WO2011037233A1 - Film adhésif pour cellule solaire, procédé de fabrication du film adhésif et module de cellules solaires - Google Patents

Film adhésif pour cellule solaire, procédé de fabrication du film adhésif et module de cellules solaires Download PDF

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Publication number
WO2011037233A1
WO2011037233A1 PCT/JP2010/066712 JP2010066712W WO2011037233A1 WO 2011037233 A1 WO2011037233 A1 WO 2011037233A1 JP 2010066712 W JP2010066712 W JP 2010066712W WO 2011037233 A1 WO2011037233 A1 WO 2011037233A1
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Prior art keywords
adhesive sheet
solar cell
weight
parts
resin
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PCT/JP2010/066712
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English (en)
Japanese (ja)
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憲一 井上
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積水フィルム株式会社
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Priority to JP2011514906A priority Critical patent/JPWO2011037233A1/ja
Publication of WO2011037233A1 publication Critical patent/WO2011037233A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • B29C48/307—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets specially adapted for bringing together components, e.g. melts within the die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10339—Specific parts of the laminated safety glass or glazing being colored or tinted
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • 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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • 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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/49—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using two or more extruders to feed one die or nozzle
    • B29C48/495—Feed-blocks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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 cell adhesive sheet used when producing a solar cell module, a manufacturing method thereof, and a solar cell module using the solar cell adhesive sheet.
  • a solar cell module consisting of a silicon or selenium semiconductor wafer has a reduced pressure on a laminate obtained by overlaying a transparent protective material on the upper surface of a solar cell element with a solar cell adhesive sheet laminated on both sides and a back surface protective material on the lower surface It is manufactured by heating while degassing below and stacking and integrating the protective material on the upper and lower surfaces of the solar cell element via an adhesive sheet.
  • Patent Document 1 As an adhesive sheet for a solar cell used in such a solar cell module, for example, in Patent Document 1, a silicon power generation element is arranged, and a sealing material film is interposed on both sides of the silicon power generation element, and the heating sheet is integrated.
  • a solar cell encapsulant film characterized in that the encapsulant film in a solar cell module formed by pressure bonding is an ethylene-vinyl acetate copolymer sheet having a melt flow rate of 14 g / 10 min or less.
  • the EVA resin layer 18 may be colored using a colorant in order to improve the efficiency as a solar cell.
  • the present invention provides an adhesive sheet for solar cells that has excellent adhesiveness and can stably seal solar cell elements over a long period of time, a method for producing the same, and a solar cell using the adhesive sheet for solar cells.
  • the adhesive sheet for solar cells of the present invention is an adhesive sheet for solar cells in which three or more resin layers containing an ethylene-based copolymer and an organic peroxide are laminated and integrated. At least one of the removed resin layers is formed in a colored layer containing 0.5 to 30 parts by weight of a colorant with respect to 100 parts by weight of the ethylene copolymer, and the total thickness of the colored layer is The total thickness of the adhesive sheet for solar cells is 50 to 95%, and at least one of the resin layers as the outermost layer is a silane coupling agent of 0.1 parts by weight relative to 100 parts by weight of the ethylene copolymer. It contains 05 to 2 parts by weight.
  • the method for producing an adhesive sheet for solar cells of the present invention includes supplying a resin composition containing an ethylene copolymer and an organic peroxide to a plurality of extruders, and melt-kneading each of them.
  • a manufacturing method for manufacturing an adhesive sheet for solar cells in which three or more resin layers made of the resin composition are laminated and integrated by supplying the resin composition to a T-die connected to each other and co-extrusion. And at least one of the resin compositions supplied to the extruder contains 0.5 to 30 parts by weight of a colorant with respect to 100 parts by weight of the ethylene-based copolymer.
  • the resin composition constituting at least one resin layer other than the outermost resin layer in the solar cell adhesive sheet is a colored layer, and the at least one resin layer of the outermost resin layer is ethylene.
  • system It contains 0.05 to 2 parts by weight of a silane coupling agent with respect to 100 parts by weight of the polymer, and the total thickness of the colored layer is 50 to 95% of the total thickness of the adhesive sheet for solar cells. It is characterized by adjusting.
  • the solar cell module of the present invention is laminated on the upper and lower solar cell adhesive sheet, the solar cell element that is sealed and integrated from above and below by the solar cell adhesive sheet, and the upper solar cell adhesive sheet.
  • a solar cell module having an integrated transparent protective material and a back surface protective material laminated and integrated on the lower solar cell adhesive sheet, wherein the lower solar cell adhesive sheet is:
  • An adhesive sheet for solar cells in which three or more resin layers containing an ethylene copolymer and an organic peroxide are laminated and integrated, and at least one of the resin layers excluding the outermost resin layer
  • the resin layer is formed in a colored layer containing 0.5 to 30 parts by weight of a colorant with respect to 100 parts by weight of the ethylene copolymer, and the total thickness of the colored layer is equal to the total thickness of the adhesive sheet for solar cells.
  • at least one of the outermost resin layers contains 0.05 to 2 parts by weight of a silane coupling agent with respect to 100 parts by weight of the ethylene copolymer. It is characterized by.
  • the sealing property of the solar cell element is not deteriorated by the colorant, and the excellent sealing property is stable over a long period of time.
  • the solar cell element can be reliably sealed over a long period of time.
  • the adhesive sheet A for solar cells is formed by laminating and integrating three or more resin layers 1, 1... Containing an ethylene copolymer and an organic peroxide.
  • Each resin layer 1a, 1b of the adhesive sheet A for solar cells contains an ethylene copolymer and an organic peroxide.
  • the ethylene-based copolymer is a copolymer of ethylene and a copolymerizable monomer that can be copolymerized with ethylene.
  • a copolymerizable monomer is not particularly limited, and examples thereof include vinyl acetate and acrylic monomers. Examples include acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, maleic acid, maleic anhydride, maleic acid ester, and propylene.
  • the ethylene copolymer is preferably an ethylene-vinyl acetate copolymer (EVA).
  • EVA ethylene-vinyl acetate copolymer
  • the said copolymerizable monomer may be copolymerized with ethylene independently, or 2 or more types may be copolymerized with ethylene.
  • the transparency of the solar cell adhesive sheet may be lowered.
  • the mechanical strength may be insufficient, so that it is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and particularly preferably 14 to 35% by weight.
  • the melt flow rate of the ethylene copolymer in the present invention refers to a value measured under conditions of a temperature of 190 ° C. and a load of 21.18 N (2.16 kgf) in accordance with JIS K7210.
  • the melt flow rate of the ethylene copolymer contained in the outermost resin layer is higher than the melt flow rate of the ethylene copolymer contained in the resin layer excluding the outermost resin layer.
  • An ethylene copolymer having a higher melt flow rate than the melt flow rate of the ethylene copolymer used for the resin layer excluding the outermost resin layer when manufacturing an adhesive sheet for solar cells by extrusion molding or the like.
  • the solar cell adhesive sheet is manufactured by extrusion molding, fine linear irregularities occur on the surface of the solar cell adhesive sheet due to the difference in fluidity between the resin layers. Therefore, it is possible to improve the uniformity of thickness.
  • the solar cell adhesive sheet having a uniform thickness can be firmly bonded to the solar cell element and the back surface protective material, and has excellent sealing properties.
  • the melt flow rate of the ethylene copolymer contained in the outermost resin layer is preferably 25 to 60 g / 10 minutes, more preferably 30 to 50 g / 10 minutes.
  • the melt flow rate of the ethylene copolymer contained in the resin layer excluding the outermost resin layer is preferably 5 to 20 g / 10 minutes.
  • the solar cell adhesive sheet A is used by being disposed on the lower surface of the solar cell element when the solar cell module is manufactured, and the solar cell element is disposed on the upper surface of the solar cell element by thermocompression bonding under reduced pressure. Together with another solar cell adhesive sheet, it is sealed and integrated, and the solar cell element and a protective material disposed on the upper and lower surfaces of the solar cell element via the solar cell adhesive sheet are bonded.
  • the adhesives and heat resistance particularly required for the adhesive sheet for solar cells the ethylene-based copolymer has a problem that heat resistance is low although it is excellent in adhesiveness. Accordingly, an organic peroxide is contained in the ethylene copolymer constituting the adhesive sheet A for solar cells, and the ethylene copolymer is crosslinked by heat applied during the production of the solar cell module. The heat resistance of the adhesive sheet A is improved.
  • Examples of the organic peroxide used for the resin layer 1 include dicumyl peroxide (136 ° C.), t-butyl peroxy-2-ethylhexyl monocarbonate (119 ° C.), and t-butyl peroxybenzoate (125 ° C.).
  • 1,1-di (t-butylperoxy) -2-methylcyclohexane (102 ° C.), 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane (106 ° C.), 1 , 1-di (t-hexylperoxy) cyclohexane (107 ° C.), 1,1-di (t-butylperoxy) cyclohexane (111 ° C.), 2,2-di (4,4-di (t-butyl) Peroxy) cyclohexyl) propane (114 ° C.), t-hexyl peroxyisopropyl monocarbonate (115 ° C.), t-butyl peroxyisopropyl Pyrmonocarbonate (118 ° C.), t-butyl peroxylaurate (118 ° C.), 2,5-dimethyl-2,5-di (benzoylperoxy) hexane
  • the crosslinking of the ethylene copolymer becomes insufficient during the production of the solar cell module, and the heat resistance of the adhesive sheet for solar cells is reduced.
  • the resin layer cross-links and stays in the T-die and adheres to the solar cell with a uniform thickness
  • the sheet cannot be obtained, or the ethylene copolymer is solidified in the T-die and the solar cell adhesive sheet cannot be extruded. .05 to 3 parts by weight is preferred.
  • the resin layer 1 may contain a crosslinking aid.
  • the crosslinking aid include polyfunctional monomers having two or more allyl groups, vinyl groups, acryloyl groups or methacryloyl groups, which stabilize polymer radicals to increase crosslinking efficiency and concentrate crosslinking points. Accelerates gel formation.
  • the polyfunctional monomer include diallyl phthalate, diallyl itaconate, diallyl maleate, triallyl isocyanurate, triallyl cyanurate, triallyl phosphate, divinylbenzene; 1,6-hexanediol di (meth) acrylate.
  • (Meth) such as ethylene oxide modified bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ⁇ -caprolactone modified dipentaerythritol Examples thereof include acrylates and (meth) acrylates of alkyl-modified dipentaerythritol, which may be used alone or in combination of two or more.
  • (meth) acrylate means an acrylate or a methacrylate.
  • the crosslinking of the solar cell adhesive sheet may be insufficient during the production of the solar cell module. Since it becomes too hard and hard, excessive stress is applied to the solar cell element, which may be undesirable in protecting the solar cell element. 01 to 1 part by weight is preferred.
  • At least one of the resin layers 1a, 1a,... Excluding the outermost resin layer 1b is a colored layer containing a colorant. That is, one or two or more resin layers 1a out of the resin layers 1a, 1a,... Excluding the outermost resin layer 1b are colored layers containing a colorant.
  • Examples of such a colorant include titanium oxide, calcium carbonate, magnesium oxide, barium sulfate, carbon black, cadmium sulfide, ultramarine blue, and iron oxide.
  • a colorant having light reflectivity is preferable, and titanium oxide is preferable. More preferred.
  • the adhesive sheet for solar cells having a uniform quality is lowered, it is limited to 0.5 to 30 parts by weight based on 100 parts by weight of the ethylene copolymer, and 1 to 15 parts by weight. preferable.
  • the solar cell adhesive sheet is insufficiently colored. If it is thick, the outermost resin layer is relatively thin, and the solar cell has a uniform thickness. Since it becomes difficult to produce an adhesive sheet, it is limited to 50 to 95% of the total thickness of the adhesive sheet for solar cells, and preferably 70 to 95%.
  • the total thickness of a colored layer means the thickness of the colored layer, when there is one colored layer, and the total thickness of the colored layer when there are a plurality of colored layers.
  • the adhesive sheet A for solar cells is excellent in the sealing property of a solar cell element, and can maintain the sealing property of a solar cell element stably over a long period of time.
  • one or both of the resin layers 1b and 1b which are the outermost layers in the solar cell adhesive sheet, contain a silane coupling agent, and when used in the production of solar cell modules, solar cells It is preferable that a silane coupling agent is contained in the resin layer 1b which is the outermost layer facing the element.
  • the adhesion with the solar cell element is improved, and the solar cell element by the solar cell adhesive sheet This improves the sealing performance and is stably maintained over a long period of time.
  • silane coupling agent a silane coupling agent having one or two or more functional groups selected from the group consisting of an amino group, a glycidyl group, a methacryloxy group, and a mercapto group is preferably used.
  • Propyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. may be used alone or in combination of two or more. Good.
  • the adhesive property of the solar cell adhesive sheet to the solar cell element is lowered. Since it causes discoloration of the sheet, it is limited to 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the ethylene copolymer.
  • the resin layers 1a and 1b constituting the solar cell adhesive sheet may contain additives such as a scorch inhibitor, an antioxidant, and an ultraviolet absorber as long as the physical properties thereof are not impaired. Good.
  • the film formation of the solar cell adhesive sheet A can be performed by a multilayer extrusion apparatus in which two or more extruders are connected to one T die via one feed block, for example, three layers A multi-layer extrusion apparatus having a minute-extruder, and an ethylene-based copolymer and an organic peroxide for the resin layer 1b as the outermost layer in two extruders of this multi-layer extrusion apparatus, and if necessary While supplying the resin composition containing the additive to be added, to the remaining one extruder, the ethylene copolymer for the colored layer, the organic peroxide and the colorant, and the additive added as necessary A resin layer that is melted and kneaded in each extruder, supplied to a feed block, and a resin layer that is the outermost layer from a T-die disposed at the tip of the feed block 1b, colored layer 1a and outermost resin layer 1
  • the film can be formed by extruding
  • melt-kneading was performed with one extruder, and the molten resin composition extruded from the extruder was branched into two. You may form into a film by supplying a feed block above.
  • the solar cell adhesive sheet A having four or more layers can be manufactured in the same manner, and a multilayer extrusion apparatus having extruders corresponding to the number of solar cell adhesive sheets is prepared.
  • the resin composition constituting each resin layer is supplied, the resin composition is melted and kneaded in each extruder, supplied to the feed block, and the resin layer from the T die disposed at the tip of the feed block Can be formed by extruding into a sheet shape so as to be laminated and integrated in a desired order, and cooling and solidifying and winding the extruded molten sheet with a cooling roll.
  • the resin composition melt-kneaded by each extruder is supplied to the feed block and extruded from the T-die disposed at the tip of the feed block.
  • the resin compositions constituting the outermost resin layers 1b and 1b are connected and integrated at both ends in the width direction of the T-die, and the remaining portions excluding the outermost resin layers 1b and 1b. It is preferable that the resin composition constituting the resin layer is covered with the resin composition constituting the outermost resin layers 1b and 1b over the entire circumference.
  • the colorant contained in the resin composition does not adhere to the inner wall surface of the T-die, and streaky irregularities on the surface of the solar cell adhesive sheet due to the colorant. Can be prevented, and the sealing performance of the solar cell element in the resulting solar cell adhesive sheet can be improved.
  • the temperature at which the resin composition constituting the resin layers 1a and 1b is melted and kneaded in the extruder is high, the organic peroxide in the resin composition is decomposed. Since the crosslinking of the ethylene copolymer may proceed, the temperature is preferably 10 ° C. or more lower than the one-hour half-life temperature of the organic peroxide used. In the case of using an oxide, the temperature is preferably 10 ° C. or more lower than the one-hour half-life temperature of the lowest organic peroxide among the organic peroxides to be used.
  • the adhesive sheet A for solar cells may be manufactured by laminating and integrating the films constituting each resin layer using a general-purpose method such as extrusion lamination, in addition to the above manufacturing method.
  • the surface of the adhesive sheet A for solar cells is preferably subjected to embossing in order to improve the deaeration property in the thermocompression bonding process at the time of manufacturing the solar cell module.
  • embossing the surface of the adhesive sheet A for solar cells a known method is used.
  • the adhesive sheet A for solar cells in a molten state immediately after being extruded from a T die is embossed on the surface. It is supplied between the embossed roll on which the pattern is applied and a support roll (for example, a rubber roll, an iron roll, etc.) disposed opposite to the embossed roll, and the embossed roll is pressed against the molten sheet to form a solar cell.
  • a method of embossing the surface of the adhesive sheet A for use The once produced solar cell adhesive sheet A may be heated again to a molten state and embossed as described above.
  • positioned facing the embossing roll is provided with the fine uneven
  • a solar cell module using the adhesive sheet A for solar cells of this invention As a method of manufacturing a solar cell module using the adhesive sheet A for solar cells of this invention, as shown in FIG. 2, it is glass on the upper surface of the solar cell element 2 via the adhesive sheet for general purpose solar cells.
  • a laminated body in which a transparent protective material 3 such as a plate is laminated and a back surface protective material 4 is laminated on the lower surface of the solar cell element 2 via the adhesive sheet A for solar cells is produced. Heat-press.
  • the outermost layer containing the silane coupling agent in the solar cell adhesive sheet A is made to face the solar cell element 2.
  • the solar cell element 2 examples include a solar cell element having a structure using a single crystal or polycrystalline wafer, and a solar cell element in which silicon, a compound semiconductor, or the like is laminated and integrated into a thin film on a substrate. It is done.
  • seat containing an ethylene-type copolymer and an organic peroxide etc. are mentioned, for example. Since the ethylene copolymer and the organic peroxide are the same as described above, the description thereof is omitted.
  • the adhesive sheet for upper and lower solar cells laminated on the upper and lower surfaces of the solar cell element is melted, and the solar cell element is sealed and integrated with the adhesive sheet for upper and lower solar cells by filling the gap between the solar cell elements 2 and 2. .
  • each resin layer of the adhesive sheet for solar cells is crosslinked with an organic peroxide to impart heat resistance.
  • the transparent protective material 3 is laminated and integrated on the upper surface of the solar cell element 2 via the upper solar cell adhesive sheet, and the lower solar cell adhesive sheet A is provided on the lower surface of the solar cell element 2.
  • the back surface protective material 4 is laminated and integrated to obtain the solar cell module B (see FIG. 2).
  • the solar cell module B having a structure in which the solar cell element is sealed and integrated using the solar cell adhesive sheet from the vertical direction has been described, but the solar cell adhesive sheet A of the present invention is described below. It can also be used for the solar cell module B having a structure.
  • a solar battery cell 6 made of silicon, a compound semiconductor, or the like is laminated and integrated in a thin film shape on a transparent substrate 5, and a solar battery adhesive sheet A is laminated on the solar battery cell 6, and solar battery adhesion is performed.
  • seat A was produced, and this laminated body was heat-pressed under pressure reduction, the transparent substrate 5, the photovoltaic cell 6, the adhesive sheet A for solar cells, and the back surface protection material 4 Can be obtained (see FIG. 3).
  • the solar battery cell 6 is sealed and integrated by the transparent substrate 5 and the solar battery adhesive sheet A.
  • the solar cell adhesive sheet A is integrated with the lower surface of the solar cell element, but the resin layer 1b which is the outermost layer of the solar cell adhesive sheet A facing the solar cell element. Contains a silane coupling agent, and the solar cell adhesive sheet A and the solar cell element are firmly integrated. The solar cell element is stably provided over a long period of time by the solar cell adhesive sheet. Sealed.
  • the adhesive sheet A for solar cells has a colored layer in at least one layer of the resin layer 1 to improve the appearance of the solar cell module B, and the colorant contained in the colored layer
  • the light generation efficiency of the solar cell element is improved by reflecting the light that has passed through the solar cell element and is incident on the solar cell adhesive sheet A to the solar cell element side. Can do.
  • Examples 1 to 3 Comparative Examples 1 to 4
  • Three-layer coextrusion equipment is prepared in which three extruders are connected to one T-die via one feed block, and two of these extruders are resin layers 1b and 1b that are the outermost layers on both sides. The other machine was for the colored layer.
  • the extruder for the first outermost resin layer 1b was fed into an ethylene-vinyl acetate copolymer (trade name “EV250” manufactured by Mitsui DuPont Polychemical Co., Ltd., vinyl acetate content: 28% by weight, melt flow rate ( MFR): 10 g / 10 min) 100 parts by weight, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane (1 hour half-life temperature: 118.8 ° C.) 0.5 parts by weight, triallyl isocyan 0.3 part by weight of nurate, 0.1 part by weight of 2,6-di-t-butyl-4-methylphenol, 0.3 part by weight of 2-hydroxy-4-methoxybenzophenone and 3 of the predetermined amount shown in Table 1 -A resin composition containing glycidoxypropyltrimethoxysilane was supplied.
  • EV250 ethylene-vinyl acetate copolymer manufactured by Mitsui DuPont Polychemical Co.
  • an ethylene-vinyl acetate copolymer (trade name “EV250” manufactured by Mitsui DuPont Polychemical Co., Ltd., vinyl acetate content: 28% by weight, melt flow rate ( MFR): 10 g / 10 min) 100 parts by weight, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane (1 hour half-life temperature: 118.8 ° C.) 0.5 parts by weight, triallyl isocyan Supplying a resin composition containing 0.3 part by weight of nurate, 0.1 part by weight of 2,6-di-t-butyl-4-methylphenol and 0.3 part by weight of 2-hydroxy-4-methoxybenzophenone did.
  • An ethylene-vinyl acetate copolymer (trade name “EV250” manufactured by Mitsui DuPont Polychemical Co., Ltd., vinyl acetate content: 28 wt%, melt flow rate (MFR): 10 g / 10 min) 100 parts by weight, 0.5 parts by weight of 2,5-dimethyl-2,5-di (benzoylperoxy) hexane (1 hour half-life temperature: 118.8 ° C.), 0.3 parts by weight of triallyl isocyanurate, , 6-di-t-butyl-4-methylphenol 0.1 parts by weight, 2-hydroxy-4-methoxybenzophenone 0.3 parts by weight, and a predetermined amount of titanium oxide shown in Table 1 Supplied.
  • the resin composition is melted and kneaded at 90 ° C. in each of the three extruders, and the molten resin composition is supplied to the feed block.
  • the resin layer 1b made of the resin composition extruded from the extruder for the resin layer 1b as the outer layer is laminated and integrated in this order, and the thickness of each resin layer is the thickness shown in Table 1.
  • the resin layer 1b that is the first outermost layer is laminated and integrated on the first surface of the colored layer, and the resin layer 1b that is the second outermost layer is laminated and integrated on the second surface of the colored layer.
  • a three-layer solar cell adhesive sheet A was formed.
  • the colored layer and the resin layer 1b as the second outermost layer did not contain a silane coupling agent.
  • the resin layer 1b made of the resin composition extruded from the extruder for the resin layer 1b serving as the first outermost layer is referred to as “first resin layer 1b” and the second outermost layer.
  • the resin layer 1b made of the resin composition extruded from the extruder for the resin layer 1b was referred to as “second resin layer 1b”.
  • the molten solar cell adhesive sheet A immediately after being co-extruded from the T-die is supplied between the embossing roll and a rubber roll disposed so as to face the embossing roll. Is pressed on the molten solar cell adhesive sheet A, the surface of the solar cell adhesive sheet A is embossed to a depth of 0.3 mm, and then wound while being cooled by a cooling roll, thereby forming three layers. A solar cell adhesive sheet A having the structure was obtained. The embossing was performed on the surface of the resin layer containing 3-glycidoxypropyltrimethoxysilane. Moreover, when embossing the adhesive sheet for solar cells of Comparative Example 1 and Comparative Example 3, any one surface of the adhesive sheet for solar cells was embossed.
  • Comparative Example 1 the resin composition was not supplied to the two extruders for the outermost layer 1b, and the resin composition was supplied only to the extruder for the colored layer to produce a single-layer solar cell adhesive sheet. .
  • Example 4 an ethylene-vinyl acetate copolymer (Mitsui DuPont) was used in each of the extruder for the resin layer 1b as the first outermost layer and the extruder for the resin layer 1b as the second outermost layer.
  • Product name “EV250” manufactured by Polychemical Co., Ltd. instead of vinyl acetate content: 28 wt%, melt flow rate: 10 g / 10 min), ethylene-vinyl acetate copolymer (trade name “NUC3166” manufactured by Nihon Unicar) Vinyl acetate content: 34 wt%, melt flow rate 40 g / 10 min), and the amount of titanium oxide supplied to the colored layer extruder was changed to 20 parts by weight.
  • a solar cell adhesive sheet was produced.
  • Example 5 an ethylene-vinyl acetate copolymer (Mitsui DuPont) was used in each of the extruder for the resin layer 1b as the first outermost layer and the extruder for the resin layer 1b as the second outermost layer.
  • Product name “EV250” manufactured by Polychemical Co., Ltd. Instead of vinyl acetate content: 28 wt%, melt flow rate: 10 g / 10 min), ethylene-vinyl acetate copolymer (Mitsui DuPont Polychemical product name) EV270 ", vinyl acetate content: 28 wt%, melt flow rate: 1 g / 10 min), and the amount of titanium oxide supplied to the colored layer extruder was changed to 20 parts by weight.
  • Example 1 A solar cell adhesive sheet was produced in the same manner as described above.
  • the solar cell adhesive sheets A obtained in the examples and comparative examples were evaluated in terms of formability and high temperature and high humidity test as shown in Table 1 below.
  • a transparent flat glass is overlaid on the embossed surface of the solar cell adhesive sheet, and a polyvinyl fluoride sheet is overlaid on the surface opposite to the embossed surface of the solar cell adhesive sheet to produce a laminated sheet,
  • This laminated sheet was heat-bonded for 15 minutes at a heating temperature of 150 ° C. and a reduced pressure of 10 mmHg, and a transparent flat glass and a polyvinyl fluoride sheet were laminated and integrated with the adhesive sheet for solar cell to produce a laminated body.
  • the obtained laminate was allowed to stand for 2000 hours in an atmosphere having a temperature of 85 ° C. and a relative humidity of 85%, and then the appearance of the laminate was visually observed and evaluated based on the following criteria.
  • the adhesive sheet for solar cell of the present invention does not deteriorate the sealing performance of the solar cell element due to the colorant, can reliably seal the solar cell element over a long period of time, and has stable excellent quality. Therefore, it can be suitably used for the production of a solar cell module that can be maintained.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Photovoltaic Devices (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un film adhésif pour cellule solaire, offrant d'excellentes performances d'adhésion et pouvant sceller de manière stable un élément de cellule solaire pendant une longue période. L'invention concerne plus spécifiquement un film adhésif (A) pour cellule solaire, comprenant trois ou plus de trois couches de résine (1, 1, 1, ...) stratifiées intégralement et comprenant chacune un copolymère d'éthylène et un peroxyde organique. Le film adhésif (A) est caractérisé en ce qu'au moins une des couches de résine (1a), (à l'exclusion des couches de résine (1b) constituant les couches extérieures du film adhésif), prenne la forme d'une couche colorée (1a) contenant 0,5 à 30 parties en masse d'un agent colorant pour 100 parties en masse du copolymère d'éthylène, en ce que la couche colorée (1a) ait une épaisseur totale de 50 à 95 % de l'épaisseur totale du film adhésif pour cellule solaire, et en ce qu'au moins une des couches de résine (1b) (constituant les couches extérieures du film adhésif) contienne 0,05 à 2 parties en masse d'un agent de couplage de type silane pour 100 parties en masse d'un copolymère d'éthylène-acétate de vinyle.
PCT/JP2010/066712 2009-09-28 2010-09-27 Film adhésif pour cellule solaire, procédé de fabrication du film adhésif et module de cellules solaires WO2011037233A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20110731A1 (it) * 2011-05-02 2012-11-03 Giovanni Battista Quagliato "modulo fotovoltaico in forma di elemento architettonico e processo per la realizzazione dello stesso"
JP2014103369A (ja) * 2012-10-24 2014-06-05 Dainippon Printing Co Ltd 封止材シート

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WO2006095762A1 (fr) * 2005-03-08 2006-09-14 Du Pont/Mitsui Polychemicals Co. Ltd. Materiau etancheifiant pour pile solaire
JP2006303233A (ja) * 2005-04-21 2006-11-02 Sekisui Chem Co Ltd 太陽電池用接着シート
JP2009298046A (ja) * 2008-06-13 2009-12-24 Du Pont Mitsui Polychem Co Ltd 多層シート
WO2010005030A1 (fr) * 2008-07-11 2010-01-14 三菱樹脂株式会社 Feuille de face arrière pour pile solaire
JP2010086998A (ja) * 2008-09-29 2010-04-15 Sekisui Chem Co Ltd 太陽電池用封止シート

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JPH11340492A (ja) * 1998-05-21 1999-12-10 Sekisui Chem Co Ltd 太陽電池モジュール及びその製造方法
JP2000091610A (ja) * 1998-09-17 2000-03-31 Dainippon Printing Co Ltd 太陽電池のカバーフィルムおよびその製造方法、およびそのカバーフィルムを用いた太陽電池モジュール
JP2005101380A (ja) * 2003-09-25 2005-04-14 Kyocera Corp 太陽電池モジュールおよびその製造方法
JP5010240B2 (ja) * 2006-11-02 2012-08-29 積水フイルム株式会社 太陽電池用接着シート
JP2009094320A (ja) * 2007-10-10 2009-04-30 Dainippon Printing Co Ltd 太陽電池モジュール用裏面充填材シート
US20090288701A1 (en) * 2008-05-23 2009-11-26 E.I.Du Pont De Nemours And Company Solar cell laminates having colored multi-layer encapsulant sheets

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Publication number Priority date Publication date Assignee Title
WO2006095762A1 (fr) * 2005-03-08 2006-09-14 Du Pont/Mitsui Polychemicals Co. Ltd. Materiau etancheifiant pour pile solaire
JP2006303233A (ja) * 2005-04-21 2006-11-02 Sekisui Chem Co Ltd 太陽電池用接着シート
JP2009298046A (ja) * 2008-06-13 2009-12-24 Du Pont Mitsui Polychem Co Ltd 多層シート
WO2010005030A1 (fr) * 2008-07-11 2010-01-14 三菱樹脂株式会社 Feuille de face arrière pour pile solaire
JP2010086998A (ja) * 2008-09-29 2010-04-15 Sekisui Chem Co Ltd 太陽電池用封止シート

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20110731A1 (it) * 2011-05-02 2012-11-03 Giovanni Battista Quagliato "modulo fotovoltaico in forma di elemento architettonico e processo per la realizzazione dello stesso"
EP2521188A1 (fr) * 2011-05-02 2012-11-07 Giovanni Battista Quagliato Module photovoltaïque ayant la forme d'un élément architectural et son procédé de fabrication
JP2014103369A (ja) * 2012-10-24 2014-06-05 Dainippon Printing Co Ltd 封止材シート

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