as an intermediate layer from the viewpoint of increasing the regular reflectance of the film mirror. preferable.
  • the same material as that constituting the above-mentioned film mirror support can be preferably used, and as the resin material constituting the hollow structure, it is used for the above-mentioned foamed material and three-dimensional structure.
  • the same resin material as that obtained can be preferably used.
  • polyester resin Polyethylene terephthalate film, thickness 50 ⁇ m
  • polyester resin Polyethylene terephthalate film, thickness 50 ⁇ m
  • melamine resin Super Becamine J-820, manufactured by DIC
  • TDI-based isocyanate (2,4-tolylene diisocyanate
  • the silver coating solution composition A is applied so that the film thickness of the silver after heat drying is 80 nm, and then heat-dried at 100 ° C. for 5 minutes in a dry oven to form a silver reflective layer did. Subsequently, a resin in which a polyester resin and a TDI (tolylene diisocyanate) isocyanate are mixed at a resin solid content ratio of 10: 2 is coated on the silver reflective layer by a gravure coating method, and the thickness is 3.0 ⁇ m. An upper adjacent layer was formed.
  • TDI tolylene diisocyanate
  • a biaxially stretched polyester film (polyethylene terephthalate film, thickness 50 ⁇ m) was bonded from above the upper adjacent layer by a dry lamination process.
  • a platinum catalyst is added to 100 parts of an addition reaction type silicone pressure-sensitive adhesive having a weight average molecular weight of 500,000 at the bottom of the polyester resin to form a 35 mass% toluene solution, and this is applied to one side of a 25 ⁇ m thick polyester film.
  • the film was coated and heated at 130 ° C. for 5 minutes to form a 35 ⁇ m-thick silicone adhesive layer (Si-based) to obtain a film mirror of Comparative Example 1.
  • polyester resin Polyethylene SP-181, Nippon Synthetic Chemical
  • melamine resin Super Becamine J-820, manufactured by DIC
  • TDI isocyanate (2,4-tolylene) Isocyanate HDMI-based isocyanate (1,6-hexamethylene diisocyanate) in a resin solid content ratio of 20: 1: 1: 2 and a solid content concentration of 10% in toluene with a gravure coating method
  • an anchor layer having a thickness of 0.1 ⁇ m.
  • the silver coating solution composition A is applied so that the film thickness of the heat-dried silver is 80 nm, and then heat-dried at 100 ° C.
  • a solar reflective mirror (B-1) was produced using the film mirror of Comparative Example 2 in the same manner as the solar reflective mirror (A-1).
  • a thin glass roll A having a width of 1,200 mm, a thickness of 100 ⁇ m, and a length of 300 m is obtained by hot-melting an alkali-free glass using an apparatus for forming a thin glass for mounting a liquid crystal display device, and then by an overflow down draw method. Was made.
  • a silver reflective layer having a thickness of 100 nm was formed as a silver reflective layer by vacuum deposition.
  • 1 part of a platinum catalyst is added to 100 parts of an addition reaction type silicone pressure-sensitive adhesive having a weight average molecular weight of 500,000 on the silver reflection layer to form a 35 mass% toluene solution, which is applied to one side of a thickness polyester film.
  • the film was heated at 130 ° C. for 5 minutes to form a 35 ⁇ m-thick silicone adhesive layer (Si-based) to obtain a film mirror of Comparative Example 3.
  • a solar reflective mirror (M-1) was produced using the film mirror of Comparative Example 3 in the same manner as the solar reflective mirror (A-1).
  • Example 1 (Method for producing thin glass roll A) A thin glass roll A having a width of 1,200 mm, a thickness of 100 ⁇ m, and a length of 300 m is obtained by hot-melting an alkali-free glass using an apparatus for forming a thin glass for mounting a liquid crystal display device, and then by an overflow down draw method. Was made.
  • a silver coating solution composition A was applied on the plasma discharge treatment surface so that the film thickness of silver after heat drying was 80 nm. .
  • the silver reflective layer was formed by heating and drying at 150 ° C. for 2 minutes in a dry oven.
  • a solar reflective mirror (C-1) was produced using the film mirror of Example 1 by the same method as the solar reflective mirror (A-1).
  • Example 2 A film mirror of Example 2 was obtained in the same manner as in Example 1 except that the formation temperature of the silver reflective layer was 200 ° C. for 1 minute in a dry oven.
  • a film mirror of Example 3 was obtained in the same manner as in Example 2 except that the silver coating liquid composition B was used instead of the silver coating liquid composition A.
  • a film mirror of Example 4 was obtained in the same manner as in Example 2 except that the silver coating liquid composition C was used in place of the silver coating liquid composition A.
  • Example 5 (Manufacturing method of thin film glass roll B) A thin glass roll B with a width of 1,200 mm, a thickness of 30 ⁇ m, and a length of 300 m is obtained by hot-melting alkali-free glass using an apparatus for forming a thin glass for mounting a liquid crystal display device, and then by an overflow down draw method. Was made.
  • a film mirror of Example 5 was obtained in the same manner as in Example 2 except that the thin film glass roll B was used in place of the thin film glass roll A.
  • Example 6 (Method for producing thin glass roll C) A thin glass roll C with a width of 1,200 mm, a thickness of 150 ⁇ m and a length of 300 m is obtained by heat-melting non-alkali glass using an apparatus for forming a thin glass for mounting a liquid crystal display device, and then by an overflow down draw method. Was made.
  • a film mirror of Example 6 was obtained in the same manner as in Example 2 except that the thin film glass roll C was used instead of the thin film glass roll A.
  • Example 7 0.3 g after applying glycol dimercaptoacetate as a corrosion inhibitor to a resin in which a polyester resin and a TDI isocyanate are mixed at a resin solid content ratio of 10: 2 on the silver reflective layer prepared in Example 2. An amount adjusted to be / m 2 was added and coated by a gravure coating method to form a 1.0 ⁇ m thick corrosion prevention layer. Further, a 35 ⁇ m-thick silicone adhesive layer (Si-based) was formed on the outer side by the same method as in Example 1 to obtain a film mirror of Example 7.
  • Example 8 Using a 3% perhydropolysilazane liquid in dibutyl ether (NL120 manufactured by Clariant) on the corrosion prevention layer prepared in Example 7, bar coating was performed so that the thickness of the dried film was 100 nm. After naturally drying for 30 minutes, annealing was performed in an oven at 90 ° C. for 30 minutes to provide a gas barrier layer. Further, a 35 ⁇ m-thick silicone adhesive layer (Si-based) was formed on the outside in the same manner as in Example 1 to obtain a film mirror of Example 8.
  • a 3% perhydropolysilazane liquid in dibutyl ether NL120 manufactured by Clariant
  • Example 9 After performing UV ozone treatment for 2 minutes on the glass surface opposite to the silver reflective layer of the thin film glass roll A of the film mirror produced in Example 8 using a UV ozone device (manufactured by Technovision), further Plasma irradiation for 1 minute was performed. Thereafter, the plasma-treated surface was immersed for 1 minute in a treatment liquid in which a fluorine-based antifouling coating agent (Optool DSX manufactured by Daikin) was diluted to 0.1% by mass with perfluorohexane, and then high temperature and high humidity (60 ° C., The film mirror of Example 9 was obtained by drying for 1 hr in an environment of 90% RH).
  • a fluorine-based antifouling coating agent Optool DSX manufactured by Daikin
  • Example 10 The thin film glass roll A described above was used as the substrate.
  • polyester resin Polyethylene Teraphthalate
  • melamine resin Super Becamine J-820, manufactured by DIC
  • TDI isocyanate (2,4-tolylene diisocyanate
  • HDMI isocyanate (1,6-hexamethylene diisocyanate) was coated in a gravure coating method with a resin mixed in toluene at a resin solid content ratio of 20: 1: 1: 2 and a solid content concentration of 10%.
  • An anchor layer having a thickness of 0.1 ⁇ m was formed.
  • a silver coating liquid composition A was applied as a silver reflective layer so that the film thickness of silver after heat drying was 80 nm.
  • the silver reflective layer was formed by heating and drying at 150 ° C. for 2 minutes in a dry oven.
  • 1 part of a platinum-based catalyst was added to 100 parts of an addition reaction type silicone pressure-sensitive adhesive having a weight average molecular weight of 500,000 and applied as a 35 mass% toluene solution on the silver reflective layer.
  • Si-based silicone adhesive layer
  • a solar reflective mirror (L-1) was produced using the film mirror of Example 10 by the same method as the solar reflective mirror (A-1).
  • the thickness of the self-supporting base material was 2 mm.
  • the metal flat plate used was 0.12 mm thick aluminum on one side, and the intermediate resin layer was filled with foamed polyethylene resin having a thickness of 1.76 mm.
  • Table 3 shows the results of measuring the mass of the obtained solar reflective mirrors K-1 and K-2 having a size of 1.0 m 2.
  • Table 3 shows the ratios when the driving power required for one tracking unit incorporating the solar reflection mirror K-1 is 100 when the solar reflection mirror is incorporated into a solar tracking type solar power generation reflector. Show.
  • a spectrophotometer “UV265” manufactured by Shimadzu Corporation was modified with an integrating sphere reflection accessory, and the incident angle of incident light was adjusted to 5 ° with respect to the normal of the reflecting surface.
  • the regular reflectance at a reflection angle of 5 ° was measured. Evaluation was measured as an average reflectance from 350 nm to 700 nm.
  • ⁇ Weather resistance test for regular reflectance> The regular reflectance of the film mirror after being left for 30 days under the conditions of a temperature of 85 ° C. and a humidity of 85% RH is measured by the same method as the above-mentioned light reflectance measurement, and the regular reflectance and forced degradation of the film mirror before forced degradation. From the regular reflectance of the subsequent film mirror, the decrease rate of regular reflectance was calculated. The evaluation criteria for the weather resistance test are described below.
  • the rate of decrease in regular reflectance is less than 5% 4: The rate of decrease in regular reflectance is 5% or more and less than 10% 3: The rate of decrease in regular reflectance is 10% or more but less than 15% 2: The rate of decrease in regular reflectance 15% or more and less than 20% 1: The rate of decrease in regular reflectance is 20% or more.
  • the obtained sample was irradiated with ultraviolet rays for 7 days in an environment of 65 ° C. using an I-Super UV tester manufactured by Iwasaki Electric Co., Ltd., and then the regular reflectance was measured by the above method to decrease the regular reflectance before and after ultraviolet irradiation. The rate was calculated.
  • the evaluation criteria for the light resistance test are described below. 5: The rate of decrease in regular reflectance is less than 5% 4: The rate of decrease in regular reflectance is 5% or more and less than 10% 3: The rate of decrease in regular reflectance is 10% or more but less than 15% 2: The rate of decrease in regular reflectance 15% or more and less than 20% 1: The decrease rate of the regular reflectance is 20% or more.
  • Table 1 shows the contents of the various film mirrors obtained, and Tables 2 and 3 show the results of evaluating the characteristics.
  • the present invention is configured as described above, it can be used as a film mirror, a film mirror manufacturing method, and a solar reflective mirror.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Sciences (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Surface Treatment Of Glass (AREA)
  • Photovoltaic Devices (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention porte sur un miroir à film, lequel miroir a une couche réfléchissante en argent sur un corps de support, et lequel est caractérisé en ce que le corps de support est constitué par un film de verre qui a une épaisseur à l'intérieur de la plage de 1,0 à 200 µm, et en ce que la couche réfléchissante en argent est formée par chauffage et calcination d'un film de revêtement qui contient un composé complexe d'argent à partir duquel un ligand peut être vaporisé et libéré.
PCT/JP2011/064879 2010-08-20 2011-06-29 Miroir à film, procédé pour sa production, et miroir pour la réflexion de la lumière solaire utilisant un miroir à film WO2012023347A1 (fr)

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JP2010184694A JP2013231744A (ja) 2010-08-20 2010-08-20 フィルムミラーと、その製造方法、それを用いた太陽光反射用ミラー
JP2010-184694 2010-08-20

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Cited By (9)

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JP2013542277A (ja) * 2010-09-29 2013-11-21 フラウンフォーファー−ゲゼルシャフト ズール フェルデルンク デル アンゲヴァンデッテン フォルシュング エ ファウ 不飽和ポリエステルおよびポリシラザンから成る樹脂およびそれにより製造される熱硬化性反応樹脂の成形材
WO2014104020A1 (fr) * 2012-12-25 2014-07-03 株式会社Ｌｅａｐ Procédé pour la production de verre comprenant différents éléments
WO2014129454A1 (fr) * 2013-02-19 2014-08-28 日本電気硝子株式会社 Stratifié en verre, élément d'imagerie optique, procédé de fabrication de stratifié en verre et procédé de fabrication d'élément d'imagerie optique
EP3129725A4 (fr) * 2014-04-07 2018-04-11 L'garde Inc. Miroir d'héliostat léger et peu coûteux utilisé pour concentrer l'énergie solaire
WO2018135124A1 (fr) * 2017-01-18 2018-07-26 旭硝子株式会社 Miroir csp et procédé de production de substrat en verre avec film pour miroirs csp
CN113447939A (zh) * 2020-03-26 2021-09-28 莱卡地球系统公开股份有限公司 测距装置
CN115362058A (zh) * 2020-03-30 2022-11-18 日东电工株式会社 多层构造体
WO2023054282A1 (fr) * 2021-09-28 2023-04-06 日東電工株式会社 Structure multicouche
WO2023163129A1 (fr) * 2022-02-28 2023-08-31 日東電工株式会社 Structure multicouche

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KR101531891B1 (ko) * 2011-04-20 2015-06-29 주식회사 잉크테크 은 잉크 조성물
WO2016009755A1 (fr) * 2014-07-14 2016-01-21 富士フイルム株式会社 Plaque réfléchissante pour génération d'énergie thermique solaire
JP2021154664A (ja) 2020-03-30 2021-10-07 日東電工株式会社 複層構造体
JP7434023B2 (ja) 2020-03-30 2024-02-20 日東電工株式会社 複層構造体
JP2022078515A (ja) 2020-11-13 2022-05-25 日東電工株式会社 複層構造体及びその製造方法
JP2022078516A (ja) 2020-11-13 2022-05-25 日東電工株式会社 複層構造体及びその製造方法
JP2022085125A (ja) 2020-11-27 2022-06-08 日東電工株式会社 複層構造体

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JP2009535661A (ja) * 2006-04-29 2009-10-01 インクテック カンパニー リミテッド 有機銀錯体化合物を含む反射膜コーティング液組成物及びこれを用いた反射膜の製造方法
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013542277A (ja) * 2010-09-29 2013-11-21 フラウンフォーファー−ゲゼルシャフト ズール フェルデルンク デル アンゲヴァンデッテン フォルシュング エ ファウ 不飽和ポリエステルおよびポリシラザンから成る樹脂およびそれにより製造される熱硬化性反応樹脂の成形材
WO2014104020A1 (fr) * 2012-12-25 2014-07-03 株式会社Ｌｅａｐ Procédé pour la production de verre comprenant différents éléments
WO2014129454A1 (fr) * 2013-02-19 2014-08-28 日本電気硝子株式会社 Stratifié en verre, élément d'imagerie optique, procédé de fabrication de stratifié en verre et procédé de fabrication d'élément d'imagerie optique
JP2015083527A (ja) * 2013-02-19 2015-04-30 日本電気硝子株式会社 ガラス積層体、光学結像部材、ガラス積層体の製造方法及び光学結像部材の製造方法
EP3129725A4 (fr) * 2014-04-07 2018-04-11 L'garde Inc. Miroir d'héliostat léger et peu coûteux utilisé pour concentrer l'énergie solaire
WO2018135124A1 (fr) * 2017-01-18 2018-07-26 旭硝子株式会社 Miroir csp et procédé de production de substrat en verre avec film pour miroirs csp
CN113447939A (zh) * 2020-03-26 2021-09-28 莱卡地球系统公开股份有限公司 测距装置
US11846709B2 (en) 2020-03-26 2023-12-19 Leica Geosystems Ag Distance measuring device
CN115362058A (zh) * 2020-03-30 2022-11-18 日东电工株式会社 多层构造体
EP4129648A4 (fr) * 2020-03-30 2023-12-27 Nitto Denko Corporation Structure multicouches
WO2023054282A1 (fr) * 2021-09-28 2023-04-06 日東電工株式会社 Structure multicouche
WO2023163129A1 (fr) * 2022-02-28 2023-08-31 日東電工株式会社 Structure multicouche

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