JP2014194985A - Protective sheet for solar cell, method for producing the same, and solar cell module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a protective sheet for a solar cell in which a substrate is less likely to peel off from a sealing material, a method for producing the same, and a solar cell module including the protective sheet for a solar cell.SOLUTION: The protective sheet for a solar cell includes a substrate 11, a first resin layer 12 laminated on at least one surface of the substrate 11, and a second resin layer 13 laminated on that surface of the first resin layer 12 which is opposite to the substrate side. The first resin layer 12 contains a component having an epoxy group, and the second resin layer 13 contains a polyamide-based resin.

Description

  The present invention relates to a solar cell protective sheet used as a surface protective sheet or a back surface protective sheet of a solar cell module, a method for producing the same, and a solar cell module using the solar cell protective sheet.

  Solar cell modules that convert solar light energy into electrical energy are attracting attention as clean energy sources that can generate electricity without emitting carbon dioxide in response to environmental problems such as air pollution and global warming.

  Generally, a solar cell module is composed of a solar cell made of crystalline silicon, amorphous silicon, or the like that performs photoelectric conversion, a sealing material (filling layer) made of an electrical insulator that seals the solar cell, and the surface of the sealing material. It is comprised from the surface protection sheet (front sheet) laminated | stacked on (light-receiving surface) and the back surface protection sheet (back sheet) laminated | stacked on the back surface of the sealing material. In order to provide the solar module with the weather resistance and durability that can withstand long-term use outdoors and indoors, the solar cells and sealing material are protected from wind, rain, moisture, dust, mechanical shock, etc. It is necessary to keep the inside of the battery module sealed from the outside air. For this reason, the protection sheet for solar cells is required to have moisture resistance and weather resistance that can withstand long-term use.

  In order to meet such requirements, Patent Documents 1 and 2 include a carrier material selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthenate (PEN), or ethylene tetrafluoroethylene copolymer (ETFE). And a technology using a plastic composite comprising a polyamide layer adjacent to both sides of a carrier material as a protective sheet for a solar cell is disclosed.

Special table 2010-527142 gazette Special table 2010-528454 gazette

  According to Patent Documents 1 and 2, the polyamide layer has high adhesiveness to the sealing material of the solar cell module, has excellent insulating properties, and has high weather resistance. Thus, the polyamide layer has excellent properties, but the adhesion to the carrier material is low, peeling occurs at the interface between the carrier material and the polyamide layer, and moisture or the like easily enters from the interface. As a result, there was a problem that the solar cells in the sealing material could not be sufficiently protected.

  The present invention has been made in view of such a situation, and a solar cell protective sheet whose base material is difficult to peel off from a sealing material, a method for producing the sheet, and a solar cell including such a solar cell protective sheet. The purpose is to provide modules.

  In order to achieve the above object, the present invention provides, firstly, a base material, a first resin layer laminated on at least one surface of the base material, and the base material in the first resin layer. A protective sheet for a solar cell comprising a second resin layer laminated on the surface opposite to the side, wherein the first resin layer contains a component having an epoxy group, and the second resin layer is a polyamide Provided is a protective sheet for a solar cell, characterized by containing an epoxy resin (Invention 1).

  In the said invention (invention 1), it is preferable that the component which has the said epoxy group consists of resin containing the copolymer formed by copolymerizing ethylene and glycidyl (meth) acrylate (invention 2).

  In the said invention (invention 1 and 2), it is preferable that the said polyamide-type resin contains the 1 type (s) or 2 or more types chosen from the group which consists of the polyamide 9T, the polyamide 11, and the polyamide 12 (invention 3).

  In the above inventions (Inventions 1 to 3), the first resin layer and the second resin layer are preferably formed by coextrusion coating on the substrate (Invention 4). ).

  In the said invention (invention 1 to 4), it is preferable that the surface in which the said 1st resin layer in the said base material is laminated | stacked is given the easily bonding process (invention 5).

  In the said invention (invention 1 to 5), it is preferable that said 2nd resin layer is a layer adhere | attached with respect to the sealing material which comprises a solar cell module (invention 6).

  Secondly, the present invention provides a substrate, a first resin layer laminated on at least one surface of the substrate, and a first layer laminated on a surface opposite to the substrate side in the first resin layer. A method for producing a protective sheet for a solar cell comprising two resin layers, the first material containing a component having an epoxy group and the second material containing a polyamide-based resin, The first resin layer and the second material formed using the first material by coextrusion coating on the substrate such that the first material is proximal to the substrate. The manufacturing method of the protective sheet for solar cells characterized by laminating | stacking said 2nd resin layer formed using on the said base material (invention 7) is provided.

  Thirdly, the present invention is a solar cell module comprising a solar cell, a sealing material that encloses the solar cell, and two protective members stacked on each of the main surfaces of the sealing material, At least one of the protective members is provided with a solar cell protective sheet according to the above invention (Invention 1 to 5) (Invention 8).

  Since the solar cell protective sheet according to the present invention has the first resin layer rich in reactivity with the base material between the second resin containing the polyamide-based resin and the base material, The separation of one resin layer is suppressed. Therefore, even when the solar cell protective sheet according to the present invention is incorporated in a solar cell module, the base material is unlikely to peel off from the sealing material in the solar cell module, and moisture or the like hardly enters the sealing material. Therefore, the solar cell module provided with the solar cell protective sheet according to the present invention is unlikely to deteriorate.

It is a schematic sectional drawing of the protection sheet for solar cells which concerns on one Embodiment of this invention. It is a schematic sectional drawing of the protection sheet for solar cells provided with the fluororesin layer based on other embodiment of this invention. It is a schematic sectional drawing of the protection sheet for solar cells provided with the vapor deposition layer and the fluororesin layer based on other embodiment of this invention. It is a schematic sectional drawing of the protection sheet for solar cells provided with the contact bonding layer and metal sheet based on other embodiment of this invention. It is a schematic sectional drawing of the solar cell module which concerns on one Embodiment of this invention. It is a schematic sectional drawing of the solar cell module which the front seat and back seat | sheet concerning other embodiment of this invention consist of the protection sheet for solar cells which concerns on this embodiment.

Hereinafter, embodiments of the present invention will be described.
1. Protective sheet for solar cell As shown in FIG. 1, a protective sheet 1 for solar cell according to an embodiment of the present invention is laminated on one surface (upper surface in FIG. 1) of the substrate 11 and the substrate 11. The 1st resin layer 12 and the 2nd resin layer 13 laminated | stacked on the surface on the opposite side to the base material 11 side in the 1st resin layer 12 are provided. In one specific example, the solar cell protective sheet 1 has a second resin layer 13 that functions as a heat-fusible layer to a sealing material, and a solar cell module surface protective sheet (front sheet) or back surface protective sheet. It is used as a (back sheet).

(1) Base material The base material 11 has only to be electrically insulative and can be laminated with the second resin layer. Usually, a material mainly composed of a resin film is used.

  As a resin film used for the base material 11, what is generally used as the resin film in the solar cell module backsheet is selected. Specific examples of such resin films include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT), polycarbonate resins, and polystyrene resins. Examples thereof include a film or sheet made of a resin such as a resin, a polyacrylonitrile resin, or a polyvinyl chloride resin. Among these resin films, a film made of a polyester resin is preferable, and a PET film is particularly preferable.

  In addition, the said resin film may contain various additives, such as a pigment, a ultraviolet absorber, a ultraviolet stabilizer, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and an antiblocking agent, as needed. Examples of the pigment include titanium dioxide and carbon black. Examples of the ultraviolet absorber include benzophenone series, benzotriazole series, oxalic acid anilide series, cyanoacrylate series, and triazine series.

  Here, when using the solar cell protective sheet 1 according to this embodiment as a back sheet of a solar cell module, the resin film preferably contains a pigment that reflects visible light. Moreover, when using the solar cell protective sheet 1 according to the present embodiment as a front sheet of a solar cell module, it is preferable not to contain a pigment that reduces the light transmittance in the visible light region, thereby improving the weather resistance. It is more preferable to contain an ultraviolet absorber for the purpose.

  The surface of the resin film on the side where the second resin layer 13 is laminated is subjected to surface treatment such as corona treatment, plasma treatment, and primer treatment in order to improve adhesion with the first resin layer 12 described later. It is preferable to apply.

  The thickness of the base material 11 is appropriately set based on the electrical insulation required for the solar cell module. For example, when the substrate 11 is a resin film, the thickness is preferably 10 μm or more and 300 μm or less. More specifically, when the substrate 11 is a PET film, the thickness is preferably 10 μm or more and 300 μm or less, and 20 μm or more and 250 μm or less from the viewpoint of electrical insulation and weight reduction. It is more preferable that it is 30 μm or more and 200 μm or less.

(2) 1st resin layer The 1st resin layer 12 in this embodiment is arrange | positioned between said base material 11 and the 2nd resin layer 13 mentioned later, and the base material 11 is 2nd resin. This is intended to make it difficult for moisture or the like to enter the second resin layer 13 from the interface on the substrate 11 side or to peel off from the layer 13.

  The first resin layer 12 in the present embodiment includes a component having an epoxy group. The first resin layer 12 is easily wetted with respect to the surface on which the first resin layer 12 of the substrate 11 is to be laminated, that is, the adherend surface, based on the epoxy group of the component. For this reason, the true contact area between the base material 11 and the first resin layer 12 increases, and the adhesion at these interfaces tends to increase. Moreover, the material which comprises the 1st resin layer 12 may spread wet so that it may enter into the recessed part in the to-be-adhered surface of the base material 11, and in this case, based on the anchoring effect (anchor effect), the base material 11 and the first The adhesion of the interface with the resin layer 12 increases. Further, when the substrate 11 includes a component having a functional group (carboxyl group, amino group, etc.) capable of reacting with an epoxy group, the component located on the adherend surface of the substrate 11 is the first resin layer. 12 can be combined with the component having an epoxy group contained in 12. Such a binding reaction contributes to increasing the adhesion between the substrate 11 and the first resin layer 12. Examples of the component that can react with the epoxy group include polyester resins, and specifically, PET and PEN.

  Thus, since the interaction at the interface between the base material 11 and the first resin layer 12 becomes large, peeling at this interface is unlikely to occur. Furthermore, since the interaction at the interface between the first resin layer 12 and the second resin layer 13 also increases as will be described later, peeling at this interface is less likely to occur. Thus, it becomes difficult for the base material 11 and the 2nd resin layer 13 to peel, and it becomes difficult to deteriorate the quality of the photovoltaic cell in a solar cell module provided with the protection sheet 1 for solar cells.

  Hereinafter, the details of the first material that is the material for providing the first resin layer 12 will be described. The first material includes a component that gives a component having an epoxy group contained in the first resin layer 12 (hereinafter referred to as “epoxy group-containing component”). The first material may be composed of an epoxy group-containing component.

  The kind of the epoxy group-containing component contained in the first material is not particularly limited. Specific examples of the epoxy group-containing component include a copolymer of a monomer having a polymerizable double bond and a monomer having an epoxy group and a polymerizable double bond or an oligomer thereof.

  Examples of the monomer having a polymerizable double bond include acyclic olefins such as ethylene and propylene; cyclic olefins such as norbornene and cyclopentadiene; styrene, p-methylstyrene, α-methylstyrene, Styrenes such as vinyltoluene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Stearyl (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, (meth) acrylic acid Dimethylaminoethyl, benzoyl (meth) acrylate Xylethyl, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, polyethylene glycol acrylate, polypropylene (meth) acrylate Acrylic acid esters such as glycol; diesters of unsaturated dibasic acids such as dimethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl maleate, dibutyl maleate, dioctyl maleate, methyl ethyl itaconate; (meth) Amides such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-substituted acrylamide, N-substituted methacrylamide, unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone; vinyl acetate And vinyl esters such as vinyl butyrate; vinyl ethers such as methyl vinyl ether and butyl vinyl ether.

  In the present specification, methyl (meth) acrylate means both methyl acrylate and methyl methacrylate. The same applies to other similar terms.

  Examples of the monomer having an epoxy group and a polymerizable double bond include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl acrylic acid. Glycidyl and β-methylglycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-6,7-epoxypentyl, α-ethylacrylic acid-6,7-epoxypentyl , (Meth) acrylic acid-3,4-epoxycyclohexyl, lactone-modified (meth) acrylic acid-3,4-epoxycyclohexyl, and 1-vinyl-3,4-epoxycyclohexane. A compound having two or more alicyclic epoxy groups in the molecule, one polymerizable unsaturated double bond in the molecule, and one group reactive with one alicyclic epoxy group; An epoxy group-containing ethylenically unsaturated monomer obtained by reacting is also an example of a monomer having an epoxy group and a polymerizable double bond.

  Among these, the monomer having a polymerizable double bond preferably contains ethylene as one kind thereof, and the monomer having an epoxy group and a polymerizable double bond preferably contains glycidyl (meth) acrylate as one kind thereof. More preferably, the epoxy group-containing component has a structure obtained by copolymerizing these monomers, and the epoxy group-containing component particularly preferably contains a copolymer containing these monomers.

  The first material may contain a crosslinking agent. The type of the crosslinking agent is arbitrary, and an organic peroxide such as dicumyl peroxide or a compound having an isocyanate group is typical. However, if the crosslinking agent is excessively contained, the first resin layer 12 formed from the first material loses its thermoplasticity. Therefore, when thermoplasticity is required, the content of the crosslinking agent has an appropriate upper limit. Is set.

  From the viewpoint of ease of manufacture, especially ease of manufacture by coextrusion coating, which will be described later, and handleability, the first resin layer 12 preferably has thermoplasticity. As described above, ethylene and (meth) acrylic It is particularly preferable to contain a copolymer having glycidyl acid as a monomer.

  When the first material contains a copolymer having ethylene and glycidyl (meth) acrylate as monomers as an epoxy group-containing component, the molecular weight (weight average molecular weight) of the copolymer is not particularly limited.

  When the first resin layer 12 has thermoplasticity, it is obtained by heating the first resin layer 12 at a temperature of 230 ° C. and a load of 2.16 kgf in accordance with JIS K7210: 1999 (ISO 1133: 1997). The melt mass flow rate of the resin material obtained is preferably 1 g / 10 min or more and 20 g / 10 min or less from the viewpoint of workability and the like. In particular, when the first resin layer 12 is formed by extrusion coating, the melt mass flow rate of the resin material is preferably 2 g / 10 min or more and 10 g / 10 min or less from the viewpoint of stably forming the first resin layer 12.

  The first material is a coloring material such as titanium dioxide, an anti-blocking agent such as silica particles, an ultraviolet absorber such as benzophenone, an ultraviolet stabilizer, a flame retardant, a plasticizer, an antistatic agent, or a lubricant, if necessary. Various additives may be included.

  The thickness of the first resin layer 12 is not particularly limited. From the viewpoint of electrical insulation and weight reduction, it is preferably 5 μm or more and 150 μm or less, more preferably 10 μm or more and 100 μm or less, and further preferably 15 μm or more and 75 μm or less.

(3) Second resin layer In one specific example, the second resin layer 13 in the present embodiment is bonded to the encapsulant, so that the solar cell protective sheet 1 including the base material 11 is solar. It is for fixing to a battery module.

  The second resin layer 13 contains a polyamide resin. As described above, the polyamide-based resin has high adhesion to the sealing material of the solar cell module, has excellent insulating properties, and also has high weather resistance. In addition, since it has hydrolysis resistance, even if moisture enters the second resin layer 13, the material constituting the second resin layer 13 is unlikely to deteriorate due to the moisture. .

  Moreover, the amide bond contained in the polyamide resin can react with the epoxy group. Therefore, chemical interaction tends to occur at the interface between the second resin layer 13 and the first resin layer 12, and peeling at this interface is unlikely to occur.

  The case where the second resin layer 13 in the present embodiment is formed of a second material containing a polyamide-based resin will be described below as a specific example. The polyamide-based resin contained in the second material is a homopolymer or copolymer having an amide bond in the main chain, and the monomer directly involved in the formation of the amide bond in this polymer is: In some cases, an amide bond is formed alone (in this case, it can be a single polymer), and in other cases, an amide bond is formed by a plurality of compounds (in this case, it is a copolymer). is there. For example, when the monomer is a lactam or an aminocarboxylic acid, a homopolymer of the monomer can be formed. Examples of the amide bond formed by a plurality of compounds include a combination of an aliphatic diamine and an aliphatic dicarboxylic acid (in this case, an aliphatic polyamide is obtained), a combination of an aromatic diamine and an aliphatic dicarboxylic acid. A combination of an aliphatic diamine and an aromatic dicarboxylic acid (in these cases a partially aromatic polyamide is obtained) and a combination of an aliphatic diamine and an aromatic dicarboxylic acid (in these cases a wholly aromatic polyamide) Is obtained).

  Specific examples of the above lactams or aminocarboxylic acids include lactams such as ε-caprolactam, undecane lactam, lauryl lactam; aliphatic aminocarboxylic acids such as aminocaproic acid, aminoundecanoic acid, aminolauric acid; para-aminomethylbenzoic acid An aromatic aminocarboxylic acid such as When the monomer that gives the polyamide-based resin contained in the second material contains lactam and / or aminocarboxylic acid, the lactam and / or aminocarboxylic acid according to the monomer is composed of one kind of compound. It may be composed of a plurality of types of compounds.

  The aliphatic diamine may be linear, branched, or alicyclic. Specific examples of linear or linear aliphatic diamines include ethylenediamine, 1-methylethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentanediamine, hexanediamine, and 3-methylpentane-1,5-diamine. , Aliphatic diamines such as nonane diamine, decamethylene diamine, undecamethylene diamine, and dodecamethylene diamine. Specific examples of the alicyclic diamine include cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and the like. Examples of the aromatic diamine include m-xylylenediamine, p-xylylenediamine, p-bis (2-aminoethyl) benzene, m-phenylenebisamine, p-phenylenebisamine and the like. When the monomer that gives the polyamide-based resin contained in the second material contains diamine and dicarboxylic acid, the diamine according to the monomer may be composed of one type of compound, or a plurality of types of compounds. You may be comprised from the compound.

  The aliphatic dicarboxylic acid may be linear, branched, or alicyclic. Examples of linear or linear aliphatic dicarboxylic acids include adipic acid, sebacic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, undecanoic acid, undecanoic acid, dodecane Dionic acid is listed. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and the like. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, and the like. When the monomer that provides the polyamide-based resin contained in the second material contains diamine and dicarboxylic acid, the dicarboxylic acid according to the monomer may be composed of one kind of compound, or a plurality of kinds You may be comprised from the compound of these.

  The polyamide resin contained in the second material may have a bond other than an amide bond as a bond related to polymerization of the monomer in the main chain. Since the amide bond is excellent in weather resistance, it is preferable that the polyamide resin has substantially only an amide bond in the main chain.

  Specific examples of the polyamide-based resin in which the bond related to the polymerization of the monomer in the main chain is substantially composed only of the amide bond include polyamide 4, polyamide 6, polyamide 10, polyamide 11, polyamide 12, polyamide 46, and polyamide. 66, polyamide 610, polyamide 6T, polyamide 9T, polyamide 6IT, polymetaxylylene adipamide (polyamide MXD6), isophthalic acid copolymerized polymetaxylylene adipamide (polyamide MXD6I), polymetaxylylene sebacamide (polyamide MXD10) , Polymetaxylylene decanamide (polyamide MXD12), poly 1,3-bisaminocyclohexane adipamide (polyamide BAC6), polyparaxylylene sebacamide (polyamide PXD10), and the like. Among these, polyamide 9T, polyamide 11, polyamide 12 and the like are preferable from the viewpoint of low water absorption.

  The molecular weight of the polyamide-based resin is not particularly limited, but is preferably 10,000 or more and 50,000 or less as a weight average molecular weight from the viewpoint of fluidity of extrusion coating.

  The second material may contain a crosslinking agent. The kind of the crosslinking agent is arbitrary, and a compound having an organic peroxide such as dicumyl peroxide or an isocyanate group or an epoxy group is typical. However, if the crosslinking agent is excessively contained, there is a concern that the handleability and ease of production (film forming property) may decrease or the adhesiveness to the sealing material may decrease. The upper limit is set as appropriate.

  The second resin layer 13 preferably has thermoplasticity from the viewpoint of improving handleability, ease of production (film forming property), and adhesion to the sealing material. In this case, the melt mass flow rate of the resin material obtained by heating the second resin layer 13 at a temperature of 230 ° C. and a load of 2.16 kgf in accordance with JIS K7210: 1999 (ISO 1133: 1997) is 1 g / 10 min. It is preferably 20 g / 10 min or less from the viewpoint of workability and the like. In particular, when the second resin layer 13 is formed by extrusion coating, the melt mass flow rate of the resin material is preferably 2 g / 10 min or more and 10 g / 10 min or less from the viewpoint of stably forming the second resin layer 13.

  If necessary, the second material is a coloring material such as titanium dioxide, an anti-blocking agent such as silica particles, an ultraviolet absorber such as benzophenone, an ultraviolet stabilizer, a flame retardant, a plasticizer, an antistatic agent, a lubricant, etc. Various additives may be included.

  The thickness of the second resin layer 13 is not particularly limited as long as it exhibits desired adhesion to an adherend such as a sealing material and does not impair the effects of the present invention. Specifically, it is preferably 1 μm or more and 200 μm or less, more preferably 10 μm or more and 18 μm or less, and further preferably 30 μm or more and 150 μm or less from the viewpoint of electrical insulation and weight reduction.

(4) Fluororesin Layer As shown in FIG. 2, the solar cell protective sheet 1 according to the present embodiment is provided on the surface of the substrate 11 on which the first resin layer 12 is not laminated (the lower surface in FIG. 2). May be provided with a fluororesin layer 14. By providing the fluororesin layer 14 in this way, the weather resistance and chemical resistance of the solar cell protective sheet 1 are improved. In addition, when the base material 11 consists of a resin film, in order to improve the adhesiveness with the fluororesin layer 14, the surface by which the fluororesin layer 14 of the said resin film is laminated | stacked has a corona treatment and a plasma treatment. It is preferable that surface treatment such as primer treatment is performed.

  The fluororesin layer 14 is not particularly limited as long as it contains fluorine. For example, the fluororesin layer 14 includes a sheet having a fluorine-containing resin (fluorine-containing resin sheet) or a coating film formed by applying a paint containing the fluorine-containing resin. Is done. Among these, from the viewpoint of making the fluororesin layer 14 thinner in order to reduce the weight of the solar cell protective sheet 1, a coating film formed by applying a paint having a fluorine-containing resin is preferable.

  As the fluorine-containing resin sheet, for example, a sheet obtained by processing a resin mainly composed of polyvinyl fluoride (PVF), ethylene chlorotrifluoroethylene (ECTFE), or ethylene tetrafluoroethylene (ETFE) is used. Examples of the resin mainly composed of PVF include E.I. I. “Tedlar” (trade name) manufactured by du Pont de Nemours and Company. Examples of the resin mainly composed of ECTFE include “Halar” (trade name) manufactured by Solvay Solexis. Examples of the resin mainly composed of ETFE include “Fluon” (trade name) manufactured by Asahi Glass Co., Ltd.

  When the fluororesin layer 14 is a fluorine-containing resin sheet, the fluororesin layer 14 is laminated on the base material 11 through an adhesive layer. The layer having adhesiveness is formed using an adhesive having adhesiveness to the substrate 11 and the fluorine-containing resin sheet. Examples of such adhesives include acrylic adhesives, polyurethane adhesives, epoxy adhesives, polyester adhesives, and polyester polyurethane adhesives. These adhesives may be used individually by 1 type, and may be used in combination of 2 or more type.

  On the other hand, when the fluororesin layer 14 is a coating film formed by applying a paint containing a fluorine-containing resin, usually, the paint containing the fluorine-containing resin is directly applied to the substrate 11 without going through an adhesive layer. By doing so, the fluororesin layer 14 is laminated on the substrate 11.

  The paint containing the fluorine-containing resin is not particularly limited as long as it is dissolved in a solvent or dispersed in water and can be applied.

  The fluorine-containing resin contained in the paint is not particularly limited as long as it does not impair the effects of the present invention and contains fluorine. However, it is usually soluble in a paint solvent (organic solvent or water) and can be crosslinked. Things are used. As the fluorine-containing resin, it is preferable to use a fluoroolefin resin having a curable functional group. Examples of such a fluoroolefin resin include tetrafluoroethylene (TFE), isobutylene, vinylidene fluoride (VdF), a copolymer comprising hydroxybutyl vinyl ether and other monomers, or TFE, VdF, hydroxybutyl vinyl ether and other Examples thereof include a copolymer composed of monomers.

  Specific examples of fluoroolefin resins include “LUMIFLON” (trade name) manufactured by Asahi Glass Co., “CEFRAL COAT” (trade name) manufactured by Central Glass Co., Ltd., and “FLUONATE” (trade name) manufactured by DIC Corporation. Polymers mainly composed of fluoroethylene (CTFE), polymers mainly composed of tetrafluoroethylene (TFE) such as “ZEFFLE” (trade name) manufactured by Daikin Industries, Ltd .; I. Polymers having a fluoroalkyl group, such as “Zonyl” (trade name) manufactured by du Pont de Nemours and Company, “Unidyne” (trade name) manufactured by Daikin Industries, Ltd. Can be mentioned. Among these, from the viewpoint of weather resistance, pigment dispersibility, and the like, a polymer containing CTFE as a main component and a polymer containing TFE as a main component are preferable, and “LUMIFLON” and “ZEFFLE” are particularly preferable.

  “LUMIFLON” is an amorphous resin containing CTFE and several types of specific alkyl vinyl ethers (VE) or hydroxyalkyl vinyl ethers as main structural units. A resin having a monomer unit of hydroxyalkyl vinyl ether such as “LUMIFLON” is preferable because it is excellent in solvent solubility, cross-linking reactivity, substrate adhesion, pigment dispersibility, hardness and flexibility.

  “ZEFFLE” is a copolymer of TFE and organic solvent-soluble hydrocarbon olefins. Among them, those containing hydrocarbon olefins with highly reactive hydroxyl groups are solvent-soluble, crosslinking reactivity, and substrate adhesion. And pigment dispersibility is preferable.

  Examples of the copolymerizable monomer that forms the fluorine-containing resin contained in the paint include vinyl acetate, vinyl propionate, butyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, Vinyl esters of carboxylic acids such as vinyl stearate, vinyl cyclohexyl carboxylate and vinyl benzoate, alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether, CTFE, vinyl fluoride (VF), VdF and fluorine And fluorine-containing monomers such as fluorinated vinyl ethers.

  Further, the fluorine-containing resin contained in the paint may be a resin composed of one or more monomers or a terpolymer. Examples of the terpolymer include “Dyneon THV” (trade name) manufactured by 3M Company, which is a terpolymer of VdF, TFE, and hexafluoropropylene. Such a terpolymer is preferable because it can impart the properties of each monomer to the resin. In particular, “Dyneon THV” is preferable because it can be produced at a relatively low temperature, can be bonded to an elastomer or a hydrocarbon-based plastic, and is excellent in flexibility and optical transparency.

  The coating material may contain a crosslinking agent, a curing catalyst, a solvent and the like in addition to the fluorine-containing resin described above, and may further contain an inorganic compound such as a pigment and a filler, if necessary.

  The solvent contained in the paint is not particularly limited as long as it does not impair the effects of the present invention. For example, methyl ethyl ketone (MEK), cyclohexanone, acetone, methyl isobutyl ketone (MIBK), toluene, xylene, methanol, isopropanol, ethanol , Heptane, ethyl acetate, isopropyl acetate, n-butyl acetate or n-butyl alcohol, and a solvent containing any one or more organic solvents is preferably used.

  The pigment or filler contained in the paint is not particularly limited as long as it does not impair the effects of the present invention. For example, titanium dioxide, carbon black, perylene pigment, mica, polyamide powder, boron nitride, zinc oxide, aluminum oxide Silica, ultraviolet absorbers, preservatives, desiccants and the like are used. Specifically, as pigments and fillers, E.I. is rutile titanium dioxide treated with silicon oxide in order to impart durability. I. “Ti-Pure R105” (trade name) manufactured by du Pont de Nemours and Company, and “CAB-O-SIL TS” manufactured by Cabot, which is a hydrophobic silica in which hydroxyl groups on the silica surface are modified by surface treatment of dimethyl silicone. “720” (trade name) is preferably used.

  The coating film of the fluorine-containing resin is preferably cured with a crosslinking agent in order to improve weather resistance and scratch resistance. The crosslinking agent is not particularly limited as long as the effects of the present invention are not impaired, and metal chelates, silanes, isocyanates, or melamines are preferably used. Assuming that the solar cell protective sheet 1 is used outdoors for a long period of time, aliphatic isocyanates are preferable as the crosslinking agent from the viewpoint of weather resistance.

  The curing catalyst contained in the coating is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include tin dibutyldilaurate for promoting the crosslinking between the fluorine-containing resin and isocyanate.

  The composition of the coating is not particularly limited as long as the effects of the present invention are not impaired. For example, the coating composition is prepared by mixing a fluorine-containing resin, a pigment, a crosslinking agent, a solvent, and a catalyst. As a composition ratio, when the entire coating is 100% by mass, the content of the fluorine-containing resin is preferably 3% by mass or more and 80% by mass or less, and particularly preferably 25% by mass or more and 50% by mass or less. The rate is preferably 5% by mass or more and 60% by mass or less, particularly preferably 10% by mass or more and 30% by mass or less, and the solvent content is 20% by mass or more and 80% by mass or less, particularly 25% by mass or more and 65% by mass or less. Preferably there is.

  As a method for applying the coating material to the substrate 11, a known method is used. For example, a fluororesin obtained by a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like. What is necessary is just to apply | coat so that the layer 14 may become desired thickness.

  The drying temperature of the coating material applied to the substrate 11 may be any temperature that does not impair the effects of the present invention, and is preferably in the range of 50 to 130 ° C. from the viewpoint of reducing the influence on the substrate 11.

  The thickness of the fluororesin layer 14 is set in consideration of weather resistance, chemical resistance, weight reduction, and the like, and is preferably 5 μm or more and 50 μm or less, and particularly preferably 10 μm or more and 30 μm or less.

(5) Vapor deposition layer, metal sheet As shown in FIG. 3, the solar cell protective sheet 1 according to the present embodiment is provided on the surface of the base material 11 on the side where the first resin layer 12 is not laminated. A vapor deposition layer 15 may be provided between the metal layer 17 and the fluororesin layer 14, or a metal sheet 17 may be laminated via an adhesive layer 16 as shown in FIG. The fluororesin layer 14 described above may be provided on the surface (the lower surface in FIGS. 3 and 4) of the sheet 17. By providing the vapor deposition layer 15 or the metal sheet 17 in this manner, the moisture resistance and weather resistance of the solar cell protective sheet 1 can be improved. In the present embodiment, the “metal sheet” means a sheet-like member made of a metal-based material (that is, a material containing a metal element).

  In addition, when the base material 11 consists of a resin film, in order to improve the adhesiveness with the vapor deposition layer 15 or the contact bonding layer 16, the surface by which the vapor deposition layer 15 or the contact bonding layer 16 of the said resin film is laminated | stacked is a corona. Surface treatment such as treatment, plasma treatment, and primer treatment is preferably performed.

  The vapor deposition layer 15 is comprised from inorganic materials, such as a metal or a semimetal, or an oxide, nitride, silicide, etc. of a metal or a semimetal, By comprising such a material, the base material 11 (protective sheet for solar cells) It is possible to impart moisture resistance (water vapor barrier property) and weather resistance to 1).

  Examples of the vapor deposition method for forming the vapor deposition layer 15 include chemical vapor deposition methods such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition, or vacuum vapor deposition, sputtering, and ion plating. A physical vapor phase method such as a method is used. Among these methods, the sputtering method is preferable in consideration of operability and controllability of the layer thickness.

  Examples of the metal used as the raw material of the vapor deposition layer 15 include aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium rim (Na), titanium (Ti), and lead. (Pb), zirconium (Zr), yttrium (Y) and the like. Examples of the semimetal include silicon (Si) and boron (B). Examples of these metal or metalloid oxides, nitrides, and oxynitrides include aluminum oxide, tin oxide, silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxynitride.

  The vapor deposition layer 15 may be made of one kind of inorganic material or may be made of a plurality of kinds of inorganic materials. When the vapor deposition layer 15 is made of a plurality of types of inorganic materials, it may be a vapor deposition layer having a laminated structure in which the layers made of the respective inorganic materials are sequentially vapor deposited, or may be a vapor deposition layer in which a plurality of types of inorganic materials are vapor deposited simultaneously. May be.

  The thickness of the vapor deposition layer 15 is appropriately set in consideration of the water vapor barrier property, and is changed depending on the type of inorganic material used, vapor deposition density, and the like. Usually, the thickness of the vapor deposition layer 15 is preferably 5 nm or more and 200 nm or less, and particularly preferably 10 nm or more and 100 nm or less.

  On the other hand, the metal sheet 17 can also provide moisture resistance (water vapor barrier property) and weather resistance to the base material 11 (protective sheet 1 for solar cells), similarly to the vapor deposition layer 15. The material of the metal sheet 17 is not particularly limited as long as it has such a function, and examples thereof include metals such as aluminum and aluminum alloys such as aluminum-iron alloys.

  The thickness of the metal sheet 17 is not particularly limited as long as the effect of the present invention is not impaired, but from the viewpoint of low pinhole occurrence frequency, high mechanical strength, high water vapor barrier property, and weight reduction, etc. It is preferably 5 μm or more and 100 μm or less, and particularly preferably 10 μm or more and 50 μm or less.

  The adhesive layer 16 is formed using an adhesive having adhesiveness to the substrate 11 and the metal sheet 17. Examples of the adhesive that gives the adhesive layer 16 include acrylic adhesives, polyurethane adhesives, epoxy adhesives, polyester adhesives, polyester polyurethane adhesives, and the like. These adhesives may be used individually by 1 type, and may be used in combination of 2 or more type.

  The thickness of the adhesive layer 16 is not particularly limited as long as the effects of the present invention are not impaired. Usually, the thickness is preferably 1 μm or more and 20 μm or less, and particularly preferably 3 μm or more and 10 μm or less.

  In the above embodiment, the solar cell protective sheet 1 in which the first resin layer 12 and the second resin layer 13 are laminated on one surface of the substrate 11 is illustrated, but for the solar cell of the present invention. The protective sheet is not limited to this, and the first resin layer and the second resin layer may be laminated on the other surface of the substrate 11 (the surface opposite to the one surface).

2. The manufacturing method of the protection sheet for solar cells The method to manufacture the protection sheet 1 for solar cells which concerns on this embodiment (The protection sheet 1 for solar cells shown in FIG. 1 as an example) is not specifically limited. If the case where said 1st resin layer 12 and said 2nd resin layer 13 have thermoplasticity is demonstrated as an example, the 1st material and 2nd material which give these resin layers will be at least one of the base material 11 The solar cell protective sheet 1 is formed as a laminate in which the base material 11, the first resin layer 12 and the second resin layer 13 are laminated in this order. According to such an extrusion coating method, the protection sheet 1 for solar cells can be manufactured with high productivity and at low cost. Moreover, since it is not necessary to separately provide an adhesive layer for adhering the solar cell protective sheet 1 to the sealing material of the solar cell module, it is possible to prevent deterioration over time due to decomposition of the adhesive or the like.

  Specifically, using a T-die extruder or a T-die film forming machine, the first material and the second material are respectively melted and kneaded, and the base material 11 is moved at a constant speed. What is necessary is just to extrude | stack these molten materials on one surface of the base material 11, and to laminate | stack them.

Here, the timing of extrusion of the first material and the second material may be individual or simultaneous. When extruding individually, a laminate composed of the substrate 11 and the first resin layer 12 is first formed by extruding the first material on the substrate 11, and the first resin layer in the laminate is formed. By extruding the second material on the surface on the 12 side, the solar cell protective sheet 1 is obtained as a laminate in which the base material 11, the first resin layer 12, and the second resin layer 13 are laminated in this order. .
On the other hand, when the timing of extrusion is the same, the first material and the second material are extruded together from two parallel slits (at this time, the discharge port of the first material is directed to the substrate 11. Thus, the first resin layer 12 and the second resin layer 13 are simultaneously formed on the substrate 11.

  This coextrusion coating has the advantage in the production process that the solar cell protective sheet 1 can be obtained in a single laminating process, and the first material that provides the first resin layer 12 immediately after coextrusion. Since the second material that provides the second resin layer 13 is in contact with the second material in a molten state, an interaction between these materials easily occurs, and the obtained first resin layer 12 and second resin layer 13 There is also an advantage that adhesion is enhanced. Therefore, when manufacturing the protection sheet 1 for solar cells provided with the structure shown by FIG. 1, manufacturing by coextrusion coating is preferable.

  As shown in FIGS. 2 to 4, when another layer is formed on the base material 11, the first resin layer 12 is formed on the surface of the base material 11 where the other layer is not formed. The second resin layer 13 may be formed.

  The temperature at which the first material and the second material are melted is such that these materials are in a molten state and the base material 11 is not deformed by the temperature (heat) of these materials in the molten state, and is 80 ° C. or higher. It is preferably 350 ° C. or lower, and particularly preferably 150 ° C. or higher and 300 ° C. or lower. In addition, when the first material and the second material are easily deteriorated, it is preferable to lower the upper limit of the temperature so as to minimize the influence of the deterioration.

  Also, the discharge amount of the first material and the second material from each of the T-die extruders depends on the thicknesses of the target first resin layer 12 and the second resin layer 13 and the transport speed of the substrate 11. It is adjusted accordingly.

  The base material 11 is transported in the longitudinal direction at a constant speed by, for example, a roll-to-roll system, and the transport speed depends on the discharge amount of the first material and the second material from the T-die extruder. Are adjusted accordingly.

  According to the above-described coextrusion coating method, the first material and the second material melted from the T-die extruder are extruded and laminated on one surface of the substrate 11 to form the first material on the substrate 11. The one resin layer 12 and the second resin layer 13 can be firmly bonded, and the solar cell protective sheet 1 can be manufactured with high productivity. In particular, since the reaction between the epoxy group of the component contained in the first material and the substrate 11 is promoted, the adhesion between the substrate 11 and the first resin layer 12 is enhanced.

3. Solar Cell Module FIG. 5 is a schematic cross-sectional view of a solar cell module according to an embodiment of the present invention. The solar cell module 10 according to the present embodiment includes a plurality of solar cells 2 made of crystalline silicon, amorphous silicon, or the like, which are photoelectric conversion elements, and a sealing material made of an electrical insulator that seals the solar cells 2 ( Packing layer) 3, a glass plate 4 laminated on the surface (upper surface in FIG. 5) of the sealing material 3, and a back surface protection sheet (laminated on the lower surface in FIG. 5) It is comprised from the protection sheet 1 for solar cells as a back sheet | seat.

  In addition, the protective sheet 1 for solar cells is laminated | stacked on the sealing material 3 so that the 2nd resin layer 13 may become the sealing material 3 side, and it adhere | attaches with respect to the sealing material 3 by this 2nd resin layer 13 Sex is enhanced. In addition, intrusion of moisture and the like from between the second resin layer 13 and the base material 11 is suppressed by the first resin layer 12 disposed therebetween. Therefore, the solar cell protective sheet 1 is excellent in weather resistance.

Preferably the material of the sealing member 3 is olefin resin, as a specific example, medium density polyethylene (MDPE, density: 930 kg / ^{m 3} or more and less than 942kg / ^{m 3),} low density polyethylene (LDPE, density: 910 kg / ^{m 3} or more and less than 930 kg / ^{m 3),} very low density polyethylene (VLDPE, density: 870 kg / ^{m 3} or more, 910 kg / ^m less than ³⁾ polyethylene resins such as polypropylene resin (PP), polyethylene - polypropylene polymer, Olefin-based elastomer (TPO), cycloolefin resin, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl acetate-maleic anhydride copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-butyl acrylate Copolymer (EBA), ethylene- (meth) acrylic acid Ether - like maleic anhydride copolymer. In addition, in this specification, (meth) acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.

  Among these resins, an ethylene-vinyl acetate copolymer (EVA) is particularly preferable from the viewpoints of high gas barrier properties against oxygen and the like, easy crosslinking, and availability.

  The method for producing the solar cell module 10 is not particularly limited. For example, the solar cell 2 is sandwiched between two sheets constituting the encapsulant 3, and the solar cell protective sheet is provided on one exposed surface of the sheet. 1. The solar cell module 10 can be manufactured by installing the glass plate 4 on the other exposed surface and pressing and integrating them while heating. At this time, the protection sheet 1 for solar cells is joined to the sealing material 3 by thermal fusion between the second resin layer 13 and the sealing material 3.

  In addition, as shown in FIG. 6, it can replace with the glass plate 4 and can also use the protection sheet 1 for solar cells as a surface protection sheet (front sheet). In this case, if a flexible substrate is used for the solar battery cell, a solar battery module having flexibility can be obtained. Thus, by making the solar cell module flexible, it becomes possible to mass-produce by roll-to-roll. In addition, since the flexible solar cell module can be fitted to an object having an arched or parabolic wall surface, it can be installed on a dome-shaped building or a soundproof wall of an expressway. .

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

[Example 1]
One side of a PET film (Lumirror X10S manufactured by Toray Industries Inc., thickness 125 μm) as a substrate is subjected to corona treatment (output 3000 W), and a T-die extruder (cylinder temperature: 230 to 280 ° C., T-die temperature: 300 ° C.) ), The first material is an ethylene-glycidyl methacrylate copolymer (LOTADER AX8840 manufactured by Arkema) and the polyamide 11 (Rilsan B manufactured by Arkema) as a second material. The first resin layer having a thickness of 15 μm is laminated on the substrate, and is opposite to the substrate side in the first resin layer. A protective sheet for a solar cell having a structure shown in FIG. 1 was obtained, in which a 25 μm second resin layer was laminated on the surface.

[Example 2]
In Example 1, a solar cell protective sheet having the structure shown in FIG. 1 was obtained in the same manner as in Example 1 except that polyamide 12 (Rilsan A manufactured by Arkema Inc.) was used instead of polyamide 11 as the second material. It was.

Example 3
In Example 1, a solar cell protective sheet having the configuration shown in FIG. 1 was obtained in the same manner as in Example 1 except that polyamide 9T (Genestar N1001D manufactured by Kuraray Co., Ltd.) was used instead of polyamide 11 as the second material. It was.

[Comparative Example 1]
One side of a PET film (Lumirror X10S manufactured by Toray Industries Inc., thickness 125 μm) as a substrate is subjected to corona treatment (output 3000 W), and a T-die film forming machine (cylinder temperature: 230-280 ° C., T-die temperature: 300) A protective sheet for a solar cell in which a polyamide 11 (Rilsan B manufactured by Arkema Co., Ltd.) is extrusion coated by discharging onto a base material, and a layer of 25 μm polyamide 11 is laminated on the base material. Obtained.

[Test Example 1] <Measurement of peel adhesion strength>
The protective sheet for solar cell produced in the example or the comparative example was cut into a rectangle of 25 mm × 200 mm, and the base material and the first resin layer were formed according to JIS K6854-3: 1999 (ISO11339: 1993) under the following conditions. The peel adhesion strength between the first resin layer and the second resin layer (second interface) was measured. The evaluation results are shown in Table 1.
Test atmosphere: 23 ° C, relative humidity 50%
Peeling speed: 300mm / min

  “Unpeelable” in Table 1 means that the peel adhesion strength is particularly high, and it was not possible to peel off under the above conditions. In addition, “not measurable” means that the adhesion of the layer made of polyamide 11 to the base material is particularly low, so the measured value is not stable when the peel adhesion strength is measured, and the degree of peel adhesion strength is evaluated. It means you couldn't. As shown in Table 1, the solar cell protective sheet of the example satisfying the conditions of the present invention can separate the base material from the first resin layer or between the first resin layer and the second resin layer. It is not easy to peel off. Therefore, a solar cell module provided with such a solar cell protective sheet is expected to be less susceptible to moisture from entering the solar cell protective sheet and less likely to deteriorate over time.

  The solar cell protective sheet according to the present invention is suitably used, for example, as a back sheet or a front sheet of a solar cell module.

DESCRIPTION OF SYMBOLS 1 ... Protective sheet for solar cells 11 ... Base material 12 ... 1st resin layer 13 ... 2nd resin layer 14 ... Fluorine resin layer 15 ... Deposition layer 16 ... Adhesion layer 17 ... Metal sheet 2 ... Solar cell 3 ... Sealing Stop material 4 ... Glass plate 10 ... Solar cell module

Claims (8)

A sun comprising a base material, a first resin layer laminated on at least one surface of the base material, and a second resin layer laminated on a surface of the first resin layer opposite to the base material side A battery protection sheet,
The first resin layer contains a component having an epoxy group,
The protective sheet for a solar cell, wherein the second resin layer contains a polyamide-based resin.   The protective sheet for solar cells according to claim 1, wherein the component having an epoxy group is made of a resin including a copolymer obtained by copolymerizing ethylene and glycidyl (meth) acrylate.   The protective sheet for solar cells according to claim 1 or 2, wherein the polyamide-based resin contains one or more selected from the group consisting of polyamide 9T, polyamide 11 and polyamide 12.   4. The solar cell according to claim 1, wherein the first resin layer and the second resin layer are formed by coextrusion coating on the base material. 5. Protective sheet.   The protective sheet for solar cells according to any one of claims 1 to 4, wherein an easy adhesion treatment is performed on a surface of the base material on which the first resin layer is laminated.   The said 2nd resin layer is a protective sheet for solar cells as described in any one of Claim 1 to 5 which is a layer adhere | attached with respect to the sealing material which comprises a solar cell module. A sun comprising a base material, a first resin layer laminated on at least one surface of the base material, and a second resin layer laminated on a surface of the first resin layer opposite to the base material side A method for producing a battery protection sheet, comprising:
A first material containing a component having an epoxy group and a second material containing a polyamide-based resin with respect to the substrate such that the first material is proximal to the substrate; The first resin layer formed using the first material and the second resin layer formed using the second material are laminated on the base material. The manufacturing method of the protection sheet for solar cells characterized by the above-mentioned. A solar battery module, comprising a solar cell, a sealing material that encloses the solar battery cell, and two protective members stacked on each of the main surfaces of the sealing material,
At least one of the said protection members consists of a protection sheet for solar cells as described in any one of Claim 1 to 5, The solar cell module characterized by the above-mentioned.

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