WO2015098520A1 - Feuille pour protection de côté arrière de cellule solaire - Google Patents

Feuille pour protection de côté arrière de cellule solaire Download PDF

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Publication number
WO2015098520A1
WO2015098520A1 PCT/JP2014/082698 JP2014082698W WO2015098520A1 WO 2015098520 A1 WO2015098520 A1 WO 2015098520A1 JP 2014082698 W JP2014082698 W JP 2014082698W WO 2015098520 A1 WO2015098520 A1 WO 2015098520A1
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Prior art keywords
layer
solar cell
back surface
resin
sheet
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PCT/JP2014/082698
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English (en)
Japanese (ja)
Inventor
規行 巽
堀江　将人
敏弘 千代
東大路　卓司
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東レ株式会社
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Priority to JP2014560169A priority Critical patent/JPWO2015098520A1/ja
Publication of WO2015098520A1 publication Critical patent/WO2015098520A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a sheet for protecting a back surface of a solar cell, which has excellent adhesion to a sealing material for solar cells and maintains adhesion even when left outdoors for a long time (excellent retention).
  • a power generating element is sealed with a transparent sealing material such as ethylene-vinyl acetate copolymer (hereinafter sometimes referred to as EVA), a transparent substrate such as glass, and a back sheet (for back surface protection).
  • EVA ethylene-vinyl acetate copolymer
  • a resin sheet called a “sheet” is bonded together.
  • Sunlight is introduced into the solar cell through the transparent substrate. Sunlight introduced into the solar cell is absorbed by the power generation element, and the absorbed light energy is converted into electrical energy. The converted electric energy is taken out by a lead wire connected to the power generation element and used for various electric devices.
  • biaxially stretched polyethylene terephthalate (hereinafter sometimes referred to as PET) that is inexpensive and has high performance is widely used as a sheet for protecting the back surface of a solar cell, and various materials can be applied by a method such as dry lamination. Studies have been made to impart barrier properties and electrical characteristics by bonding.
  • polyester resins such as PET have poor adhesion to the sealing material. Therefore, conventionally, it is common to laminate a polyolefin resin sheet excellent in adhesion to a sealing material on a polyester resin such as PET and use the polyolefin resin sheet as a sealing material adhesion surface of a solar cell back surface protection sheet. Met.
  • polyester sheets Patent Documents 1, 2, and 3 that are provided with an easy-adhesion layer on the surface of a biaxially stretched polyester film and can be directly bonded to a sealing material have been disclosed.
  • JP 2006-152013 A Japanese Patent No. 4803317 JP 2012-69835 A
  • the conventional easy-adhesion layers listed in Patent Documents 1 to 3 have very weak adhesion to the sealing material, and are not only used during the processing of solar cells but also used outdoors as solar cells. There has been a problem that it is easy to peel off at the interface with the sealing material or at the easily adhesive layer.
  • the solar cell in view of the conventional problems, is excellent in adhesion with a sealing material and maintains adhesion even when left outdoors for a long time (excellent retention property). It aims at providing the sheet
  • the present invention has the following configuration. That is, it has a base material layer (P1 layer) made of a polyester resin and an easy adhesion layer (P2 layer) adjacent to at least one side of the P1 layer, and the P2 layer is the following (1), (2) It is a solar cell back surface protection sheet characterized by satisfying the requirements. (1) Contains three components, a urethane resin component, a melamine resin component, and an epoxy resin component. (2) The contact angle of water is 74 ° or more.
  • the present invention compared to a conventional laminated sheet in which an easy-adhesion layer is provided on the surface of a biaxially stretched polyester film, it has excellent adhesiveness with a sealing material, and even when placed outdoors for a long period of time.
  • the sheet for protecting the back surface of a solar cell of the present invention has a base material layer (P1 layer) made of a polyester resin and an easy adhesion layer (P2 layer) adjacent to at least one side of the P1 layer.
  • P1 layer base material layer
  • P2 layer easy adhesion layer
  • (1) and (2) are satisfied.
  • (1) Contains three components, a urethane resin component, a melamine resin component, and an epoxy resin component.
  • the contact angle of water is 74 ° or more.
  • the P1 layer in the present invention contains a polyester resin as a main component.
  • the main constituent component of the polyester resin means that the polyester resin is contained in an amount exceeding 50% by mass with respect to the resin constituting the P1 layer.
  • Specific examples of the polyester resin constituting the P1 layer include polyethylene terephthalate, polyethylene-2,6-naphthalate, polypropylene terephthalate, polybutylene terephthalate, and polylactic acid.
  • the polyester resin used in the present invention includes 1) polycondensation of dicarboxylic acid or an ester-forming derivative thereof (hereinafter collectively referred to as “dicarboxylic acid component”) and a diol component, and 2) carboxylic acid or carboxylic acid in one molecule. It can be obtained by a polycondensation of an acid derivative and a compound having a hydroxyl group, and 1) 2).
  • the polymerization of the polyester resin can be performed by a conventional method.
  • dicarboxylic acid component malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalonic acid
  • Aliphatic dicarboxylic acids such as ethylmalonic acid
  • alicyclic dicarboxylic acids such as adamantane dicarboxylic acid, norbornene dicarboxylic acid, cyclohexane dicarboxylic acid, decalin dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4
  • dicarboxyl obtained by condensing oxyacids such as l-lactide, d-lactide, and hydroxybenzoic acid, and derivatives thereof, or a combination of a plurality of such oxyacids, at least one carboxy terminus of the dicarboxylic acid component described above.
  • oxyacids such as l-lactide, d-lactide, and hydroxybenzoic acid, and derivatives thereof, or a combination of a plurality of such oxyacids, at least one carboxy terminus of the dicarboxylic acid component described above.
  • oxyacids such as l-lactide, d-lactide, and hydroxybenzoic acid, and derivatives thereof, or a combination of a plurality of such oxyacids, at least one carboxy terminus of the dicarboxylic acid component described above.
  • Compounds can also be used.
  • the diol component includes aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 1,3-butanediol. , Cycloaliphatic dimethanol, spiroglycol, isosorbide and other alicyclic diols, bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9,9'-bis (4-hydroxyphenyl) fluorene, etc. Aromatic diols are typical examples. Moreover, these may be used independently or may be used in multiple types as needed. In addition, a dihydroxy compound formed by condensing a diol with at least one hydroxy terminal of the diol component described above can also be used.
  • aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-but
  • examples of the compound having a carboxylic acid or a carboxylic acid derivative and a hydroxyl group in one molecule include oxyacids such as l-lactide, d-lactide and hydroxybenzoic acid, and derivatives thereof, oligomers of oxyacids, dicarboxylic acids Examples thereof include those obtained by condensing an oxyacid with one carboxyl group of the acid.
  • the dicarboxylic acid component and the diol component constituting the polyester resin may be copolymerized by selecting one from the above, or may be copolymerized by selecting a plurality of each.
  • the polyester resin constituting the P1 layer may be a single type or a blend of two or more types of polyester resins.
  • the resin constituting the P1 layer in the present invention is mainly a polyester resin, but the intrinsic viscosity IV is 0.65 dl / g or more and 0.80 dl / g or less, and the terminal carboxyl group amount is 25 equivalents / It is preferably less than tons.
  • the polyester resin is preferably composed mainly of polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the main component means that it is contained in excess of 50% by mass with respect to the polyester resin.
  • the intrinsic viscosity IV of the PET is preferably 0.65 dl / g or more, more preferably 0.69 dl / g or more.
  • the intrinsic viscosity IV When the intrinsic viscosity IV is less than 0.65 dl / g, the moisture and heat resistance of the sheet may be deteriorated. Moreover, when intrinsic viscosity IV exceeds 0.80 dl / g, when the P1 layer is manufactured, the extrudability of the resin is poor, and sheet molding may be difficult. Furthermore, even if the intrinsic viscosity IV satisfies the above range, if the terminal carboxyl group amount exceeds 25 equivalents / ton, the adhesion with the P2 layer is improved, but the moisture and heat resistance of the sheet is deteriorated, which is not preferable. There is. Therefore, when the resin constituting the P1 layer contains PET as a main constituent, by satisfying the above range, a sheet for protecting a back surface of a solar cell that is extremely excellent in moldability and long-term durability can be obtained.
  • the number average molecular weight of the polyester resin constituting the P1 layer is preferably 8000 to 40000, more preferably 9000 to 30000, and still more preferably 10,000 to 20000.
  • the number average molecular weight of the polyester resin constituting the P1 layer refers to the gel permeation chromatography method by separating the P2 layer from the solar cell back surface protective sheet of the present invention and dissolving it in hexafluoroisopronol (HEIP).
  • HEIP hexafluoroisopronol
  • PET-5R polyethylene terephthalate
  • Mw 55800 polyethylene terephthalate
  • the number average molecular weight of the polyester resin constituting the P1 layer is less than 8000, it is not preferable because the long-term durability of the sheet such as moisture and heat resistance may be deteriorated.
  • it exceeds 40,000 even if the polymerization is difficult or the polymerization can be performed, it may be difficult to extrude the resin with an extruder and film formation may be difficult.
  • the P1 layer is preferably uniaxially or biaxially oriented.
  • the long-term durability of the sheet such as moist heat resistance and heat resistance can be improved by orientation crystallization.
  • a method of containing particles having respective functions is also preferably used.
  • titanium oxide particles in the range of 1% by mass to 30% by mass with respect to the resin constituting the P1 layer. This makes it possible to reduce the coloring due to deterioration of the sheet for protecting the back surface of the solar cell over a long period by utilizing the ultraviolet absorbing ability and the light reflectivity by the titanium oxide particles, and the sun mounted with the sheet for protecting the back surface of the solar cell of the present invention. Both of the effects of increasing the power generation efficiency of the battery can be expected.
  • a more preferable range is 1% by mass or more and 25% by mass or less, further preferably 2% by mass or more and 25% by mass or less, and particularly preferably 3% by mass or more and 20% by mass or less.
  • a rutile type titanium oxide from the viewpoint of achieving both excellent ultraviolet resistance and light reflectivity.
  • 0.1 particles made of a carbon-based material such as fullerene, carbon fiber, or carbon nanotube are used as the resin constituting the P1 layer. It is preferable to contain in the range of mass% or more and 5 mass% or less. This makes it possible to exhibit the effect of reducing coloring due to deterioration of the sheet for protecting the back surface of the solar cell over a long period of time by making use of the ultraviolet absorbing ability and light hiding property of the carbon particles. If it is less than 0.1% by mass, the UV resistance may be insufficient. If it exceeds 5% by mass, the adhesion with the P2 layer may be deteriorated. A more preferable range is 0.2% by mass or more and 4% by mass or less, and further preferably 0.5% by mass or more and 3% by mass or less.
  • a method of melt-kneading the polyester resin and the particles using a vent type twin-screw kneading extruder or a tandem type extruder is preferably used.
  • a high-concentration master pellet having a particle content larger than the amount of particles contained in the polyester resin constituting the P1 layer is prepared, mixed with the polyester resin and diluted to obtain a desired particle content P1 layer. It is preferable to produce it from the viewpoint of heat and humidity resistance.
  • the P1 layer in the solar cell back surface protection sheet of the present invention may include a heat-resistant stabilizer and an oxidation-resistant stabilizer as long as the effects of the present invention are not impaired.
  • an ultraviolet absorber is selected as an additive, the ultraviolet resistance of the solar cell back surface protective sheet of the present invention can be further enhanced.
  • anti-static agents are added to improve electrical insulation, or organic or inorganic fine particles or bubbles are included to express light reflectivity, or a color material to be colored is added to create a design. Can also be given.
  • the P1 layer in the present invention may have a laminated structure.
  • a laminated structure of a P11 layer excellent in heat and moisture resistance and a layer P12 layer containing a high concentration of an ultraviolet absorber or titanium oxide particles having an ultraviolet absorbing ability is preferably used.
  • the configuration of the solar cell back surface protection sheet of the present invention is preferably P12 layer / P11 layer // P2 layer from the viewpoint of coexistence of moisture and heat resistance.
  • the resin and particles used for the P11 layer and the P12 layer those exemplified for the P1 layer can be suitably used as appropriate.
  • the P1 layer preferably has a thickness of 30 ⁇ m or more and less than 500 ⁇ m.
  • the thickness of the P1 layer is less than 30 ⁇ m, the electrical insulation is insufficient, and when it is used under a high voltage, dielectric breakdown may occur, which may not be preferable as a solar cell back surface protection sheet.
  • the thickness is greater than 500 ⁇ m, the processability is poor, and when used as a solar battery back surface protection sheet, the overall thickness of the solar battery cell may become too thick, which may be undesirable.
  • a preferable range is 38 ⁇ m or more and 400 ⁇ m or less, and more preferably 50 ⁇ m or more and 300 ⁇ m or less.
  • the solar cell back surface protection sheet of the present invention needs to be provided with a P2 layer as an easy adhesion layer adjacent to the P1 layer. At this time, the P2 layer needs to be provided on at least one side of the P1 layer.
  • the P2 layer is characterized by containing three components of a urethane resin component, a melamine resin component, and an epoxy resin component.
  • the urethane resin component mentioned here includes not only urethane resins but also components obtained by reacting urethane resins with each other or with urethane resins and other components (melamine resin or epoxy resin).
  • the melamine resin component includes not only melamine resins but also components obtained by reacting melamine resins with each other or with melamine resins and other components (urethane resin or epoxy resin).
  • the epoxy resin component includes not only an epoxy resin but also a component obtained by reacting an epoxy resin with each other or with an epoxy resin and another component (urethane resin or melamine resin).
  • the term “the three components” as used herein means that the surface of the P2 layer has an X-ray photoelectron spectrometer (ESCA), a Fourier infrared spectrophotometer (FT-IR) ATR method, a time-of-flight secondary Ion mass spectrometer (TOF-SIMS) or P2 layer is dissolved and extracted with a solvent, proton nuclear magnetic resonance spectroscopy ( 1 H-NMR), carbon nuclear magnetic resonance spectroscopy ( 13 C-NMR), Fourier infrared It can be confirmed by analyzing the structure with a spectrophotometer (FT-IR) and performing a qualitative analysis of the P2 layer performed by pyrolysis gas chromatography mass spectrometry (GC-MS).
  • ESA X-ray photoelectron spectrometer
  • the urethane resin component contained in the P2 layer of the present invention is obtained by reacting a resin containing a urethane bond obtained by a reaction between a polyol compound and a polyisocyanate compound in the main chain, and the resin and other components. Resin.
  • the urethane resin component preferably includes a urethane resin having a polyester skeleton in which the polyol component is a polyester polyol (hereinafter sometimes referred to as a polyester urethane resin).
  • the polyester polyol preferably has a polyester structure synthesized from a dicarboxylic acid component and a diol component shown below.
  • Dicarboxylic acid components include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalonic acid, ethylmalonic acid, etc.
  • Aliphatic dicarboxylic acids such as decalin dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5- Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 5- Sodium sulfoisophthalate , Phenyl ene boys carboxylic acid, anthracene dicarboxylic acid, phenanthrene carboxylic acid, 9,9'-bis (4-carboxyphenyl)
  • diol component examples include aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, Arocyclic diols such as methanol, spiroglycol and isosorbide, aromatic diols such as bisphenol A, 1,3-benzenedimethanol, 1,4-benzendimethanol and 9,9'-bis (4-hydroxyphenyl) fluorene Is mentioned.
  • aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, Arocyclic diols such as methanol, spiroglycol and isosorbide, aromatic diols such as bisphenol A, 1,3
  • the urethane resin component contained in the P2 layer of the present invention has excellent adhesion retention with the sealing material even after the acceleration test.
  • the solar battery can be made more durable.
  • the polyisocyanate component used for the urethane resin one or a mixture of two or more known aromatic, aliphatic and alicyclic diisocyanates can be used.
  • diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, isophorone diisocyanate, dimaryl diisocyanate, Examples thereof include lysine diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, dimerized isocyanate obtained by converting the carboxyl group of dimer acid to an isocyanate group, and adducts, biurets, and isocyanurates. Further, as the diisocyanates,
  • the urethane resin preferably has a hydrophilic group.
  • the hydrophilic group includes a functional group that becomes an anion in an aqueous medium such as a carboxyl group, a sulfonic acid group, a sulfuric acid group, and a phosphoric acid group.
  • a polyol component having a carboxyl group, a sulfonic acid group, a sulfuric acid group, a phosphoric acid group or the like may be used.
  • the polyol compound having a carboxyl group include 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, and 2,2-bis (hydroxypropyl).
  • Propionic acid bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 2,2-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2 -Hydroxyethyl) -3-carboxyl-propionamide and the like.
  • the molecular weight of the urethane resin can be appropriately adjusted using a chain extender.
  • chain extender include compounds having two or more active hydrogens such as amino groups and hydroxyl groups capable of reacting with isocyanate groups.
  • diamine compounds, dihydrazide compounds, and glycols can be used.
  • urethane resins can be used by obtaining commercially available resins such as, for example, Hydran series, Bondic series manufactured by DIC Corporation, and Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • the melamine resin component contained in the P2 layer in the present invention is a resin having a triazine ring in its molecule and three amino groups around it, and a resin obtained by reacting the resin with other components.
  • the melamine resin is preferably tri-type, and by using the tri-type melamine resin, the adhesion retention after the acceleration test can be further improved.
  • melamine resins can be obtained by using commercially available resins such as, for example, Becamine series manufactured by DIC Corporation, and Nicarak series manufactured by Sanwa Chemical Co., Ltd.
  • the epoxy resin component contained in the P2 layer in the present invention is a resin having a glycidyl group in the molecule and a resin obtained by reacting the resin with other components.
  • the number of functional groups of the epoxy resin is preferably three or more, and by using an epoxy resin having three or more functional groups, the adhesion retention after the acceleration test can be further enhanced. Further, the upper limit of the number of functional groups of the epoxy resin is not limited to this range, but those having 4 functional groups or less are common.
  • epoxy resins can be used by obtaining commercially available resins such as EPICLON series, ADDITIVE series manufactured by DIC Corporation, and Denacol series manufactured by Nagase ChemteX Corporation.
  • P2 layer in this invention is a layer formed from the coating composition containing a urethane resin, a melamine resin, and an epoxy resin, and 80 mass% by solid content weight in the coating composition in which urethane resin forms P2 layer It is preferable to contain 99% by mass or less. More preferably, it is 90 mass% or more.
  • the coating composition which forms P2 layer in P2 layer in this invention when the urethane resin contains 80 mass% or more by solid content weight, in the solar cell back surface protection sheet
  • the upper limit of the solid content weight of the urethane resin in the coating composition for forming the P2 layer is not limited to this range, but is 99% by mass or less from the viewpoint of adhesion retention after the acceleration test. It is preferable to do this.
  • the weight ratio Wm / We (weight of melamine resin / weight of epoxy resin) of the melamine resin and the epoxy resin in the coating composition forming the P2 layer in the present invention is preferably in the range of 2 to 5, More preferably, it is in the range of 2.5-4.
  • the weight ratio Wm / We of the melamine resin and the epoxy resin in the coating composition for forming the P2 layer in the present invention is in the range of 2 to 5, adhesion retention after the acceleration test can be further improved.
  • the P2 layer needs to have a water contact angle of 74 ° or more.
  • the contact angle of water is a contact angle with water obtained by a method defined in JIS K-6768 (1999), preferably 76 ° or more, more preferably 79 ° or more. If the contact angle of water in the P2 layer is less than 74 °, even if adhesion with the sealing material is obtained, adhesion retention after the acceleration test is insufficient.
  • the coating composition forming the P2 layer contains three components of urethane resin, melamine resin, and epoxy resin, and the coating composition It can be obtained by setting the solid content weight ratio of the urethane resin contained therein to 70% by mass or more.
  • the solid content weight ratio of the urethane resin contained in the coating composition that forms the P2 layer is 80% by mass or more, and the coating material that forms the P2 layer. It can be obtained by setting the weight ratio Wm / We of the melamine resin and the epoxy resin contained in the composition in the range of 2 to 5.
  • the upper limit of the contact angle with water of the P2 layer is not limited, but is preferably less than 99 °.
  • the contact angle of the P2 layer with water is 99 ° or more, the adhesion with the P1 layer may be lowered, and as a result, the adhesion between the solar cell back surface protection sheet of the present invention and the sealing material is insufficient. There is a case.
  • the P2 layer contains three components of a urethane resin component, a melamine resin component, and an epoxy resin component, and the contact angle of water is set to 74 ° or more, whereby a sealing material It is possible to achieve both the adhesion and the adhesion retention after the acceleration test.
  • the solar cell back surface protection sheet of the present invention is mounted on a solar cell, the solar cell is excellent in durability even when placed outdoors for a long period of time. It can be a battery.
  • Various additives such as a surfactant and an ultraviolet absorber can be added.
  • the solar cell back surface protection sheet of the present invention when the solar cell back surface protection sheet of the present invention is mounted on a solar cell by adding an ultraviolet absorber to the P2 layer, the solar cell back surface protection sheet and the sealing material are irradiated by ultraviolet light from the power generation cell side. It can suppress that adhesiveness falls.
  • the ultraviolet absorber inorganic particles such as titanium oxide and zinc oxide, those containing an ultraviolet absorber, and a resin component copolymerized with a molecular skeleton having ultraviolet absorbing ability are preferably used and preferably contained.
  • the amount is from 1% to 50%, more preferably from 5% to 40%, and even more preferably from 10% to 30% by weight of the solid content in the coating composition forming the P2 layer.
  • blocking at the time of winding can be prevented by adding silica particles as an anti-blocking agent to the P2 layer. Further, by adding a surfactant to the P2 layer, it is possible to increase the affinity of the coating liquid for the P1 layer and suppress coating unevenness.
  • the thickness of the P2 layer in the solar cell back surface protective sheet of the present invention is preferably 0.1 ⁇ m or more and 2.0 ⁇ m or less, more preferably 0.2 ⁇ m or more and 1.2 ⁇ m or less, and further preferably 0.5 ⁇ m or more and 1.0 ⁇ m. It is as follows. When the thickness of the P2 layer in the solar cell back surface protective sheet of the present invention is less than 0.1 ⁇ m, the adhesion to the sealing material may be insufficient. On the other hand, if the thickness of the P2 layer is more than 2.0 ⁇ m, the winding property may deteriorate due to insufficient drying, or the coating property may deteriorate.
  • the P2 layer in the present invention may have a laminated structure for the purpose of improving easy adhesion.
  • an anchor coat layer (referred to as P21 layer) having excellent adhesion with the P1 layer is provided in advance on one surface of the P1 layer, and a layer (referred to as P22 layer) that is further excellent in easy adhesion on the P21 layer.
  • the providing method is also preferably used.
  • the structure of the sheet is laminated in the order of P1 layer // P21 layer / P22 layer, and the thickness of the P2 layer is represented by P21 layer + P22 layer.
  • the P21 layer has good adhesiveness with the resin constituting the P1 layer and the P22 layer
  • the P22 layer is excellent in adhesiveness with the resin constituting the P21 layer and the sealing material.
  • the resin used for the P21 layer and the P22 layer those exemplified for the P2 layer can be suitably used as appropriate.
  • the solar cell back surface protective sheet of the present invention is provided with a layer having other functions such as gas barrier property and ultraviolet resistance on one side surface of the P1 layer (however, the surface opposite to the surface in contact with the P2 layer). be able to.
  • thermo laminating method a method of separately preparing materials to be laminated with the P1 layer and thermocompression bonding with a heated group of rolls
  • a method of bonding together with an adhesive a method of bonding together with an adhesive
  • coating method a method of dissolving the material for forming the material to be laminated in a solvent and applying the solution onto the P1 layer prepared in advance
  • electromagnetic wave irradiation after applying a curable material onto the P1 layer
  • a method of curing by heat treatment or the like a method of depositing / sputtering a material to be laminated on the P1 layer, a method combining these, and the like can be used.
  • the solar cell back surface protection sheet of the present invention is excellent in moisture and heat resistance.
  • the elongation at break after applying the wet heat treatment to the solar cell back surface protective sheet of the present invention is preferably 10% or more, more preferably 20% or more, and further preferably 40% or more. The details of the method for measuring the elongation at break after the wet heat treatment here will be described later.
  • the breaking elongation after applying wet heat treatment is less than 10%
  • the solar cell equipped with the solar cell back surface protection sheet of the present invention is placed outdoors for a long time
  • cracks and the like due to deterioration may occur and the appearance of the solar cell may deteriorate.
  • polyethylene having an intrinsic viscosity IV of 0.65 dl / g or more and a terminal carboxyl group content of 25 equivalents / ton or less is used for the polyester resin constituting the P1 layer.
  • a preferable method is to use terephthalate.
  • the solar cell back surface protective sheet of the present invention preferably has excellent ultraviolet resistance. Specifically, it is preferable that the color tone change ⁇ b when the ultraviolet ray treatment test is performed using the P1 layer of the solar cell back surface protective sheet of the present invention as an incident surface is less than 10, more preferably less than 3. Details of the method for measuring the color tone change ⁇ b when the ultraviolet treatment test is performed will be described later.
  • the solar cell back surface protection sheet of the present invention when the color change ⁇ b when the ultraviolet treatment test is performed with the P1 layer as the incident surface exceeds 10, the solar cell mounted with the solar cell back surface protection sheet of the present invention is long. When placed outdoors during the period, the appearance of the solar cell may deteriorate due to discoloration due to ultraviolet rays.
  • a solar cell back surface protection sheet excellent in moist heat resistance and ultraviolet resistance is used for a long time outdoors with the solar cell mounted with the solar cell back surface protection sheet of the present invention. Even if it is placed, it can be a solar cell having no appearance defect.
  • the manufacturing method of the raw material which comprises P1 layer can be manufactured with the following method.
  • the resin used as the raw material of the P1 layer of the present invention can be obtained by subjecting dicarboxylic acid or its ester derivative and diol to a transesterification reaction or an esterification reaction by a well-known method.
  • reaction catalysts include alkali metal compounds, alkaline earth metal compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, and phosphorus compounds.
  • an antimony compound, a germanium compound, or a titanium compound is preferably added as a polymerization catalyst at an arbitrary stage before the PET production method is completed.
  • the polyester resin As such a method, for example, when a germanium compound is taken as an example, it is preferable to add the germanium compound powder as it is.
  • the polyester resin In order to control the number average molecular weight of the polyester resin, for example, when the number average molecular weight is 10,000 to 20,000, the polyester resin having a number average molecular weight of about 9500 is once polymerized by the above method, and then 190 ° C.
  • a so-called solid-phase polymerization method in which heating is performed at a temperature lower than the melting point of the polyester resin under reduced pressure or a flow of an inert gas such as nitrogen gas is preferable. This method is preferably performed in that the number average molecular weight can be increased without increasing the terminal carboxyl group amount of the thermoplastic resin.
  • the P1 layer manufacturing method is a method in which the P1 layer raw material is heated and melted in an extruder and extruded from a die onto a cast drum cooled (processed into a sheet). Method).
  • the raw material for the P1 layer is dissolved in a solvent, and the solution is extruded from a die onto a support such as a cast drum or an endless belt to form a film, and then the solvent is dried and removed from the film layer.
  • a method of processing into a shape (solution casting method) or the like can also be used.
  • the material of each layer to be laminated is mainly composed of a thermoplastic resin
  • the two different thermoplastic resins are put into two extruders and melted to join.
  • a method of co-extrusion onto a cast drum cooled from the die and processing it into a sheet can be preferably used.
  • a uniaxial or biaxially stretched sheet base material is selected as the laminate including the P1 layer and / or the P1 layer, as a manufacturing method thereof, first, an extruder (in the case of a laminated structure, a plurality of extruders) ), Melt and extrude from the die (coextrusion in the case of a laminated structure), and cool and solidify by static electricity on a drum cooled to a surface temperature of 10 to 60 ° C. to produce an unstretched sheet .
  • an extruder in the case of a laminated structure, a plurality of extruders
  • Melt and extrude from the die coextrusion in the case of a laminated structure
  • static electricity on a drum cooled to a surface temperature of 10 to 60 ° C.
  • the unstretched sheet is led to a group of rolls heated to a temperature of 70 to 140 ° C., stretched 3 to 4 times in the longitudinal direction (longitudinal direction, that is, the traveling direction of the sheet), and the temperature is 20 to 50 ° C. Cool with rolls.
  • both ends of the sheet are guided to a tenter while being gripped by clips, and stretched 3 to 4 times in a direction (width direction) perpendicular to the longitudinal direction in an atmosphere heated to a temperature of 80 to 150 ° C.
  • the stretching ratio is 3 to 5 times in each of the longitudinal direction and the width direction, but the area ratio (longitudinal stretching ratio ⁇ lateral stretching ratio) is preferably 9 to 15 times.
  • the area ratio is less than 9 times, the durability of the resulting biaxially stretched sheet is insufficient, and conversely when the area magnification exceeds 15 times, there is a tendency that tearing tends to occur during stretching.
  • the simultaneous biaxial stretching method in addition to the sequential biaxial stretching method in which the stretching in the longitudinal direction and the width direction is separated as described above, the simultaneous biaxial stretching method in which the stretching in the longitudinal direction and the width direction is performed simultaneously. Either one does not matter.
  • the method for forming the P2 layer on the P1 layer in the sheet of the present invention is not particularly limited, but it is preferable to use a coating technique.
  • a coating method a known method can be applied, and for example, a roll coating method, a dip coating method, a bar coating method, a die coating method, a gravure roll coating method, or a combination of these methods can be used. it can.
  • the bar coating method is preferable from the viewpoint of a wide selection range of the coating agent, while the die coating method and the gravure roll coating method can be preferably selected from the viewpoint of thick film coating property when it is desired to increase the thickness of the P2 layer.
  • the P2 layer is formed by in-line coating provided in the manufacturing process of the P1 layer from the viewpoint of simplifying the process.
  • the heat setting temperature of the P1 layer is preferably 150 ° C. or more and 250 ° C. or less, more preferably 170 ° C. from the viewpoint of the compatibility between the drying temperature of the coating composition, the thermal dimensional stability of the base material layer P1 and the heat and humidity resistance. It is more than 230 degreeC, More preferably, it is 180 degreeC or more and 220 degrees C or less.
  • a corona treatment may be applied to the surface of the base material layer P1 immediately before the coating step. Good.
  • Examples of the solvent for the coating composition for forming the P2 layer in the sheet of the present invention include toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethylformamide, dimethylacetamide, Methanol, ethanol, water and the like can be exemplified, and the properties of the coating liquid may be either emulsion type or dissolution type.
  • the method of emulsifying the urethane resin, melamine resin, and epoxy resin contained in the coating composition for forming the P2 layer is not particularly limited, and is widely used as a solid / liquid stirring device or an emulsifier. It can be made by equipment known to the vendor.
  • the solar cell back surface protection sheet of the present invention can be manufactured by the above manufacturing method.
  • the obtained sheet for protecting the back surface of the solar battery has excellent adhesion to the sealing material of the solar battery cell, maintains adhesion even when left outdoors for a long time (excellent retention), and is moisture resistant. It has the performance of being excellent in heat resistance and ultraviolet resistance.
  • the solar cell of the present invention is characterized by using the solar cell back surface protective sheet.
  • the solar cell back surface protection sheet By using the solar cell back surface protection sheet, it is possible to increase the durability as compared with the conventional solar cell.
  • An example of the configuration is shown in FIG.
  • a power generating element connected with a lead wire for taking out electricity (not shown in FIG. 1) is sealed with a transparent sealing material 2 such as EVA resin, a transparent substrate 4 such as glass, and a solar cell back surface protection Although it is configured to be bonded as the sheet 1, it is not limited to this and can be used for any configuration.
  • the solar cell back surface protection sheet shows an example of a single body, the solar cell back surface protection sheet should be a composite sheet in which other films are laminated according to other required characteristics. Is also possible.
  • the solar cell back surface protection sheet 1 plays a role of protecting the power generation cell installed on the back surface of the sealing material 2 sealing the power generation element.
  • the solar cell back surface protection sheet is preferably arranged so that the P2 layer is in contact with the sealing material 2.
  • the power generating element 3 converts light energy of sunlight into electric energy, and is based on crystalline silicon, polycrystalline silicon, microcrystalline silicon, amorphous silicon, copper indium selenide, compound semiconductor, dye enhancement Arbitrary elements such as a sensitive system can be used in series or in parallel according to the desired voltage or current depending on the purpose. Since the transparent substrate 4 having translucency is located on the outermost surface layer of the solar cell, a transparent material having high weather resistance, high contamination resistance, and high mechanical strength characteristics in addition to high transmittance is used. In the solar cell of the present invention, the transparent substrate 4 having translucency can be made of any material as long as the above characteristics are satisfied. Examples thereof include glass, ethylene tetrafluoride-ethylene copolymer (ETFE), polyfluoride.
  • ETFE ethylene tetrafluoride-ethylene copolymer
  • Vinyl fluoride resin PVDF
  • PVDF polyvinylidene fluoride resin
  • TFE polytetrafluoroethylene resin
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • CFE polytrifluoroethylene chloride resin
  • Fluorinated resins such as polyvinylidene fluoride resin, olefinic resins, acrylic resins, and mixtures thereof.
  • glass it is more preferable to use a tempered glass.
  • stretched the said resin uniaxially or biaxially from a viewpoint of mechanical strength is used preferably.
  • the adhesiveness with EVA resin etc. which are the sealing materials of an electric power generation element, it is also preferably performed to give the surface a corona treatment, a plasma treatment, an ozone treatment, and an easy adhesion treatment. .
  • the sealing material 2 for sealing the power generation element covers and fixes the unevenness of the surface of the power generation element with resin, protects the power generation element from the external environment, and has a translucent base for the purpose of electrical insulation.
  • a material having high transparency, high weather resistance, high adhesion, and high heat resistance is used in order to adhere to the material or back sheet and the power generation element. Examples thereof include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA) resin, ethylene-methacrylic acid copolymer (EMAA), Ionomer resins, polyvinyl butyral resins, and mixtures thereof are preferably used.
  • the solar cell of the present invention can be suitably used for various applications without being limited to outdoor use and indoor use such as a solar power generation system and a power source for small electronic components.
  • Measurement method and evaluation method of characteristics (1) Component qualitative property of P2 layer The component qualitative property of the P2 layer in Examples and Comparative Examples was performed by separating the P2 layer of the solar cell back surface protection sheet and performing pyrolysis gas chromatography mass spectrometry (GC-MS).
  • Pyrolytic device PY-2010DD frontier lab
  • gas chromatograph GC-14AF gas chromatograph
  • FID flame ionization detector
  • column is used for the column.
  • a methylsilicone capillary column was connected for use. Further, derivatization was performed with TMAH (tetramethylammonium hydroxide) as necessary. The presence or absence of each component was determined as follows, and in the table, the P2 layer was described as Y when each component was contained, and N when not contained.
  • the terminal carboxyl group amount was measured by the following method according to the method of Malice. (Document M. J. Malice, F. Huizinga, Anal. Chim. Acta, 22 363 (1960)). 2 g of a measurement sample (polyester resin (raw material) or solar cell back surface protection sheet P1 layer only) 2 g was dissolved in 50 ml of o-cresol / chloroform (weight ratio 7/3) at a temperature of 80 ° C. The solution was titrated with a 05N KOH / methanol solution, and the terminal carboxyl group concentration was measured and indicated by the value of equivalent / polyester 1t.
  • the indicator at the time of titration used phenol red, and the place where it changed from yellowish green to light red was set as the end point of titration. If there is insoluble matter such as inorganic particles in the solution in which the measurement sample is dissolved, the solution is filtered to measure the weight of the insoluble matter, and the value obtained by subtracting the weight of the insoluble matter from the measurement sample weight The following correction was made.
  • Thickness of P2 layer Using a microtome, a small piece cut in a direction perpendicular to the surface of the solar cell back surface protection sheet was prepared, and the cross section was taken as a field emission scanning electron microscope JSM-6700F (JEOL Ltd. ))) And magnified to 10,000 times. From the cross-sectional photograph, the thickness of the P2 layer was calculated from the magnification. In addition, the thickness used the cross-sectional photograph of five places arbitrarily selected from the different measurement visual field, and used the average value.
  • Adhesion evaluation with sealing material 5-1
  • Adhesion with sealing material Based on JIS K 6854-2 (1999) an EVA sheet as a sealing material and a solar cell back surface protection sheet
  • the adhesiveness was evaluated from the peel strength with the surface on the P2 layer side.
  • the measurement test piece is a 500 ⁇ m thick EVA sheet (vinyl acetate copolymerization ratio: 28 mol%) on a semi-tempered glass having a thickness of 3 mm, and the P2 layer side of the sheet of the example and the comparative example is the EVA sheet side.
  • a layer obtained by press treatment using a commercially available vacuum laminator under conditions of a hot platen temperature of 145 ° C., a vacuum drawing of 4 minutes, a press of 1 minute, and a holding time of 10 minutes was used.
  • the peel strength test is performed at 180 ° peel, the width of the test piece is 10 mm, two test pieces are prepared, the place is changed for each test piece, the measurement is performed at three places, and the average value of the obtained measurement values is peeled off
  • the initial adhesion was determined as follows using the strength value.
  • seat of this invention fractured
  • the wet heat resistance was determined as follows.
  • breaking elongation after the wet heat test is 40% or more of the breaking elongation before the wet heat test: A When the breaking elongation after the wet heat test is 20% or more and less than 40% of the breaking elongation before the wet heat test: B When the breaking elongation after the wet heat test is 10% or more and less than 20% of the breaking elongation before the wet heat test: C When the breaking elongation after the wet heat test is less than 10% of the breaking elongation before the wet heat test: D The wet heat resistance is good in A to C, and A is the best among them.
  • the longitudinal direction of the wiring material protruding from the cell of the produced 1-cell module wiring and the longitudinal direction of the copper foil A-SPS 0.23 ⁇ 6.0 made by Hitachi Cable as the take-out electrode cut into 180 mm are perpendicular to each other. Then, the flux was applied to the portion where the wiring material and the take-out electrode overlapped, and solder welding was performed to produce a wire with the take-out electrode.
  • 190 mm ⁇ 190 mm 3.2 mm thick white plate heat-treated glass for solar cells manufactured by Asahi Glass Co., Ltd. 190 mm ⁇ 190 mm 500 ⁇ m thick EVA sheet (vinyl acetate copolymerization ratio: 28 mol%), produced wiring with takeout electrode, 190 mm ⁇ A 190 mm 500 ⁇ m thick EVA sheet and a solar cell back surface protection sheet cut out to 190 mm ⁇ 190 mm are stacked in order so that the P2 layer side surface is located on the EVA side, and the glass is brought into contact with the hot platen of the vacuum laminator And laminating under the conditions of a hot platen temperature of 145 ° C., a vacuuming of 4 minutes, a press of 1 minute, and a holding time of 10 minutes to produce a solar cell. At this time, the wiring with the extraction electrode was set so that the glass surface was on the cell surface side.
  • PET raw material A used in Examples 1 to 16, 18, 20 and Comparative Examples 1 to 6)
  • a polycondensation reaction was performed using 100 parts by mass of terephthalic acid as the dicarboxylic acid component, 100 parts by mass of ethylene glycol as the diol component, and magnesium acetate, antimony trioxide, and phosphorous acid as the catalyst.
  • the obtained polyethylene terephthalate was dried and crystallized at 160 ° C. for 6 hours, and then subjected to solid phase polymerization at 220 ° C. and a vacuum degree of 0.3 Torr for 9 hours to have a melting point of 255 ° C. and an intrinsic viscosity of 0.80 dl / g.
  • PET-A polyethylene terephthalate
  • PET raw material B (used in Example 19) A polycondensation reaction was performed using 100 parts by mass of terephthalic acid as the dicarboxylic acid component, 100 parts by mass of ethylene glycol as the diol component, and magnesium acetate, antimony trioxide, and phosphorous acid as the catalyst. Next, the obtained polyethylene terephthalate was dried and crystallized at 160 ° C. for 6 hours to obtain a polyethylene terephthalate (PET-B) raw material having a melting point of 255 ° C., an intrinsic viscosity of 0.65 dl / g, and a terminal carboxyl group content of 25 equivalents / ton. It was.
  • PET-B polyethylene terephthalate
  • reaction temperature reached 220 ° C.
  • 0.042 parts by mass of 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt was added.
  • a transesterification reaction was carried out, and 0.023 parts by mass of trimethyl phosphoric acid was added.
  • the reaction product is transferred to a polymerization apparatus, heated to a temperature of 290 ° C., subjected to a polycondensation reaction under a high vacuum of 30 Pa, and the stirring torque of the polymerization apparatus is a predetermined value (specifically depending on the specifications of the polymerization apparatus).
  • polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.65 in this polymerization apparatus was a predetermined value.
  • the obtained polyethylene naphthalate was dried and crystallized at 160 ° C. for 6 hours, and then subjected to solid phase polymerization at 220 ° C. and a vacuum degree of 0.3 Torr for 9 hours, melting point 255 ° C., intrinsic viscosity 0.70 dl / g, A PEN raw material having a terminal carboxyl group attachment amount of 25 equivalents / ton was obtained.
  • PET raw material A-based titanium oxide master used in Examples 1 to 15, 20 and Comparative Examples 1 to 6) Above 1. 100 parts by mass of the PET resin (PET-A) obtained according to the above and 100 parts by mass of rutile-type titanium oxide particles having an average particle diameter of 210 nm are melt-kneaded in a vented 290 ° C. extruder to obtain a titanium oxide raw material (PETa- TiO 2 ) was prepared.
  • PET raw material B base titanium oxide master (used in Example 19) 2. 100 parts by mass of the PET resin (PET-B) obtained according to the above and 100 parts by mass of rutile-type titanium oxide particles having an average particle diameter of 210 nm are melt-kneaded in a vented 290 ° C. extruder to obtain a titanium oxide raw material (PETb- TiO 2 ) was prepared.
  • PEN raw material-based titanium oxide master (used in Example 17) 4. above. 100 parts by mass of the PEN resin obtained according to the above and 100 parts by mass of rutile-type titanium oxide particles having an average particle diameter of 210 nm are melt-kneaded in a vented 300 ° C. extruder to produce a titanium oxide raw material (PEN-TiO 2 ). did.
  • PET raw material A base carbon particle master (used in Example 18) Above 1. 100 parts by mass of the PET resin (PET-A) obtained according to the above and 100 parts by mass of carbon particles having an average particle diameter of 40 nm were melt-kneaded in a vented 290 ° C. extruder to obtain a carbon particle raw material (PETa-CB). Produced.
  • Coating agents A to I (used in Examples 1 to 9 and 16 to 20) DIC Corporation polyester urethane resin coating “Hydran” (registered trademark) AP-201 as urethane resin and DIC Corporation tri-type melamine resin coating “Beckamine” (registered trademark) PM-80 as epoxy resin, as epoxy resin
  • DIC Corporation polyester urethane resin coating “Hydran” (registered trademark) AP-201 as urethane resin
  • DIC Corporation tri-type melamine resin coating “Beckamine” (registered trademark) PM-80 as epoxy resin
  • Coating agent J (used in Example 10) A coating agent J was obtained in the same manner as coating agent A, except that a polyether urethane resin coating agent “HYDRAN” (registered trademark) WLS-202 manufactured by DIC Corporation was used as the urethane resin.
  • a polyether urethane resin coating agent “HYDRAN” registered trademark
  • Coating agent K (used in Example 11) A coating K was obtained in the same manner as coating A except that the polycarbonate urethane resin coating “HYDRAN” (registered trademark) WLS-213 manufactured by DIC Corporation was used as the urethane resin.
  • Coating agent L (used in Examples 12 and 13) Coating agent L was obtained in the same manner as coating agent A, except that dilution with pure water was performed so that the solid content concentration was 6% by mass.
  • Coating agent M (used in Examples 14 and 15) Coating agent M was obtained in the same manner as coating agent A, except that the solid content concentration was 23% by mass with dilution with pure water.
  • Coating agent N (used in Example 21) A coating agent N was obtained in the same manner as coating agent A, except that a hexa-type melamine resin coating agent “Beckamine” (registered trademark) J-101 manufactured by DIC Corporation was used as the melamine resin.
  • Coating agent O used in Comparative Example 1
  • DIC Corporation Polyester Urethane Resin “Hydran” (Registered Trademark) AP-201 was used alone as the urethane resin to dilute with pure water to a solid content concentration of 17% by mass to obtain Coating O .
  • Coating agent P (used in Comparative Example 2) DIC Corporation polyester urethane resin coating “Hydran” (registered trademark) AP-201 as urethane resin and DIC Corporation tri-type melamine resin coating “Beccamin” (registered trademark) PM-80 as melamine resin in Table 3 After mixing at a solid content weight ratio, the mixture was diluted with pure water so that the solid content concentration was 17% by mass, and a coating agent P was obtained.
  • Coating agent R (used in Comparative Example 4) DIC Corporation polyester urethane resin coating “Hydran” (registered trademark) AP-201 as urethane resin and DIC Corporation tri-type melamine resin coating “Beckamine” (registered trademark) PM-80 as epoxy resin, as epoxy resin
  • DIC Corporation polyester urethane resin coating “Hydran” (registered trademark) AP-201 as urethane resin
  • DIC Corporation tri-type melamine resin coating “Beckamine” (registered trademark) PM-80 as epoxy resin
  • Coating agent S (used in Comparative Example 5) A coating S was obtained in the same manner as the coating A except that an acrylic resin-based coating “Nicazole” (registered trademark) RX7013ED manufactured by Nippon Carbide Industries Co., Ltd. was used instead of the urethane resin.
  • Coating agent T (used in Comparative Example 6) A coating agent T was obtained in the same manner as the coating agent A except that a polyester resin-based coating material Pes Resin TR620K manufactured by Takamatsu Yushi Co., Ltd. was used instead of the urethane resin.
  • PET raw material A (PET-A) vacuum-dried at 180 ° C. for 2 hours and PET raw material A-based titanium oxide master (PETa-TiO 2 ) were blended so that the amount of particles was the concentration shown in Table 1, and inside the extruder at 280 ° C. And kneaded and introduced into a T die die. Subsequently, it was melt-extruded into a sheet form from a T-die die and adhered and cooled and solidified by an electrostatic application method on a drum maintained at a surface temperature of 25 ° C. to obtain an unstretched sheet.
  • PET raw material A PET-A
  • PET raw material A-based titanium oxide master PET raw material A-based titanium oxide master
  • the tenter While holding both ends of the obtained uniaxially stretched sheet with a clip, the tenter is guided to a preheating zone at a temperature of 80 ° C. in the tenter, and then continuously heated at 90 ° C. in a direction perpendicular to the longitudinal direction (width direction).
  • the film was stretched 3.5 times.
  • heat treatment was performed at 220 ° C. for 20 seconds in a heat treatment zone in the tenter, and further relaxation treatment was performed in the 4% width direction at 220 ° C. Then, it was gradually cooled gradually to form a sheet having a total thickness of 125 ⁇ m.
  • the P2 layer contains three components of a urethane resin component, a melamine resin component, and an epoxy resin component. Except for Examples 10 and 11, the urethane resin component contains a polyester urethane resin. It was confirmed to be a urethane resin component.
  • the solar cell back surface protection sheet has good initial adhesion and adhesion retention with the sealing material, and in particular, the example in which the contact angle with water of the P2 layer is in a preferable range (76 ° or more) is sealed.
  • the contact angle with the water of the P2 layer is in a more preferable range (79 ° or more) is excellent in the close contact retention with the material. It turned out that it is a sheet for use. It was also found that all the solar cell back surface protection sheets obtained were excellent in heat and moisture resistance and UV resistance. Furthermore, the solar cell carrying the obtained solar cell back surface protection sheet was produced, and the durability of the solar cell was evaluated. As a result, as shown in Table 4, it was found that the solar cell on which the sheet for protecting the back surface of the solar cell, which was very excellent in adhesion and retention with the sealing material, had very excellent durability.
  • Example 12 to 15 The coating agent corresponding to the number of the example in the coating agent described in Table 2 in the P2 layer is the same as that in Example 1 except that the count of the metering bar is adjusted so as to be the thickness of the P2 layer shown in Table 2. Similarly, a sheet was obtained. When the characteristics of the P2 layer of the obtained sheet were evaluated, the contact angle with water and the thickness were as shown in Table 2.
  • the P2 layer contained three components, a urethane resin component, a melamine resin component, and an epoxy resin component, and the thickness of the P2 layer was thinner than that of Example 1.
  • Nos. 12 and 13 were found to be solar cell back surface protection sheets in a range that is inferior in initial adhesion to the sealing material and in close contact retention but no problem.
  • Examples 14 and 15 in which the thickness of the P2 layer was thicker than Example 1 had initial adhesion and adhesion retention with a very excellent sealing material equivalent to Example 1, As for No. 15, application stripes were confirmed visually.
  • the solar cell on which the obtained solar cell back surface protection sheets of Examples 14 and 15 are mounted has extremely excellent durability, and the solar cell back surface protection sheets of Examples 12 and 13 are mounted.
  • the solar cell was found to be in a range where there is no problem although it is inferior in durability.
  • Example 16 A sheet was obtained in the same manner as in Example 1 except that only PET raw material A (PET-A) was used for the P1 layer.
  • PET-A PET raw material A
  • the P1 layer was separated from the obtained sheet and the polymer characteristics were measured, the intrinsic viscosity IV and the amount of terminal carboxyl groups were as shown in Table 2.
  • the obtained sheet has initial adhesion and adhesion retention with a very excellent sealing material equivalent to that in Example 1, and is slightly inferior in UV resistance, but very excellent moisture and heat resistance. It turned out that it is a solar cell back surface protection sheet which has. Furthermore, it turned out that the solar cell carrying the obtained sheet
  • Example 17 A sheet was obtained in the same manner as in Example 1 except that the PEN material (PEN) and the PEN-based titanium oxide master (PEN-TiO 2 ) were used for the P1 layer.
  • the P1 layer was separated from the obtained sheet and the polymer characteristics were measured, the intrinsic viscosity IV and the amount of terminal carboxyl groups were as shown in Table 2.
  • the obtained sheet is inferior to Example 1 but has excellent initial adhesiveness and adhesiveness retention with a sealing material, and has a very excellent moisture and heat resistance sheet.
  • seat for solar cell back surface protection was inferior compared with Example 1, it turned out that it has the outstanding durability.
  • Example 18 A sheet was obtained in the same manner as in Example 1 except that PET raw material A (PET-A) and PET raw material A-based CB master (PETa-CB) were used for the P1 layer.
  • PET raw material A PET raw material A
  • PET raw material A-based CB master PET raw material A-based CB master
  • the P1 layer was separated from the obtained sheet and the polymer characteristics were measured, the intrinsic viscosity IV and the amount of terminal carboxyl groups were as shown in Table 2.
  • the obtained sheet has initial adhesion and adhesion retention with a very excellent sealing material equivalent to that of Example 1, and has a very excellent ultraviolet resistance for protecting the back surface of a solar cell. It turned out to be a sheet. Furthermore, it turned out that the solar cell carrying the obtained sheet
  • Example 19 A sheet was obtained in the same manner as in Example 1 except that PET raw material B (PET-B) and PET raw material B-based titanium oxide master (PETb-TiO 2 ) were used for the P1 layer.
  • PET raw material B PET raw material B
  • PETb-TiO 2 PET raw material B-based titanium oxide master
  • the obtained sheet has initial adhesiveness and adhesion retention with a very excellent sealing material equivalent to that of Example 1, and has no problem although moisture and heat resistance is inferior to that of Example 1. It turned out that it is a solar cell back surface protection sheet. Furthermore, although the solar cell carrying the obtained sheet
  • the PET raw material A PET-A
  • PET raw material A-based titanium oxide master PETa-TiO 2
  • the raw materials were melted and kneaded separately by two extruders, introduced into a T-die die through feed blocks from the two extruders to obtain a laminated sheet of P11 / P12. Obtained.
  • the screw rotation speeds of the two extruders were adjusted so that the stacking ratio of P11 / P12 was 7/1.
  • the intrinsic viscosity IV and the amount of terminal carboxyl groups were as shown in Table 2.
  • the obtained sheet was found to be a sheet for protecting the back surface of a solar cell having very excellent easy adhesion equivalent to that of Example 1, and having very excellent moist heat resistance and ultraviolet resistance. It was. Furthermore, it turned out that the solar cell carrying the obtained sheet
  • Example 21 As described in Table 2, a sheet was obtained in the same manner as in Example 1 except that the coating agent N was applied to the P2 layer. When the characteristics of the P2 layer of the obtained sheet were evaluated, the contact angle with water and the thickness were as shown in Table 2.
  • the obtained sheet was found to be a sheet for protecting the back surface of a solar cell, which was inferior to that of Example 1 but had excellent initial adhesion and adhesion retention with an excellent sealing material. Furthermore, although the solar cell carrying the obtained sheet
  • the solar cell back surface protection sheet of the present invention can be suitably used as a back surface protection sheet of a solar cell module.
  • it can be suitably used as an easy-adhesive sheet in applications that require adhesion with an ethylene-vinyl acetate copolymer resin.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Laminated Bodies (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Le but de la présente invention est de fournir une feuille de protection du côté arrière d'une cellule solaire, qui présente une excellente adhérence à un matériau d'étanchéité et qui conserve l'adhérence même lorsqu'elle est disposée en extérieur pendant une longue durée (qui possède notamment une excellente capacité de maintien d'adhérence). La feuille de protection du côté arrière d'une cellule solaire (1) selon la présente invention comprend: une couche de base (couche P1) faite d'une résine de polyester; et une couche hautement adhésive (couche P2) adjacente à au moins un côté de la couche P1. La couche P2 répond aux conditions (A) et (B) suivantes. (A): contenir trois composants, à savoir un composant de résine d'uréthanne, un composant de résine de mélamine et un composant de résine époxy. (B): avoir un angle de contact avec l'eau de 74° ou plus.
PCT/JP2014/082698 2013-12-27 2014-12-10 Feuille pour protection de côté arrière de cellule solaire WO2015098520A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017182040A (ja) * 2016-03-29 2017-10-05 三菱ケミカル株式会社 積層ポリエステルフィルムおよびその製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002301787A (ja) * 1997-09-25 2002-10-15 Mitsubishi Chemicals Corp 蒸着プラスチックフイルムの製造方法
JP2010016286A (ja) * 2008-07-07 2010-01-21 Toppan Printing Co Ltd 太陽電池裏面封止用シート
WO2013136861A1 (fr) * 2012-03-15 2013-09-19 Dic株式会社 Agent de thermoscellage, corps stratifié l'utilisant et module de cellules solaires
JP2013253189A (ja) * 2012-06-08 2013-12-19 Toyobo Co Ltd 易接着フィルムおよびその製造方法
WO2015001951A1 (fr) * 2013-07-05 2015-01-08 東レ株式会社 Substrat protecteur côté inférieur, module de photopile et procédé de production d'un module de photopile

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002301787A (ja) * 1997-09-25 2002-10-15 Mitsubishi Chemicals Corp 蒸着プラスチックフイルムの製造方法
JP2010016286A (ja) * 2008-07-07 2010-01-21 Toppan Printing Co Ltd 太陽電池裏面封止用シート
WO2013136861A1 (fr) * 2012-03-15 2013-09-19 Dic株式会社 Agent de thermoscellage, corps stratifié l'utilisant et module de cellules solaires
JP2013253189A (ja) * 2012-06-08 2013-12-19 Toyobo Co Ltd 易接着フィルムおよびその製造方法
WO2015001951A1 (fr) * 2013-07-05 2015-01-08 東レ株式会社 Substrat protecteur côté inférieur, module de photopile et procédé de production d'un module de photopile

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017182040A (ja) * 2016-03-29 2017-10-05 三菱ケミカル株式会社 積層ポリエステルフィルムおよびその製造方法

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