WO2015099059A1 - Feuille multicouche, feuille arrière pour cellule solaire, et module de cellules solaires - Google Patents

Feuille multicouche, feuille arrière pour cellule solaire, et module de cellules solaires Download PDF

Info

Publication number
WO2015099059A1
WO2015099059A1 PCT/JP2014/084351 JP2014084351W WO2015099059A1 WO 2015099059 A1 WO2015099059 A1 WO 2015099059A1 JP 2014084351 W JP2014084351 W JP 2014084351W WO 2015099059 A1 WO2015099059 A1 WO 2015099059A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
resin layer
multilayer sheet
polyester
adhesive
Prior art date
Application number
PCT/JP2014/084351
Other languages
English (en)
Japanese (ja)
Inventor
康史 宮村
拓也 赤羽
小茂田　含
Original Assignee
電気化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 電気化学工業株式会社 filed Critical 電気化学工業株式会社
Priority to JP2015555007A priority Critical patent/JP6571006B2/ja
Priority to CN201480071203.8A priority patent/CN105848895A/zh
Publication of WO2015099059A1 publication Critical patent/WO2015099059A1/fr

Links

Images

Classifications

    • 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
    • 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
    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/19—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their edges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B32B2250/05—5 or more 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • 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 technology relates to a multilayer sheet, a solar cell backsheet and a solar cell module using the multilayer sheet.
  • a solar battery module seals a solar battery cell with a synthetic resin, covers a surface irradiated with sunlight with transparent tempered glass, and a back sheet for solar battery (back protection sheet for solar battery module). It has a structure protected by.
  • a back sheet for a solar cell used at that time for example, a multilayer sheet structure in which a plurality of resin films are laminated has been proposed (for example, Patent Documents 1 to 5).
  • Patent Document 1 discloses a back protective sheet for a solar cell having a configuration in which a specific density polyethylene-based resin is laminated or a specific density polyethylene-based resin is laminated on a thermoplastic polyester resin film in order to improve environmental resistance performance.
  • Patent Document 2 proposes a back sheet in which an outer film and a moisture-proof film are laminated and integrated with an ethylene-vinyl acetate copolymer adhesive.
  • a film in which an inorganic oxide coating film is formed on the surface of a base film is used as a moisture-proof film, and a fluororesin film is used as an outer film.
  • a flexible polypropylene resin film is laminated.
  • the halogen mass ratio is 50% or more on one or both sides of the base sheet made of polyphenylene ether.
  • a certain fluororesin layer is laminated.
  • a solar cell backsheet composed of these multilayer sheets is generally formed by laminating a plurality of films via an adhesive.
  • stacking a polyester base material, a polycarbonate-type base material, a fluorine-type base material, or an acrylic base material the acrylic adhesive which has a hydrolysis resistance, an electrical insulation, and a moisture barrier property It has been proposed to use
  • the above-described conventional multilayer sheet can satisfy the weather resistance, moisture resistance and other characteristics as it is in a solar cell backsheet and a solar cell module using the solar cell backsheet. It has been demanded. And the multilayer sheet produced by multilayer coextrusion is inferior in heat-and-moisture resistance of the adhesive resin layer, and the adhesiveness tends to decrease in a long-time high-temperature and high-humidity environment.
  • the present disclosure is intended to provide a multilayer sheet that can be produced by a multilayer coextrusion method, which is a low-cost manufacturing method, and that has an adhesive resin layer with high long-term wet heat resistance and excellent weather resistance.
  • the present inventor obtained the following knowledge as a result of diligent experiment studies for the above-mentioned purpose.
  • the inventors have a first resin layer containing a polycarbonate resin composition, a polyamide resin composition, a polyester resin composition, or a modified polyphenylene ether resin composition, and a polyvinylidene fluoride resin composition. It has been found that the weather resistance, heat resistance, moisture resistance, electrical insulation, and other required characteristics of the solar battery backsheet are improved by laminating the second resin layer formed from the above.
  • the present inventor examined a method for laminating these resin layers.
  • a plurality of films are bonded together via an adhesive as in the case of a conventional multilayer sheet
  • each process of film formation, winding, adhesive coating, drying and bonding is performed through each resin film.
  • Processing costs increase.
  • the resin of each layer is melted using an extruder, and the coextrusion film forming and the adhesive layer and the layer to be bonded are bonded and bonded together by joining them in a molten state. A method to match them can be considered.
  • the present disclosure provides a first resin layer formed from a resin composition containing a polycarbonate resin, a polyamide resin, a polyester resin, or a modified polyphenylene ether resin, and a second resin layer formed from a polyvinylidene fluoride resin composition.
  • an adhesive resin layer formed from a resin composition containing a polyester block copolymer having an aromatic polyester as a hard segment and a polyether and / or an aliphatic polyester as a soft segment Provided is a multilayer sheet in which the first resin layer and the second resin layer are laminated by multilayer coextrusion through the adhesive resin layer.
  • the polyester block copolymer used for the adhesive resin layer may contain 5 to 90% by mass of the hard segment.
  • the polyvinylidene fluoride-based resin composition constituting the second resin layer is a white inorganic compound based on 100 parts by mass of a resin component containing 50 to 99% by mass of polyvinylidene fluoride and 1 to 50% by mass of polymethyl methacrylate.
  • the pigment may be contained in an amount of 1 to 40 parts by mass.
  • the resin composition constituting the first resin layer may contain a flame retardant and / or a weathering agent.
  • this multilayer sheet can be formed into a film by melt coextrusion molding at a temperature range of 130 to 260 ° C., for example. Further, in this multilayer sheet, a resin layer containing one or more selected from the group consisting of a polyester resin, a polyolefin resin, and a polyamide resin as a resin component may be laminated on the first resin layer.
  • the solar cell backsheet according to the present disclosure uses the multilayer sheet described above.
  • a resin layer containing an ethylene-vinyl acetate copolymer as a resin component is laminated on the surface of the first resin layer opposite to the surface on which the adhesive resin layer is provided. May be.
  • the solar cell module which concerns on this indication uses the said solar cell backsheet.
  • a multilayer sheet that can be produced by a multilayer coextrusion method, which is an inexpensive manufacturing method, and that has a high long-term wet heat resistance and excellent weather resistance.
  • FIG. 1 is a diagram schematically showing a configuration of a multilayer sheet 10 of the present embodiment.
  • the multilayer sheet 10 of the present embodiment includes a first resin layer 1, a second resin layer 2, and an adhesive resin layer 3, and the first resin layer 1 and the second resin layer 3 are provided.
  • the resin layer 2 is laminated by multilayer coextrusion through the adhesive resin layer 3.
  • the first resin layer 1 is formed from a resin composition containing a polycarbonate resin, a polyamide resin, a polyester resin, or a modified polyphenylene ether resin.
  • the second resin layer 2 is formed from a polyvinylidene fluoride resin composition.
  • the adhesive resin layer is formed from a resin composition containing a polyester block copolymer having an aromatic polyester as a hard segment and a polyether and / or an aliphatic polyester as a soft segment.
  • a resin composition containing a polyester block copolymer having an aromatic polyester as a hard segment and a polyether and / or an aliphatic polyester as a soft segment.
  • the first resin layer 1 is provided on the adhesive resin layer 3 so as to face the second resin layer 2 and has a role as a reinforcing material in the multilayer sheet.
  • the first resin layer 1 is formed from a resin composition containing a polycarbonate resin, a polyamide resin, a polyester resin, or a modified polyphenylene ether resin.
  • This resin composition preferably contains a polycarbonate resin, a polyamide resin, a polyester resin, or a modified polyphenylene ether resin as a main component.
  • the main component in this case refers to a resin that is contained in an amount of 50% by mass or more in the resin component of the resin composition forming the first resin layer 1.
  • the content of the resin contained as a main component in the resin composition is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, based on the resin component of the resin composition. More preferably, it is 70 to 100% by mass.
  • Commercially available products can be used as the above-mentioned resins that can be used as the main component of the resin composition that forms the first resin layer 1, and these resins will be described in detail below.
  • the polycarbonate resin is a polymer obtained by reacting a dihydroxydiaryl compound with a carbonate ester such as phosgene or diphenyl carbonate.
  • the raw material of the polycarbonate resin is not particularly limited.
  • the dihydroxydiaryl compound include bis (hydroxyaryl) alkanes, bis (hydroxyaryl) cycloalkanes, dihydroxydiaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, and dihydroxydiaryl sulfones.
  • bis (hydroxyaryl) alkanes include 2,2-bis (4-hydroxyphenyl) propane (also called bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxy). Phenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl) -3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis ( 4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) Propane and the like.
  • bis (hydroxyaryl) cycloalkanes include 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane and the like.
  • dihydroxydiaryl ethers include 4,4′-dihydroxydiphenyl ether and 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether.
  • dihydroxydiaryl sulfides include 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, and the like.
  • dihydroxydiaryl sulfoxides include 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, and the like.
  • dihydroxydiaryl sulfones include 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone and the like.
  • a polycarbonate resin is used for the resin composition forming the first resin layer 1
  • a polycarbonate resin polymerized using one or more of the specific examples of the dihydroxydiaryl compound can be used as a raw material. .
  • the polycarbonate resin is a polymer obtained by polymerizing 2,2-bis (4-hydroxyphenyl) propane (also called bisphenol A) as a main component as a dihydroxydiaryl compound as a raw material. This is preferable from the viewpoint of heat and humidity resistance.
  • the main component here is 80 mol% or more of all the dihydroxy diaryl compounds used for polycarbonate resin, More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more.
  • a plurality of types of polycarbonate resins may be used.
  • a polycarbonate resin obtained by polymerizing 2,2-bis (4-hydroxyphenyl) propane commonly referred to as bisphenol A
  • bisphenol A 2,2-bis (4-hydroxyphenyl) propane
  • Polyamide resin examples of the polyamide resin (PA resin) include polycaproamide (nylon 6), poly- ⁇ -aminoheptanoic acid (nylon 7), poly- ⁇ -aminononanoic acid (nylon 9), polyundecanamide (nylon 11), Polylaurin lactam (nylon 12), polyethylenediamine adipamide (nylon 2.6), polytetramethylene adipamide (nylon 4.6), polyhexamethylene adipamide (nylon 6/6), polyhexamethylene Bacamide (Nylon 6 ⁇ 10), Polyhexamethylene dodecamide (Nylon 6 ⁇ 12), Polyoctamethylene dodecamide (Nylon 6 ⁇ 12), Polyoctamethylene adipamide (Nylon 8 ⁇ 6), Polydecamethylene adiamide Pamide (Nylon 10.6), Polydecamethylene Sebacamide (Nylon 10.6) 10), polydodecamethylene dodecamide (nylon 12 and 12), metaxylenediamine-6 nylon (
  • the polyamide resin may be a copolymer.
  • the polyamide resin of the copolymer include caprolactam / laurin lactam copolymer, caprolactam / hexamethylene diammonium adipate copolymer, laurin lactam / hexamethylene diammonium adipate copolymer, hexamethylene diammonium adipate / hexamethylene Examples thereof include diammonium sebacate copolymer, ethylene diammonium adipate / hexamethylene diammonium adipate copolymer, and caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer.
  • These polyamides may contain, as a film flexibility modifying component, aromatic sulfonamides, plasticizers such as p-hydroxybenzoic acid and esters, low elastic modulus elastomer components, and lac
  • metaxylenediamine-6 nylon also known as poly (metaxylylene adipamide)
  • MXD6 metaxylenediamine-6 nylon
  • polyester resin examples include polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polyethylene naphthalate (polyethylene-2,6-naphthalate), and polytrimethylene terephthalate.
  • PET polyethylene terephthalate
  • PPT polypropylene terephthalate
  • PBT polybutylene terephthalate
  • polyethylene naphthalate polyethylene-2,6-naphthalate
  • polytrimethylene terephthalate polytrimethylene terephthalate
  • polyester resin what copolymerized the diol type monomer and the dicarboxylic acid type monomer can also be used.
  • the diol monomer in this case include diethylene glycol, neopentyl glycol, and polyalkylene glycol.
  • dicarboxylic acid monomer examples include adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 2,6-n
  • a polyester resin containing at least one selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate is used. Is preferred. Of these, polybutylene terephthalate (PBT) is more preferred.
  • modified polyphenylene ether resin is a resin obtained by alloying a polyphenylene ether (PPE resin) having an aromatic polyether structure with another synthetic resin.
  • PPE resin and other synthetic resins that are alloyed are not particularly limited, but polystyrene resins are preferable.
  • Modification by mixing a PPE resin with another synthetic resin is preferable from the viewpoint of easy production, but may be modification by copolymerizing another monomer with a phenol-based monomer.
  • PPE resins include poly (2,6-dimethylphenylene-1,4-ether), poly (2-methyl-6-ethylphenylene-1,4-ether), and poly (2,6-diethylphenylene- 1,4-ether), poly (2-methyl-6-n-propylphenylene-1,4-ether), poly (2-methyl-6-n-butylphenylene-1,4-ether), poly (2 -Methyl-6-chlorophenylene-1,4-ether), poly (2-methyl-6-bromophenylene-1,4-ether), and poly (2-ethyl-6-chlorophenylene-1,4-ether) ) And the like. These may be used alone or in combination of two or more.
  • polystyrene resin that is alloyed with the PPE resin
  • examples of the polystyrene resin that is alloyed with the PPE resin include polystyrene (PS), styrene- ⁇ -methylstyrene copolymer, and styrene-butadiene copolymer represented by high impact polystyrene (HIPS). . These may be used alone or in combination of two or more.
  • PS polystyrene
  • HIPS high impact polystyrene
  • modified polyphenylene ether resin When a modified polyphenylene ether resin is used for the resin composition forming the first resin layer 1, it is preferable to use a modified polyphenylene ether resin in which polyphenylene ether (PPE) and high impact polystyrene are mixed.
  • PPE polyphenylene ether
  • a flame retardant can be mix
  • the first resin layer 1 contains a flame retardant
  • the multilayer sheet can be made difficult to ignite.
  • the flame retardant compounded in the resin composition forming the first resin layer 1 is not particularly limited, and examples thereof include a chlorine-based flame retardant, a brominated flame retardant, a phosphorus-based flame retardant, and an inorganic flame retardant. Can be used.
  • Examples of the chlorine-based flame retardant include chlorinated paraffin, perchlorocyclopentadecane, and chlorendic acid.
  • Examples of the brominated flame retardant include tetrabromobisphenol A (TBA), decabromodiphenyl oxide, TBA epoxy oligomer, TBA polycarbonate, octabromodiphenyl ether, and tribromophenol.
  • Examples of the phosphorus flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tributyl phosphate, trischloroethyl phosphate, and trischloropropyl phosphate.
  • Examples of the inorganic flame retardant include aluminum hydroxide, magnesium hydroxide, and antimony trioxide.
  • the resin composition forming the first resin layer 1 may contain a weathering agent such as an ultraviolet absorber, a light stabilizer, and an antioxidant.
  • a weathering agent such as an ultraviolet absorber, a light stabilizer, and an antioxidant.
  • the weathering agent is not particularly limited.
  • the ultraviolet absorber for example, benzophenone, benzotriazole, salicylate, acrylonitrile, metal complex, ultrafine titanium oxide, ultrafine zinc oxide, and the like can be used.
  • the light stabilizer for example, a hindered amine compound and a hindered piperidine compound can be used.
  • the antioxidant for example, phenol, amine, sulfur and phosphoric acid can be used.
  • the benzophenone-based UV absorber the light stabilizer composed of a hindered amine compound, or the phenol-based antioxidant is chemically added to the main chain or side chain constituting the polymer.
  • a polymer-type ultraviolet absorber, a light stabilizer, an antioxidant, or the like that is bonded can also be used.
  • the weathering agent such as an ultraviolet absorber, a light stabilizer and an antioxidant is blended in the resin composition forming the first resin layer 1, the weathering agent is effective and mechanical properties such as impact strength. From the viewpoint of not lowering the temperature, the total amount of the weathering agent is preferably 0.1 to 10% by mass of the entire resin composition.
  • a weathering agent can also be used together with the flame retardant mentioned above, it can also be used independently.
  • the melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg measured by A method defined in JIS K7210 of the first resin layer 1 is 0.5 to 25 g / 10 min from the viewpoint of moldability. It is preferably 1 to 20 g / 10 minutes, more preferably 2 to 15 g / 10 minutes.
  • the thickness of the first resin layer 1 is preferably 25 to 500 ⁇ m, more preferably 30 to 400 ⁇ m, and further preferably 35 to 350 ⁇ m.
  • the second resin layer 2 (hereinafter, also referred to as “polyvinylidene fluoride-based resin layer 2”) is a polyfluoride in which 50% by mass or more of the resin component constituting the second resin layer 2 is a polyvinylidene fluoride resin. It is comprised with the vinylidene-type resin composition.
  • the polyvinylidene fluoride resin is a main component of 50% by mass or more (50 to 100% by mass) in the resin component in the polyvinylidene fluoride resin composition.
  • the content of the polyvinylidene fluoride resin in the resin component in the composition is preferably 50 to 99% by mass, more preferably 60 to 99% by mass, and further preferably 70 to 95% by mass.
  • the polyvinylidene fluoride resin contained in the polyvinylidene fluoride resin composition is preferably a homopolymer of vinylidene fluoride, but may be a copolymer of vinylidene fluoride and other monomers.
  • other monomers that form a copolymer with vinylidene fluoride include, for example, vinyl fluoride, tetrafluoroethylene, trifluorochloroethylene, hexafluoropropylene, hexafluoroisobutylene, and various fluoroalkyls.
  • examples thereof include fluorinated vinyl compounds such as vinyl ether, and known vinyl monomers such as styrene, ethylene, butadiene and propylene.
  • the amount of monomers other than vinylidene fluoride in the polyvinylidene fluoride resin is 50% by mass or less. Is preferred.
  • the method for producing the polyvinylidene fluoride resin described above is not particularly limited, and the polymerization can be performed by a general method such as suspension polymerization or emulsion polymerization.
  • a solvent such as water, a polymerization initiator, a suspending agent (or emulsifier), a chain transfer agent, etc.
  • the reactor is degassed and degassed to form a gaseous vinylidene fluoride monomer.
  • the polymerization of the vinylidene fluoride monomer may be promoted while controlling the reaction temperature.
  • an inorganic peroxide such as persulfate or an organic peroxide can be used, and specifically, dinormal propyl peroxydicarbonate (NPP) or diisopropyl peroxydioxide. Examples include carbonate.
  • NPP dinormal propyl peroxydicarbonate
  • diisopropyl peroxydioxide examples include carbonate.
  • Chain transfer agents include acetone, isopropyl acetate, ethyl acetate, diethyl carbonate, dimethyl carbonate, ethyl carbonate, propionic acid, trifluoroacetic acid, trifluoroethyl alcohol, formaldehyde dimethyl acetal, 1,3-butadiene epoxide, 1, Examples include 4-dioxane, ⁇ -butyllactone, ethylene carbonate, vinylene carbonate.
  • acetone and ethyl acetate are preferable from the viewpoint of availability and ease of handling.
  • water-soluble cellulose ethers such as partially saponified polyvinyl alcohol, methyl cellulose and hydroxyethyl cellulose, water-soluble polymers such as acrylic acid polymers and gelatin can be used as the suspending agent (or emulsifier).
  • a resin other than the polyvinylidene fluoride resin can be blended with the polyvinylidene fluoride resin composition, and the resin is preferably a polymethacrylate resin from the viewpoint of flexibility and workability.
  • the “polymethacrylic ester resin” referred to here is a polymethacrylic ester obtained by polymerizing a methacrylic ester produced by an ACH method, a modified ACH method, a direct method or an ethylene method by radical polymerization or the like.
  • Polymethacrylate resin has the effect of enhancing the adhesion with other resins when it is formed into a film.
  • the polyvinylidene fluoride resin is inferior in adhesiveness to other materials, but the adhesiveness can be improved by blending a polymethacrylate resin.
  • the amount of the polymethacrylic ester resin in the resin component exceeds 50% by mass, the amount of the polyvinylidene fluoride resin decreases, so that the weather resistance decreases.
  • the addition effect mentioned above is hard to be acquired as the amount of polymethacrylate-type resin is less than 1 mass%.
  • the content of the polymethacrylate resin is preferably 1 to 50% by mass in the resin component of the composition.
  • the content is more preferably 1 to 40% by mass, and further preferably 5 to 30% by mass.
  • the structure of the polymethacrylic acid ester resin blended in the polyvinylidene fluoride resin composition is not particularly limited as long as it is a vinyl polymer based on a methacrylic acid ester monomer.
  • the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate and hexyl methacrylate.
  • alkyl groups such as propyl group, butyl group, pentyl group, and hexyl group in the methacrylic acid ester monomer may be linear or branched.
  • methyl methacrylate is suitable, and polymethyl methacrylate is preferred as the polymethacrylic ester resin.
  • blended with the polyvinylidene fluoride type-resin composition which comprises the 2nd resin layer 2 is a homopolymer of a methacrylate ester monomer, or several methacrylate ester monomers
  • the copolymer may be used.
  • the polymethacrylic ester resin may have a structural unit derived from ethylene, propylene, butadiene, styrene, ⁇ -methylstyrene, acrylonitrile, acrylic acid, and the like, which are known vinyl compounds other than methacrylic esters. Good.
  • the content of the polyvinylidene fluoride resin is preferably 50 to 95 parts by mass, and 60 to 95 parts by mass. More preferred is 70 to 90 parts by mass.
  • the content of the polymethacrylate resin is preferably 5 to 50 parts by mass, more preferably 5 to 40 parts by mass, and still more preferably 10 to 30 parts by mass.
  • the polyvinylidene fluoride resin composition may be mixed with white inorganic pigments such as magnesium oxide, barium sulfate, titanium oxide, basic lead carbonate and zinc oxide for the purpose of imparting light reflectivity. it can.
  • white inorganic pigments such as magnesium oxide, barium sulfate, titanium oxide, basic lead carbonate and zinc oxide.
  • rutile crystal titanium dioxide having a large refractive index and coloring power and a small photocatalytic action is suitable.
  • the content of the white inorganic pigment in the polyvinylidene fluoride-based resin composition is less than 1 part by mass per 100 parts by mass of the resin component constituting the second resin layer 2, the intended light reflection characteristics cannot be obtained. There is. Moreover, when the content of the white inorganic pigment exceeds 40 parts by mass per 100 parts by mass of the resin component constituting the first resin layer, dispersion in the composition becomes non-uniform or film formation is difficult. It may become. Therefore, when a white inorganic pigment is blended in the polyvinylidene fluoride resin composition, the content of the white inorganic pigment is 1 to 40 masses with respect to 100 mass parts of the resin component constituting the second resin layer 2. Parts, preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight. Thereby, the multilayer sheet
  • a toning inorganic pigment may be added to the polyvinylidene fluoride resin composition together with the white inorganic pigment described above.
  • Inorganic pigments for toning use complex oxide pigments in which two or more of oxides of metallic materials such as chromium, zinc, iron, nickel, aluminum, cobalt, manganese and copper are selected and solid-dissolved by firing Etc. can be used. These complex oxide pigments can be used alone or in combination of two or more.
  • the inorganic pigment for toning when contained in the polyvinylidene fluoride resin composition, it is 0.01 to 7 parts by mass with respect to 100 parts by mass of the resin component constituting the second resin layer 2. It is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass. Thereby, the reflectance of sunlight can be adjusted in the range which does not affect the power generation characteristic of a solar cell module, and the external appearance and color of a solar cell module can be changed.
  • the above-mentioned polyvinylidene fluoride resin composition is prepared by blending, for example, a polyvinylidene fluoride resin and, if necessary, a methacrylic ester resin, a white inorganic pigment, a toning inorganic pigment, and the like by melt-kneading. Obtainable. At that time, for melt kneading, various mixers and kneaders equipped with a heating device such as a twin screw extruder, continuous and batch type kneader can be used. This is a twin screw extruder. Further, in the case of melt kneading, a dispersant may be added as necessary within a range not affecting the above-described effects.
  • the melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg measured by the A method defined in JIS K7210 of the polyvinylidene fluoride resin layer (second resin layer) 2 is 0.00. It is preferably 5 to 25 g / 10 minutes, more preferably 1 to 20 g / 10 minutes, and further preferably 2 to 15 g / 10 minutes.
  • the thickness of the second resin layer 2 is preferably 5 to 50 ⁇ m, more preferably 7 to 45 ⁇ m, and even more preferably 10 to 40 ⁇ m.
  • the adhesive resin layer 3 is located between the first resin layer 1 and the second resin layer 2 described above, and serves as an adhesive layer between the first resin layer 1 and the second resin layer 2. .
  • the adhesive resin layer 3 is formed from a resin composition containing a polyester block copolymer having an aromatic polyester as a hard segment and a polyether and / or an aliphatic polyester as a soft segment.
  • the resin composition forming the adhesive resin layer 3 (hereinafter also referred to as “adhesive resin composition”) is a polyester block copolymer having an aromatic polyester as a hard segment and a polyether and / or aliphatic polyester as a soft segment. It is preferable to contain a polymer as a main component.
  • the main component in this case refers to a resin contained in the resin component of the adhesive resin composition in an amount of 50% by mass or more.
  • the content of the polyester block copolymer contained as a main component in this adhesive resin composition is preferably 50 to 100% by mass, more preferably 65 to 100% by mass, and 80 to 100% by mass. More preferably.
  • the polyester block copolymer has a structural unit of an aromatic polyester as a hard segment and a structural unit of a polyether and / or an aliphatic polyester as a soft segment.
  • hard segment and “soft segment” have the same meaning as commonly used in thermoplastic elastomers that are block copolymers.
  • the “hard segment” represents a molecular constrained portion that serves as a crosslinking point of a crosslinked rubber that prevents plastic deformation
  • the “soft segment” represents a flexible portion that exhibits rubber elasticity.
  • the polyester block copolymer preferably contains 5 to 90% by mass of a hard segment having an aromatic polyester structure in the copolymer. If the adhesive resin layer 3 is formed from a resin composition containing a polyester block copolymer containing 5 to 90% by mass of a hard segment, the adhesiveness to the first resin layer 1 and the second resin layer 2 is improved. It becomes possible to raise. From the viewpoint of enhancing the adhesiveness, the hard block content in the polyester block copolymer is more preferably 5 to 85% by mass, further preferably 5 to 80% by mass, and particularly preferably 10 to 50% by mass.
  • the content of the soft segment in the polyester block copolymer is preferably 10 to 95% by mass, more preferably 15 to 90% by mass, further preferably 20 to 90% by mass, in the copolymer. It is particularly preferred to be in the range of 85% by weight. Further, from the viewpoint of enhancing the adhesive strength of the adhesive resin layer 3, it is preferable that the polyester block copolymer contains more soft segments than hard segments.
  • each content (mass%) of the hard segment and soft segment in a polyester-type block copolymer is a value computed based on the chemical shift and content of a hydrogen atom using NMR.
  • the polyester block copolymer includes a polyester / polyether block copolymer having an aromatic polyester unit in the hard segment and a polyether unit in the soft segment, and an aromatic polyester unit in the hard segment and a soft segment.
  • a polyester / polyester block copolymer having an aliphatic polyester unit is preferred.
  • the adhesive resin layer 3 is preferably formed from a resin composition containing a polyester / polyether block copolymer and / or a polyester / polyester block copolymer as the polyester block copolymer. .
  • the hard segment in the polyester block copolymer is a portion having a structure of an aromatic polyester, may be constituted only by the structure of the aromatic polyester, and may contain a structure other than the aromatic polyester. .
  • the structure of the aromatic polyester is preferably the main structure in the hard segment.
  • the main structure in this case refers to the case where the hard polyester contains 50% by mass or more of the structure of the aromatic polyester.
  • the aromatic polyester contained in the hard segment is preferably an aromatic polyester formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
  • aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, anthracene dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid. And acid, diphenoxyethanedicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, and sodium 3-sulfoisophthalate.
  • ester-forming derivative of the aromatic dicarboxylic acid examples include alkyl esters, aryl esters, carbonates and acid halides of aromatic dicarboxylic acids.
  • aromatic dicarboxylic acids and ester-forming derivatives thereof may be used for forming the hard segment.
  • diol examples include aliphatic diols, alicyclic diols, and aromatic diols.
  • aliphatic diol examples include diols having a molecular weight of 400 or less, such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, and decamethylene glycol. It is done.
  • alicyclic diol examples include 1,1-cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, and tricyclodecane dimethanol.
  • aromatic diol examples include xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxy) diphenylpropane, 2,2′-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4′-dihydroxy-p-terphenyl, and 4,4′-dihydroxy -P-quarterphenyl and the like.
  • ester-forming derivative of the diol include an acetyl isomer and an alkali metal salt of the diol. One or more of these diols and ester-forming derivatives thereof may be used for forming the hard segment.
  • the soft segment in the polyester-based block copolymer is a portion having a polyether and / or aliphatic polyester structure, and may be composed only of the structure of the polyether and / or aliphatic polyester. May be included.
  • the structure of the polyether and / or aliphatic polyester is preferably the main structure in the soft segment.
  • the main structure in this case is that the structure of the polyether or aliphatic polyester is contained in the soft segment in an amount of 50% by mass or more, or the total amount of the structural parts of both the polyether and the aliphatic polyester is contained in an amount of 50% by mass or more. Refers to cases.
  • polyether in the soft segment examples include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, Examples thereof include an ethylene oxide addition polymer of poly (propylene oxide) glycol and a copolymer glycol of ethylene oxide and tetrahydrofuran.
  • poly aliphatic polyester contained in the soft segment in the polyester block copolymer include poly ( ⁇ -caprolactone), polyenanthlactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate. These polyethers and aliphatic polyesters may have one kind or two or more kinds in the soft segment.
  • a commercially available product may be used as the polyester block copolymer.
  • the commercially available products include, for example, a product name “Primalloy (registered trademark)” series which is a polyester-based thermoplastic elastomer manufactured by Mitsubishi Chemical Corporation, and a product name “Perprene (registered trademark)” which is a thermoplastic polyester elastomer manufactured by Toyobo Co., Ltd. ) "Series, the product name” Hytrel (registered trademark) "series, which is a thermoplastic polyetherester elastomer manufactured by Toray DuPont Co., Ltd., and the like.
  • the adhesive resin layer 3 preferably has a softening point of 60 to 190 ° C.
  • the softening point of the adhesive resin layer 3 is more preferably 60 to 180 ° C., still more preferably 70 to 170 ° C.
  • the softening point was measured under the conditions of a test load of 10 N and a heating rate of 50 ° C./h by a method based on the “Vicat softening temperature (VST) test method” defined in JIS K7206. Value.
  • the melt flow rate (MFR) at 230 ° C. and a load of 2.16 kg measured by the A method defined in JIS K7210 of the adhesive resin layer 3 is 0.1 to 30 g / 10 min from the viewpoint of moldability and adhesiveness. It is preferably 1 to 30 g / 10 minutes, more preferably 3 to 30 g / 10 minutes.
  • the thickness of the adhesive resin layer 3 is preferably 5 to 50 ⁇ m, more preferably 7 to 45 ⁇ m, and further preferably 10 to 40 ⁇ m.
  • the thickness of each layer mentioned above is not specifically limited, It can set suitably according to a use and the characteristic calculated
  • the thickness of the first resin layer 1 can be 50 to 500 ⁇ m
  • the thicknesses of the second resin layer 2 and the adhesive resin layer 3 can be 5 to 50 ⁇ m, respectively. If the thickness of each resin layer is within the above numerical range, the multilayer sheet 10 of the present embodiment can be suitably used for a solar cell module as a solar cell backsheet.
  • the melt flow rate (MFR) of each resin layer constituting the multilayer sheet 10 of the present embodiment is 0.5 to 25 g / 10 for the first resin layer 1 and the second resin layer 2.
  • the MFR of the adhesive resin layer 3 is preferably 0.1 to 30 g / 10 min.
  • the MFR of each resin layer can be adjusted by changing the degree of polymerization (or molecular weight) of the resin component contained therein. Specifically, it can be adjusted according to the polymerization temperature when polymerizing the resin component, the type and amount of the polymerization initiator, the type and amount of the chain transfer agent, and the like. Moreover, you may use commercially available resin that MFR of each resin layer becomes in the range mentioned above.
  • the multilayer sheet 10 in which the first resin layer 1 and the second resin layer 2 are laminated via the adhesive resin layer 3 includes the first resin layer 1, the second resin layer 2, and the adhesive resin layer 3. It is manufactured by forming a film by multilayer coextrusion. More specifically, in the multilayer sheet 10 of the present embodiment, each resin composition constituting the first resin layer 1, the second resin layer 2, and the adhesive resin layer 3 is melted by separate extruders. Then, the film can be formed by a co-extrusion method that merges and integrates.
  • melt coextrusion molding at a material temperature of 130 to 260 ° C., for example. Thereby, while making the resin composition which comprises each layer into the stable melt-flow state, generation
  • a more preferable material temperature during film formation is 180 to 250 ° C.
  • various screw designs such as a dull image type, a rotor type, and a flute mixing type can be used as a mixing part, and even those shapes that do not have a mixing part are melted and formed into a sheet. It is possible. Further, in the twin-screw extruder, a kneading disk, a rotor segment, a reverse screw flight, or the like may be disposed as a mixing unit, but a full flight screw without these may be disposed.
  • the cylinder can be used in either a vent type or a no vent type.
  • the thickness of each resin layer can be adjusted within the above-described range by adjusting the discharge rate of the material from the extruder.
  • the discharge speed is adjusted by changing the screw rotation speed.
  • twin screw extruder it is performed by changing the feed speed of the raw material to be fed into the extruder by the feeder, changing the screw rotation speed of the extruder, or changing the rotation speed of the gear pump. be able to.
  • the sheet 10 is preferable.
  • the first resin layer 1, the adhesive resin layer 3, and the second resin layer 2 that are individually formed are laminated in this order, and each of these resin layers is melted or softened. It is also possible to fuse between the resin layers by applying pressure under the temperature conditions.
  • each resin composition constituting the first resin layer 1, the second resin layer 2, and the adhesive resin layer 3 is brought into a molten state, and the melts are laminated by the coextrusion method. Therefore, the multilayer sheet 10 can be in a state where the interface between the first resin layer 1 and the adhesive resin layer 3 and the interface between the second resin layer 2 and the adhesive resin layer 3 are thermally fused. It is. Thus, it is possible to form a fusion
  • the adhesive resin layer 3 capable of forming a fusion interface between the first resin layer 1 and the second resin layer 2
  • a conventional solvent-type adhesive containing an organic solvent or the like By using the adhesive resin layer 3 capable of forming a fusion interface between the first resin layer 1 and the second resin layer 2, there is a concern with a conventional solvent-type adhesive containing an organic solvent or the like. The risk of damage to the resin layers 1 and 2 by the solvent can be eliminated.
  • a high adhesive force can be easily secured as compared with a solventless adhesive such as a hot melt adhesive, and the decrease in the adhesive force is small even at a high temperature of about 100 ° C. Can do.
  • the manufacturing process can be simplified and the manufacturing cost can be reduced as compared with the case where an adhesive is used.
  • the multilayer sheet 10 of the present embodiment uses the polyvinylidene fluoride resin layer 2 and thus has excellent weather resistance and heat resistance.
  • the first resin layer 1 includes a specific resin, and further includes an adhesive resin containing a polyester block copolymer having an aromatic polyester as a hard segment and a polyether and / or an aliphatic polyester as a soft segment. Since the layers are used, the interlayer adhesion between the first resin layer 1 and the second resin layer 2 can be improved. As a result, it becomes possible to realize a multilayer sheet having excellent weather resistance, heat resistance, mechanical strength, elastic modulus, electrical insulation and moisture resistance, and good interlayer adhesion as a solar cell backsheet. .
  • the polyester resin and the polyamide resin used as the third resin layer those similar to the polyester resin and the polyamide resin described in the description of the first resin layer 1 can be used, respectively.
  • the polyolefin resin used as the third resin layer include high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), polybutene, polymethylpentene, and polycycloolefin.
  • a resin film molded separately from the multilayer sheet can be used.
  • a 3rd resin layer is formed by providing a resin film on the 1st resin layer in a multilayer sheet.
  • a commercial item can also be used as a resin film.
  • a 1st resin layer and a 3rd resin layer can be adhere
  • Commercially available products can be used as the adhesive at this time, and for example, urethane adhesives, acrylic adhesives, synthetic rubber adhesives, silicone adhesives, and the like can be used.
  • the third resin layer may be formed by forming a film by extrusion molding on the first resin layer 1 in the multilayer sheet 10 according to the first embodiment. Along with the formation of the layer, it may be formed by coextrusion.
  • a third resin layer containing one or more selected from the group consisting of a polyester resin, a polyolefin resin, and a polyamide resin as a resin component is provided on the first resin layer. Therefore, the electrical insulation of the multilayer sheet can be improved. Therefore, even when it is difficult to form the first resin layer thickly, the electrical insulation of the multilayer sheet can be improved without forming the first resin layer relatively thick.
  • a solar cell backsheet (hereinafter also simply referred to as a backsheet) according to a second embodiment of the present disclosure will be described.
  • the back sheet of this embodiment uses the multilayer sheet of the first embodiment described above or its modification.
  • the backsheet of this embodiment can be used for solar cells of various types such as crystalline silicon, polycrystalline silicon, amorphous silicon, compound, and organic.
  • a thin film solar cell using amorphous silicon or the like may require a high degree of moisture resistance compared to a crystalline solar cell.
  • a moisture-proof layer or a moisture-proof coating layer having a high moisture-proof property made of, for example, an inorganic oxide or the like may be further provided on the multilayer sheet of the first embodiment or its modification.
  • the first resin layer and the second resin layer formed from the polyvinylidene fluoride resin composition are formed from a resin composition containing the polyester block copolymer.
  • a multilayer sheet laminated through an adhesive resin layer is used. Since such a multilayer sheet is used, the backsheet is excellent in various properties required for solar cell backsheets such as weather resistance, heat resistance, mechanical strength, elastic modulus, electrical insulation and moisture resistance, and has flame retardancy. And has good interlayer adhesion. Furthermore, this can be laminated and integrated by batch molding by a coextrusion method, which can be realized at a low production cost.
  • the back sheet of this modification uses the multilayer sheet of the first embodiment or its modification described above.
  • the back sheet of this modification is a resin containing an ethylene-vinyl acetate copolymer (EVA) as a resin component on the surface opposite to the surface of the multilayer sheet on which the adhesive resin layer of the first resin layer is provided. Layers (EVA resin layers) are laminated.
  • EVA ethylene-vinyl acetate copolymer
  • the EVA resin layer is laminated on the surface opposite to the surface on which the adhesive resin layer of the first resin layer is provided. Is done.
  • an EVA resin layer is laminated
  • the EVA resin layer can be formed of an EVA resin composition that is generally used as a sealing material for solar cell modules.
  • an EVA resin composition for example, an ethylene-vinyl acetate copolymer resin having a vinyl acetate content of 10 to 30% by mass as a main component is used as a crosslinking agent at 100 ° C. with respect to 100 parts by mass of the EVA resin.
  • examples include those containing 1 to 5 parts by mass of an organic peroxide that generates radicals.
  • the back sheet and the sealing material are integrated by providing the EVA resin layer on the surface side opposite to the surface side on which the adhesive resin layer of the first resin layer is provided. It has become a structured. Therefore, in the assembly process of a general solar cell module, glass, a sealing material sheet, a cell, a sealing material sheet, and a back sheet are laminated in order, but the laminating operation of the sealing material sheet and the back sheet at that time Can be omitted. In addition, in the back sheet of this modification, it is possible to prevent the sealing material and the back sheet from being displaced in the solar cell module.
  • the EVA resin layer may be provided on the surface side opposite to the surface on which the adhesive resin layer of the second resin layer is provided.
  • FIG. 2 is a cross-sectional view schematically showing the structure of the solar cell module of the present embodiment.
  • solar cells 15 that are photovoltaic elements are sealed with a sealing material 13 made of a synthetic resin such as EVA resin.
  • the transparent substrate 12 which consists of glass etc. is laminated
  • Sheets 10) are stacked, and a frame 14 is provided around them. At that time, the back sheet (multilayer sheet 10) is disposed such that the first resin layer is on the sealing material 13 side.
  • the solar cell module 11 of this embodiment includes a first resin layer formed from a resin composition containing PC resin, polyamide resin, polyester resin, or modified PPE resin on a back sheet (multilayer sheet 10), and PVDF.
  • a second resin layer formed from a resin-based resin composition and a resin composition containing a polyester-based block copolymer in which an aromatic polyester is a hard segment and a polyether and / or an aliphatic polyester is a soft segment.
  • a multilayer sheet laminated by multilayer coextrusion through an adhesive resin layer is used. Since this multilayer sheet is used, the solar cell module 11 is excellent in weather resistance, heat resistance, mechanical strength, elastic modulus, electrical insulation and moisture resistance, and high reliability is obtained.
  • this embodiment can also take the following structures.
  • a first resin layer formed from a resin composition containing a polycarbonate resin, a polyamide resin, a polyester resin, or a modified polyphenylene ether resin, and a second resin layer formed from a polyvinylidene fluoride resin composition
  • an adhesive resin layer formed from a resin composition containing a polyester block copolymer having an aromatic polyester as a hard segment and one or both of a polyether and an aliphatic polyester as a soft segment;
  • a multilayer sheet in which the first resin layer and the second resin layer are laminated by multilayer coextrusion through the adhesive resin layer.
  • the polyvinylidene fluoride resin composition constituting the second resin layer is based on 100 parts by mass of a resin component containing 50 to 99% by mass of polyvinylidene fluoride and 1 to 50% by mass of polymethyl methacrylate.
  • the resin layer containing an ethylene-vinyl acetate copolymer as a resin component is laminated on the surface of the first resin layer opposite to the surface on which the adhesive resin layer is provided. 11].
  • the solar cell backsheet as described in 11].
  • the MFR value is a value measured at 230 ° C. and a 2.16 kg load based on the JIS K7210 method A.
  • the raw material for the adhesive resin layer is a polyester block copolymer (trade name, manufactured by Mitsubishi Chemical Corporation) having a hard segment having an aromatic polyester structure of 32% by mass and a soft segment having a polyether structure of 68% by mass. : Primalloy (registered trademark) A1700, MFR: 10 g / 10 min, softening point: 74 ° C.).
  • Extruder 1 (for the first resin layer): screw rotation speed 100 rotations / minute, discharge speed 150 kg / hour, extruder barrel set temperature 230 ° C.
  • Extruder 2 (for the second resin layer): screw rotation speed 25 rotations / minute, discharge speed 15 kg / hour, extruder barrel set temperature 230 ° C.
  • Extruder 3 (for adhesive resin layer): Screw rotation speed 25 rotations / minute, discharge speed 15 kg / hour, extruder barrel set temperature 230 ° C.
  • Resins discharged from extruders 1 to 3 are merged in a feed block, discharged from a coat hanger die set to a lip opening of 0.5 mm, introduced into a take-out machine, and sandwiched between two cooling rolls for cooling. Thus, a multilayer sheet was obtained. The obtained multilayer sheet was then introduced into a winder and wound into a roll.
  • the thickness of each layer in the multilayer sheet of Example 1 is 300 ⁇ m for the PC resin layer (first resin layer), 20 ⁇ m for the adhesive resin layer, 20 ⁇ m for the PVDF resin layer (second resin layer), Was completely glued.
  • a solar cell module was produced using the multilayer sheet of Example 1 produced by the method described above. Specifically, a glass plate having a thickness of 3 mm, a sealing material sheet made of an ethylene-vinyl acetate copolymer having a thickness of 400 ⁇ m, four polycrystalline silicon cells assembled with series wiring, a sealing material sheet, Back sheets (multilayer sheets of Example 1) were laminated in this order, and laminated by applying pressure and heating at 135 ° C. for 10 minutes in a vacuum laminator to produce a solar cell module.
  • Adhesive strength evaluation of each layer of the multilayer sheet Each of the multilayer sheets of Example 1 conforms to “Adhesive—Peeling peel strength test method—Part 3: T-type peel” defined in JIS K6854-3. The peel strength between the layers was measured at room temperature (25 ° C.). At this time, the shape of the sample was a strip shape having a width of 15 mm ⁇ a length (adhesion portion) of 250 mm, and the tensile speed during the peeling test was 200 mm / min. In addition, the peel adhesion strength after leaving the multilayer sheet in an environment of 100 ° C. for 100 hours and the peel adhesion strength after leaving in an environment of 125 ° C. and 100% humidity for 100 hours are also evaluated. did. Furthermore, the peel adhesion strength after leaving for 1000 hours in an environment of temperature 85 ° C. and humidity 85% and after leaving for 3000 hours was also evaluated.
  • Example 2 As a raw material for the first resin layer, a crystalline polyamide resin obtained from a polycondensation reaction of metaxylenediamine and adipic acid: metaxylenediamine-6 nylon (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade names: nylon MXD6, MFR) : 5 g / 10 min) was used, and a multilayer sheet was prepared and evaluated in the same manner as in Example 1 described above. Further, using this multilayer sheet, a solar cell module was produced and evaluated in the same manner as in Example 1.
  • metaxylenediamine-6 nylon manufactured by Mitsubishi Gas Chemical Co., Ltd., trade names: nylon MXD6, MFR
  • Example 3 Example 1 described above, except that polybutylene terephthalate resin (manufactured by Polyplastics Co., Ltd., trade name: DURANEX (registered trademark) 700FP, MFR: 7 g / 10 min) was used as the raw material for the first resin layer.
  • a multilayer sheet was prepared and evaluated in the same manner as described above. Further, using this multilayer sheet, a solar cell module was produced and evaluated in the same manner as in Example 1.
  • Example 4 Examples described above except that a modified polyphenylene ether resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: Iupiace (registered trademark) LN40, MFR: 11 g / 10 min) was used as a raw material for the first resin layer.
  • a multilayer sheet was prepared and evaluated in the same manner as in No. 1. Further, using this multilayer sheet, a solar cell module was produced and evaluated in the same manner as in Example 1.
  • Example 5 A multilayer sheet was prepared in the same manner as in Example 1 except that polyvinylidene fluoride resin: 55 parts by mass and polymethyl methacrylate resin: 45 parts by mass were prepared as raw materials for the second resin layer. (The MFR of the blend material forming the second resin layer: 2 g / 10 min). Further, using this multilayer sheet, a solar cell module was produced and evaluated in the same manner as in Example 1.
  • Example 6 A multilayer sheet was prepared in the same manner as in Example 1 except that 90 parts by weight of polyvinylidene fluoride resin and 10 parts by weight of polymethyl methacrylate resin were prepared as raw materials for the second resin layer. Evaluated (MFR of blend material forming second resin layer: 6 g / 10 min). Further, using this multilayer sheet, a solar cell module was produced and evaluated in the same manner as in Example 1.
  • Example 7 As a raw material for the adhesive resin layer, a polyester block copolymer (Mitsubishi Chemical Co., Ltd., trade name: having 19% by mass of an aromatic polyester structure in the hard segment and 81% by mass of polyether structure in the soft segment A multilayer sheet was prepared and evaluated in the same manner as in Example 1 except that Primalloy (registered trademark) B1900NS, MFR: 24 g / 10 min, softening point: 92 ° C. was used. Further, using this multilayer sheet, a solar cell module was produced and evaluated in the same manner as in Example 1.
  • Primalloy registered trademark
  • Example 8 As a raw material for the adhesive resin layer, a polyester block copolymer having 28% by mass of an aromatic polyester structure in a hard segment and 72% by mass of a polyether structure in a soft segment (trade name: Perprene, manufactured by Toyobo Co., Ltd.) (Registered trademark) P95C, MFR: 17 g / 10 min, softening point: 162 ° C.) A multilayer sheet was prepared and evaluated in the same manner as in Example 1 described above. Further, using this multilayer sheet, a solar cell module was produced and evaluated in the same manner as in Example 1.
  • Example 9 The same raw material as in Example 1 was prepared, the screw speed of the extruder 1 was changed to 10 revolutions / minute, and the discharge speed was 15 kg / hour, and the thickness of the first resin layer was 30 ⁇ m.
  • the polyethylene terephthalate (PET) film (thickness 320 ⁇ m) is bonded by heating and pressurizing, and the first resin layer and the adhesive resin layer
  • a multilayer sheet was prepared and evaluated in the same manner as in Example 1 except that a multilayer sheet in which the multilayer sheet having the second resin layer and the PET film were integrated was prepared. Further, using this multilayer sheet, a solar cell module was produced and evaluated in the same manner as in Example 1.
  • Example 2 A multilayer sheet was produced in the same manner as in Example 1 except that an ethylene / glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Bond First (registered trademark) 7B) was used as a raw material for the adhesive resin layer. Was made. Since the multilayer sheet of Comparative Example 2 had a very low initial peel strength, various evaluations could not be performed.
  • an ethylene / glycidyl methacrylate copolymer manufactured by Sumitomo Chemical Co., Ltd., trade name: Bond First (registered trademark) 7B
  • a multilayer sheet was produced in the same manner as described above. Since the multilayer sheet of Comparative Example 3 had a very low initial peel strength, various evaluations could not be performed.
  • the peel adhesion strength after 100 hours at room temperature (25 ° C.) and 100 ° C. and after 100 hours at 125 ° C. and 100% humidity exceeds 10 N / 15 mm.
  • the result was a material breakage (material breakage), indicating high adhesion between each layer.
  • material breakage here means that material destruction occurred before the first resin layer or the second resin layer was peeled off.
  • the multilayer sheets of Examples 1 to 9 resulted in material breakage (material breakage) with a peel adhesion strength exceeding 10 N / 15 mm after a 1000 hour environmental test at a temperature of 85 ° C. and a humidity of 85%. Even after a time environmental test, it showed high adhesion between each layer. Further, even after a long time of 3000 hours after this environmental test, it was confirmed that the multilayer sheets of Examples 1 to 9 maintained a high adhesive force without significantly decreasing the peel adhesive strength.
  • the rate of decrease in the maximum power was small even after the high-temperature and high-humidity environmental test. This is presumably because the adhesive strength between the resin layers in the multilayer sheet was maintained, so that the penetration of moisture into the solar cell module was small, and the characteristics of the solar cells were well maintained.
  • a multilayer sheet suitable for a solar cell back sheet can be realized with excellent weather resistance, heat resistance, and moisture resistance and good interlayer adhesion.

Landscapes

  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Laminated Bodies (AREA)
  • Photovoltaic Devices (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne une feuille multicouche présentant une excellente résistance aux intempéries, résistance à la chaleur, et résistance à l'humidité ainsi qu'une bonne adhérence intercouche. L'invention concerne également une feuille arrière pour une cellule solaire, et un module de cellules solaires. La feuille multicouche comprend : une première couche de résine formée à partir d'une composition de résine contenant une résine de polycarbonate, une résine de polyamide, une résine polyester, ou une résine d'éther de polyphénylène modifié ; une deuxième couche de résine formée à partir d'une composition de résine de fluorure de polyvinylidène ; et une couche de résine adhésive formée à partir d'une composition de résine contenant un copolymère séquencé de polyester ayant un segment dur de polyester aromatique et un polyester et/ou segment souple de polyéther aliphatique. Les première et deuxième couches de résine sont stratifiées par l'intermédiaire la couche de résine adhésive par coextrusion multicouche.
PCT/JP2014/084351 2013-12-27 2014-12-25 Feuille multicouche, feuille arrière pour cellule solaire, et module de cellules solaires WO2015099059A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2015555007A JP6571006B2 (ja) 2013-12-27 2014-12-25 多層シート、太陽電池用バックシート及び太陽電池モジュール
CN201480071203.8A CN105848895A (zh) 2013-12-27 2014-12-25 多层片材、太阳能电池用背板以及太阳能电池模块

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-272371 2013-12-27
JP2013272371 2013-12-27

Publications (1)

Publication Number Publication Date
WO2015099059A1 true WO2015099059A1 (fr) 2015-07-02

Family

ID=53478903

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/084351 WO2015099059A1 (fr) 2013-12-27 2014-12-25 Feuille multicouche, feuille arrière pour cellule solaire, et module de cellules solaires

Country Status (3)

Country Link
JP (1) JP6571006B2 (fr)
CN (1) CN105848895A (fr)
WO (1) WO2015099059A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017163062A (ja) * 2016-03-11 2017-09-14 信越化学工業株式会社 太陽電池モジュール及び太陽電池モジュールの製造方法
JPWO2017217546A1 (ja) * 2016-06-17 2019-04-11 凸版印刷株式会社 多層シートの製造方法、成形容器の製造方法、及び多層シート

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113382862A (zh) * 2019-02-26 2021-09-10 日本瑞翁株式会社 层叠膜
CN112606504A (zh) * 2020-11-24 2021-04-06 苏州奥美材料科技有限公司 一种高cti值高阻燃复合薄膜及其制备方法
CN116995233A (zh) * 2022-04-25 2023-11-03 深圳市研一新材料有限责任公司 一种电池用粘结剂及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08207217A (ja) * 1995-02-03 1996-08-13 Elf Atochem Japan Kk 多層構造物の製造法
WO2011065234A1 (fr) * 2009-11-30 2011-06-03 電気化学工業株式会社 Composition de résine de fluorure de polyvinylidène, film, feuille de support, et module de pile solaire
JP2012087292A (ja) * 2010-09-22 2012-05-10 Daicel-Evonik Ltd フィルム状封止剤及び封止方法
WO2013108816A1 (fr) * 2012-01-17 2013-07-25 電気化学工業株式会社 Feuille multicouches, feuille de support arrière pour cellules solaires et module de cellules solaires

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU4258096A (en) * 1994-11-29 1996-06-19 Elf Atochem S.A. Process for producing a multi-layered article
KR101360867B1 (ko) * 2010-04-23 2014-02-13 코오롱인더스트리 주식회사 태양광모듈용 백 시트 및 이의 제조방법
JP5978519B2 (ja) * 2011-09-02 2016-08-24 東京尽陽株式会社 太陽電池用バックシート及び太陽電池モジュール

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08207217A (ja) * 1995-02-03 1996-08-13 Elf Atochem Japan Kk 多層構造物の製造法
WO2011065234A1 (fr) * 2009-11-30 2011-06-03 電気化学工業株式会社 Composition de résine de fluorure de polyvinylidène, film, feuille de support, et module de pile solaire
JP2012087292A (ja) * 2010-09-22 2012-05-10 Daicel-Evonik Ltd フィルム状封止剤及び封止方法
WO2013108816A1 (fr) * 2012-01-17 2013-07-25 電気化学工業株式会社 Feuille multicouches, feuille de support arrière pour cellules solaires et module de cellules solaires

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017163062A (ja) * 2016-03-11 2017-09-14 信越化学工業株式会社 太陽電池モジュール及び太陽電池モジュールの製造方法
JPWO2017217546A1 (ja) * 2016-06-17 2019-04-11 凸版印刷株式会社 多層シートの製造方法、成形容器の製造方法、及び多層シート

Also Published As

Publication number Publication date
JPWO2015099059A1 (ja) 2017-03-23
JP6571006B2 (ja) 2019-09-04
CN105848895A (zh) 2016-08-10

Similar Documents

Publication Publication Date Title
JP5611303B2 (ja) フッ素重合体をベースにした可撓性フィルム
JP6571006B2 (ja) 多層シート、太陽電池用バックシート及び太陽電池モジュール
JP5952838B2 (ja) 多層シート、太陽電池用バックシート及び太陽電池モジュール
JP5993236B2 (ja) 多層シート、太陽電池用バックシート及び太陽電池モジュール
KR102174324B1 (ko) 라미네이트 강판, 이의 제조 방법 및 이에 사용되는 시트
JP6373267B2 (ja) 多層シート及びその製造方法、太陽電池用バックシート並びに太陽電池モジュール
JP6417391B2 (ja) 多層シート、太陽電池用バックシート及び太陽電池モジュール並びに多層シートの製造方法
JPWO2013018459A1 (ja) 樹脂積層体フィルム、樹脂積層体フィルムの製造方法、及び太陽電池モジュール用シート
WO2018147357A1 (fr) Feuille multicouche, feuille de support pour cellules solaires et module de cellules solaires
KR101831901B1 (ko) 내후성 다층 필름 및 이의 제조방법
JP2012074419A (ja) 太陽電池モジュール用裏面保護シート、太陽電池モジュール用裏面一体化シート及び太陽電池モジュール
KR101762337B1 (ko) 폴리머 필름, 태양 전지 패널 보호 필름 및 이를 포함하는 태양광 발전 장치
JP2012074420A (ja) 太陽電池モジュール用裏面保護シート、太陽電池モジュール用裏面一体化シート及び太陽電池モジュール
JP5415247B2 (ja) 太陽電池用表面保護シート
KR20170141170A (ko) 내후성 다층 필름 및 이의 제조방법
JP4833781B2 (ja) 壁装用オーバーフィルム
JP2015191944A (ja) 裏面保護シート及びそれを用いた太陽電池モジュール
JP5639798B2 (ja) 太陽電池モジュール
KR101658184B1 (ko) 폴리머 필름, 태양 전지 패널 보호 필름 및 이를 포함하는 태양광 발전 장치
JP4727998B2 (ja) 金属被覆用積層フィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14873858

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015555007

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14873858

Country of ref document: EP

Kind code of ref document: A1