WO2012002416A1 - Feuille protectrice pour cellule solaire, et cellule solaire - Google Patents

Feuille protectrice pour cellule solaire, et cellule solaire Download PDF

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Publication number
WO2012002416A1
WO2012002416A1 PCT/JP2011/064874 JP2011064874W WO2012002416A1 WO 2012002416 A1 WO2012002416 A1 WO 2012002416A1 JP 2011064874 W JP2011064874 W JP 2011064874W WO 2012002416 A1 WO2012002416 A1 WO 2012002416A1
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layer
solar cell
protective sheet
film
inorganic layer
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PCT/JP2011/064874
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English (en)
Japanese (ja)
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細谷　陽一
浩也 吉岡
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富士フイルム株式会社
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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
    • B32B27/06—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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier 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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • 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
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • 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
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • 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 protective sheet and a solar cell.
  • the present invention relates to a solar cell front sheet.
  • the present invention is intended to solve the problems of the prior art, and an object thereof is to provide a solar cell protective sheet excellent in all of transmittance, barrier properties, light resistance and adhesion.
  • the technique of adding an inorganic ultraviolet absorber to the surface fluororesin film or providing a layer containing an organic ultraviolet absorber has not only light resistance but also barrier properties and It has been found that the adhesion may be inferior.
  • the inventors of the present application have conducted intensive studies, and as a result, they have reached to provide an inorganic layer having an ultraviolet absorbing ability separately from the fluororesin film.
  • the means of the present invention is a means that can be avoided by those skilled in the art because the number of layers constituting the solar cell protective sheet increases.
  • the present invention has a great significance in that not only the light resistance is improved, but also the barrier property and adhesion are improved.
  • a plastic film has a first inorganic layer, an organic layer, and a second inorganic layer, and the first inorganic layer and the second inorganic layer have different compositions
  • the second inorganic layer includes an oxide containing at least one of cerium, zinc, titanium, iron, zirconium, tungsten, and strontium, and the outermost layer on the side where the second inorganic layer is provided
  • a protective sheet for solar cells which is a fluororesin film.
  • the present invention makes it possible to provide a solar cell protective sheet that is excellent in transmittance, barrier properties, light resistance and adhesion.
  • FIG. 1 is a figure showing an example of an embodiment of a protection sheet for solar cells of the present invention.
  • FIG. 2 is a diagram showing an example of the solar cell element of the present invention.
  • the organic EL element in the present invention refers to an organic electroluminescence element.
  • the solar cell protective sheet of the present invention has a first inorganic layer, an organic layer, and a second inorganic layer (hereinafter sometimes referred to as “inorganic ultraviolet blocking layer”) on a plastic film,
  • the first inorganic layer and the second inorganic layer have different compositions, and the first inorganic layer is an oxide containing at least one of cerium, zinc, titanium, iron, zirconium, tungsten, and strontium.
  • the outermost layer on the side where the second inorganic layer is provided is a fluororesin film.
  • FIG. 1 shows an example of a preferred embodiment of the solar cell protective sheet of the present invention, wherein 1 is a base film, 2 is an organic layer, and 3 is a first inorganic layer (barrier layer). 4 is a second inorganic layer (inorganic ultraviolet blocking layer), 5 is an adhesive layer, and 6 is a fluororesin film.
  • the organic layer 2 and the barrier layer 3 are integrated to improve the barrier ability.
  • the second inorganic layer as the inorganic ultraviolet blocking layer also serves as a barrier layer, and synergistically improves the barrier property.
  • the solar cell protective sheet of the present invention may have other constituent layers within a range not departing from the gist of the present invention.
  • the protective sheet for a solar cell of the present invention is preferably configured so that the thickness of the entire sheet is 50 ⁇ m or more, and more preferably 100 ⁇ m or more.
  • the upper limit is not particularly defined, but can be, for example, 2000 ⁇ m or less.
  • the solar cell protective sheet of the present invention preferably has a total light transmittance of 85% or more, and preferably 90% or more.
  • the reflectance in the present invention is preferably 15% or less, more preferably 10% or less. By setting it as such a range, it becomes possible to improve the conversion efficiency of a solar cell element more. (Measurement method of reflectance) Using Shimadzu UV2550, diffuse reflectance was measured using a standard white plate as barium sulfate.
  • a polyester film is preferably used as the base film.
  • the type of polyester used for the polyester base film is not particularly defined, but aromatic polyester is preferable, polyethylene terephthalate (PET), polymethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN). Is more preferable, and PET or PEN is more preferable.
  • the mixture of 2 or more types of polyester may be sufficient.
  • the number average molecular weight of the polyester is preferably 13,000 to 50,000, and more preferably 15,000 to 35,000.
  • the thickness of the polyester base film is preferably 5 ⁇ m to 1000 ⁇ m, and more preferably 10 ⁇ m to 500 ⁇ m. That is, the film of the present invention includes both a film having a thickness of less than 250 ⁇ m and a sheet having a thickness of 250 ⁇ m or more. By setting it as such thickness, the improvement of dimensional stability and the nick of a film become difficult to occur, and it becomes possible to supply a protective sheet for a solar cell having a stable barrier ability.
  • Organic layer is preferably an organic layer containing an organic polymer as a main component.
  • the main component means that the first component of the component constituting the organic layer is an organic polymer, and usually 80% by weight or more of the component constituting the organic layer is an organic polymer.
  • the organic polymer include polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, and polyurethane.
  • the organic layer in the present invention preferably has a glass transition temperature (Tg) of 100 ° C. or lower, and more preferably 85 ° C. or lower.
  • Tg glass transition temperature
  • the lower limit is not particularly defined, but is preferably ⁇ 20 ° C. or higher.
  • the organic layer in the present invention is preferably formed by curing a polymerizable composition containing a polymerizable compound.
  • the polymerizable compound is preferably a radical polymerizable compound and / or a cationic polymerizable compound having an ether group as a functional group, more preferably a compound having an ethylenically unsaturated bond at the terminal or side chain, and / or A compound having an epoxy or oxetane at the terminal or side chain. Of these, compounds having an ethylenically unsaturated bond at the terminal or side chain are preferred.
  • Examples of compounds having an ethylenically unsaturated bond at the terminal or side chain include (meth) acrylate compounds, acrylamide compounds, styrene compounds, maleic anhydride, etc., (meth) acrylate compounds and / or Styrenic compounds are preferred, and (meth) acrylate compounds are more preferred.
  • (meth) acrylate that can be used in the present invention, (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and the like are preferable.
  • styrene compound styrene, ⁇ -methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxystyrene, 4-carboxystyrene and the like are preferable.
  • the polymerizable composition may contain a polymerization initiator.
  • a photopolymerization initiator When a photopolymerization initiator is used, its content is preferably 0.1 mol% or more, more preferably 0.5 to 2 mol% of the total amount of the polymerizable compounds.
  • photopolymerization initiator examples include Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure, commercially available from Ciba Specialty Chemicals. 819), Darocure series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Ezacure series (eg, Ezacure TZM, Ezacure, commercially available from Lamberti) TZT, Ezacure KTO46, etc.).
  • Irgacure series for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irg
  • a method for forming the organic layer is not particularly defined, but for example, it can be formed by a solution coating method or a vacuum film forming method.
  • the solution coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a slide coating method, or a method described in US Pat. No. 2,681,294. It can be applied by an extrusion coating method using a hopper.
  • Film-forming methods such as vapor deposition and plasma CVD, are preferable.
  • a polymer may be applied by solution, or a hybrid coating method containing an inorganic substance as disclosed in Japanese Patent Application Laid-Open Nos. 2000-323273 and 2004-25732 may be used.
  • a composition containing a polymerizable compound is usually cured by irradiation with light, but the irradiation light is usually ultraviolet light from a high-pressure mercury lamp or a low-pressure mercury lamp.
  • the radiation energy is preferably 0.1 J / cm 2 or more, 0.5 J / cm 2 or more is more preferable.
  • a (meth) acrylate compound is employed as the polymerizable compound, the polymerization is inhibited by oxygen in the air, and therefore it is preferable to reduce the oxygen concentration or oxygen partial pressure during polymerization.
  • the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less.
  • the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. Further, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of 0.5 J / cm 2 or more under a reduced pressure condition of 100 Pa or less.
  • the polymerization rate of the polymerizable compound constituting the organic layer is preferably 85% or more, more preferably 88% or more, further preferably 90% or more, and particularly preferably 92% or more.
  • the polymerization rate here means the ratio of the reacted polymerizable group among all the polymerizable groups (for example, acryloyl group and methacryloyl group) in the polymerizable composition.
  • the polymerization rate can be quantified by an infrared absorption method.
  • the thickness of the organic layer in the present invention is preferably in the range of 0.3 ⁇ m to 10 ⁇ m, and more preferably in the range of 5 ⁇ m to 10 ⁇ m.
  • the smoothness of the organic layer is preferably less than 1 nm and more preferably less than 0.5 nm as an average roughness (Ra value) of 1 ⁇ m square.
  • the surface of the organic layer is required to be free of foreign matters such as particles and protrusions. For this reason, it is preferable that the organic layer is formed in a clean room.
  • the degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less. A higher hardness of the organic layer is preferable, but if it is too high, problems such as bending resistance occur.
  • the hardness of the organic layer can be expressed as a microhardness based on the nanoindentation method.
  • the microhardness of the organic layer is 0.03 to 0.5 GPa, and more preferably 0.03 to 0.3 Pa. By setting it as such a range, it becomes possible to improve bending resistance and to improve the scratch resistance to a level at which there is no practical problem.
  • the first inorganic layer in the present invention is a layer that serves as a barrier layer.
  • the barrier layer is usually a thin film layer made of a metal compound.
  • any method can be used as long as the target thin film can be formed.
  • PVD physical vapor deposition method
  • CVD chemical vapor deposition methods
  • liquid phase growth method such as plating and a sol-gel method.
  • the component contained in the barrier layer is not particularly limited as long as it satisfies the above performance.
  • the barrier layer of the present invention preferably consists essentially of these components.
  • “substantially” means, for example, that it is not included as an intentionally added component, and means that components such as impurities are not excluded. For example, it means that 99% by weight or more is composed of these components.
  • the smoothness of the barrier layer formed according to the present invention is preferably less than 1 nm, more preferably 0.5 nm or less, as an average roughness (Ra value) of 1 ⁇ m square.
  • the barrier layer is preferably formed in a clean room.
  • the degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less.
  • the thickness of the barrier layer is not particularly limited, but is usually 5 to 500 nm, preferably 50 to 400 nm, more preferably 100 to 200 nm per layer.
  • the organic layer and the barrier layer can be laminated by sequentially forming the organic layer and the barrier layer repeatedly according to a desired layer structure.
  • the barrier layer is formed by a vacuum film formation method such as a sputtering method, a vacuum vapor deposition method, an ion plating method, or a plasma CVD method
  • the organic layer is also preferably formed by a vacuum film formation method such as the flash vapor deposition method.
  • a vacuum film formation method such as the flash vapor deposition method.
  • an organic layer or a barrier layer on the surface of a plastic film.
  • a barrier layer or an organic layer on the surface of the organic layer or barrier layer.
  • the structure which provides a 2nd inorganic layer (ultraviolet absorption layer) in the surface or interlayer of these layers is also preferable.
  • the number of organic layers and barrier layers stacked is not particularly defined, but is usually 3 to 30 layers.
  • the second inorganic layer in the present invention is a layer corresponding to the inorganic ultraviolet blocking layer.
  • the inorganic ultraviolet blocking layer contains an oxide containing at least one of cerium, zinc, titanium, iron, zirconium, tungsten and strontium, and preferably contains an oxide containing at least one selected from cerium, zinc and titanium. Including.
  • the composition constituting each inorganic ultraviolet blocking layer may be the same or different.
  • the inorganic ultraviolet blocking layer of the present invention preferably consists essentially of these components.
  • “substantially” means, for example, that it is not included as an intentionally added component, and means that components such as impurities are not excluded.
  • the inorganic ultraviolet blocking layer any method can be used as long as it can form a target thin film.
  • a physical vapor deposition method PVD
  • PVD physical vapor deposition method
  • CVD chemical vapor deposition methods
  • liquid phase growth method such as plating and a sol-gel method.
  • the smoothness of the inorganic ultraviolet blocking layer formed according to the present invention is preferably less than 1 nm, more preferably 0.5 nm or less, as an average roughness (Ra value) of 1 ⁇ m square.
  • the inorganic ultraviolet blocking layer is preferably formed in a clean room.
  • the degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less.
  • the thickness of the inorganic ultraviolet blocking layer is not particularly limited, it is usually 5 to 1500 nm, preferably 50 to 1000 nm, more preferably 200 to 500 nm per layer.
  • the fluororesin film is usually adhered to an adjacent layer with an adhesive.
  • the adhesive layer in the present invention is not particularly defined as long as it contains an adhesive.
  • an ultraviolet (UV) curable adhesive or a thermosetting adhesive can be preferably used, and an ultraviolet curable adhesive is more preferable.
  • the type of the adhesive is not particularly defined, but examples of the UV curable adhesive include epoxy-based, acrylate-based, and urethane-based examples, and urethane-based adhesives are more preferable.
  • examples of the thermosetting adhesive include epoxy-based, acrylate-based, and urethane-based examples, and urethane-based adhesives are more preferable.
  • an easy adhesion layer may be provided.
  • the easy-adhesion layer is a kind of a layer called a primer layer, an undercoat layer, an undercoat layer, or the like, and is a layer provided for the purpose of adjusting the interface state between layers. By providing such a layer, there is an advantage of particularly improving the adhesiveness.
  • Fluororesin film is a resin film mainly composed of a fluororesin.
  • the fluororesin constituting the fluororesin film include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA) made of a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, tetrafluoroethylene and hexafluoropropylene, and the like.
  • FEP tetrafluoroethylene and perfluoroalkyl vinyl ether and hexafluoropropylene
  • EPE tetrafluoroethylene and ethylene or propylene
  • PCTFE polychlorotrifluoroethylene resin
  • ECTFE chlorotrifluoroethylene
  • PVDF vinylidene fluoride resin
  • PVF vinyl fluoride resin
  • polyvinyl fluoride resin PVF
  • ETFE tetrafluoroethylene and ethylene or propylene
  • the fluororesin film of the present invention may contain a component other than the fluororesin, but it is preferable that 50% by weight or more of the component is composed of a fluororesin. Moreover, it is preferable that the fluororesin film of the present invention does not substantially contain fine particles.
  • “substantially” means, for example, that it is not included as an intentionally added component, and means that components such as impurities are not excluded. For example, it means that 99% by weight or more is composed of these components.
  • the thickness of the fluororesin film in the present invention is preferably in the range of 10 ⁇ m to 1000 ⁇ m, and more preferably in the range of 20 ⁇ m to 500 ⁇ m.
  • the solar cell element of the present invention refers to a system that converts sunlight into electricity.
  • An example of the structure is shown in FIG. That is, the front sheet layer 7, the filling adhesive resin layer 8, the solar cell element main part 9, the filling adhesive resin layer 10, and the back sheet layer 11 are the basic configuration from the side where sunlight enters.
  • the solar cell protective sheet of the present invention is preferably used for the front sheet layer, but can also be used for the back sheet layer and the like.
  • This solar cell element is incorporated in the roof of a house, or is installed in farm ponds, ranches, wastewater and sewage treatment facilities, volcanoes and hot spring areas, buildings and fences, and used for electronic parts.
  • Some of the solar cell modules transmit light called daylighting type or see-through type and are used for soundproof walls such as windows, highways and railways. In this invention, it can be set as a particularly flexible type.
  • the solar cell element in which the solar cell protective sheet of the present invention is preferably used is not particularly limited, but for example, a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, or a tandem structure type Amorphous silicon-based solar cell elements composed of, etc., III-V compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI group compound semiconductor solar cells such as cadmium tellurium (CdTe) I- such as element, copper / indium / selenium system (so-called CIS system), copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur system (so-called CIGS system), etc.
  • III-V compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP)
  • II-VI group compound semiconductor solar cells such
  • the solar cell element is a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur.
  • CIS system copper / indium / selenium system
  • CIGS system copper / indium / gallium / selenium system
  • CIGSS system group I-III-VI compound semiconductor solar cell element
  • CIGSS system group I-III-VI compound semiconductor solar cell element
  • Comparative Example 1 The following polymerizable compounds (total 14 parts by weight) and a polymerization initiator (Ciba Specialty Chemicals, IRGACURE 907, 1 part by weight) on polyethylene terephthalate having a thickness of 100 ⁇ m (Teonex Q65FA, manufactured by Teijin DuPont), 2-butanone (1 part by weight) 185 parts by weight) was applied with a wire bar, and cured by irradiation with an ultraviolet ray irradiation amount of 0.5 J / cm 2 in an atmosphere of 100 ppm nitrogen to produce an organic layer.
  • the film thickness of the organic layer was 500 nm.
  • Al 2 O 3 was formed on the surface of the organic layer by vacuum sputtering (reactive sputtering) so as to have a film thickness of 40 nm. Further, an organic layer was provided thereon in the same manner as described above to obtain a film (A).
  • composition of polymerizable compound Compounds A to D shown below were used in the ratios shown below.
  • An ethylene-tetrafluoroethylene copolymer film (Nephron ETFE film (EF-0050) made by Daikin) which is a fluororesin film having a thickness of 50 ⁇ m on the surface of the film (A) on which the Al 2 O 3 layer is provided. ) Were laminated via a urethane-based adhesive to obtain a sample 101.
  • Comparative Example 2 In Comparative Example 1, Sample 102 was obtained in the same manner as Comparative Example 1, except that a benzotriazole ultraviolet absorber (manufactured by BASF, TINUVIN 328) was added to the urethane adhesive in a proportion of 25% by weight.
  • a benzotriazole ultraviolet absorber manufactured by BASF, TINUVIN 328
  • Comparative Example 3 In Comparative Example 1, 25 wt. Of CeO 2 fine particles dispersed in a butanol solvent (Taki Chemical Co., Ltd., Nidral U-15, which is a water-dispersed CeO 2 suspension) replaced with a butanol solvent in a urethane adhesive. A sample 103 was obtained in the same manner except that the coating solution added so as to have a ratio of% was used.
  • a butanol solvent Teaki Chemical Co., Ltd., Nidral U-15, which is a water-dispersed CeO 2 suspension
  • Example 1 In Comparative Example 1, CeO 2 was vacuum sputtered (RF sputtering: target is CeO 2 ) so as to have a film thickness of 300 nm on the organic layer of the film (A), and then the organic layer was formed in the same manner. Sample 105 was obtained.
  • RF sputtering target is CeO 2
  • Example 2 In Comparative Example 1, except that an organic layer was formed after vacuum sputtering (RF sputtering: target is TiO 2 ) of TiO 2 so as to have a film thickness of 300 nm on the organic layer of film (A). Sample 106 was obtained.
  • RF sputtering target is TiO 2
  • Example 3 In Comparative Example 1, Sample 107 was similarly prepared except that an organic layer was formed after vacuum sputtering (RF sputtering: target was ZnO) of ZnO so as to have a film thickness of 300 nm on the organic layer of the film (A).
  • RF sputtering: target was ZnO vacuum sputtering
  • ZnO ZnO
  • Example 4 A sample 108 was obtained in the same manner as in Example 1, except that the film thickness of CeO 2 was changed to 30 nm.
  • Example 5 A sample 109 was obtained in the same manner as in Example 1 except that the film thickness of CeO 2 was changed to 1200 nm.
  • Sample 110 was prepared in the same manner as in Comparative Example 1 except that a simple Ag was deposited by electron beam deposition (EB deposition) so that the film thickness was 300 nm on the organic layer of the film (A), and then a fluororesin film was bonded. Obtained.
  • EB deposition electron beam deposition
  • Example 6 In Example 1, instead of vacuum sputtering (reactive sputtering) with Al 2 O 3 , a sample was prepared in the same manner except that CeO 2 was vacuum sputtered (RF sputtering: target was CeO 2 ) so as to have a film thickness of 40 nm. 111 was obtained.
  • Total light transmittance According to JIS K7361-1, the total light transmittance was measured using a haze meter (NDH 5000 manufactured by Nippon Denshoku Industries Co., Ltd.).
  • the adhesion of the protective film was evaluated by a cross-cut test based on JIS K5400. On the surface of the protective film, cuts of 90 ° with respect to the film surface were made with a cutter knife at intervals of 1 mm, and 100 grids with intervals of 1 mm were produced. A 2 cm wide Mylar tape [manufactured by Nitto Denko, polyester tape (No. 31B)] was applied thereto, and the tape attached using a tape peeling tester was peeled off. Of the 100 grids on the protective film, the number of cells remaining without peeling (n) was counted.
  • Example 5 Creation of solar cell Using ethylene vinyl acetate (EVA) resin film as an adhesive, samples 105 to 108 having the above-described examples were used as front sheets, and Example 1 of JP2009-99973A was used. A solar cell was prepared by pasting on the surface of the CIS film of the CIS-based thin film solar cell described. It was confirmed to operate as a solar cell.
  • EVA ethylene vinyl acetate
  • Plastic film 2 Organic layer 3 First inorganic layer (barrier layer) 4 Second inorganic layer (inorganic UV absorbing layer) 5 Adhesive Layer 6 Fluoropolymer Film 7 Front Sheet Layer 8 Filled Adhesive Resin Layer 9 Solar Cell Element Essential Part 10 Filled Adhesive Resin Layer 11 Back Sheet Layer

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
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  • Laminated Bodies (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne une feuille protectrice pour cellule solaire, dont la transmissivité, les propriétés de barrière, la résistance à la lumière et les propriétés d'adhésion sont excellentes. Elle concerne spécifiquement une feuille protectrice pour une cellule solaire, qui comprend une première couche inorganique, une couche organique et une seconde couche inorganique qui sont toutes formées sur une pellicule plastique, la première couche inorganique et la seconde couche inorganique ayant des compositions chimiques différentes l'une de l'autre, la première couche inorganique comprenant un oxyde contenant au moins un élément sélectionné parmi le cérium, le zinc, le titane, le fer, le zirconium, le tungstène et le strontium, et la couche de surface la plus extérieure formée sur un côté sur lequel la seconde couche inorganique a été formée étant une pellicule de fluororésine.
PCT/JP2011/064874 2010-07-02 2011-06-29 Feuille protectrice pour cellule solaire, et cellule solaire WO2012002416A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010152156A JP2012015408A (ja) 2010-07-02 2010-07-02 太陽電池用保護シートおよび太陽電池
JP2010-152156 2010-07-02

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WO2012002416A1 true WO2012002416A1 (fr) 2012-01-05

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000068536A (ja) * 1998-08-26 2000-03-03 Dainippon Printing Co Ltd 太陽電池モジュール
JP2000138388A (ja) * 1998-10-29 2000-05-16 Dainippon Printing Co Ltd 太陽電池モジュ−ル用表面保護シ−トおよびそれを使用した太陽電池モジュ−ル
JP2002203980A (ja) * 2000-12-28 2002-07-19 Canon Inc 太陽電池モジュール、太陽電池アレイ、建材一体型太陽電池、壁材一体型太陽電池、及び屋根一体型太陽電池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000068536A (ja) * 1998-08-26 2000-03-03 Dainippon Printing Co Ltd 太陽電池モジュール
JP2000138388A (ja) * 1998-10-29 2000-05-16 Dainippon Printing Co Ltd 太陽電池モジュ−ル用表面保護シ−トおよびそれを使用した太陽電池モジュ−ル
JP2002203980A (ja) * 2000-12-28 2002-07-19 Canon Inc 太陽電池モジュール、太陽電池アレイ、建材一体型太陽電池、壁材一体型太陽電池、及び屋根一体型太陽電池

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