WO2009157545A1 - 太陽電池用積層シート及びこれを用いた太陽電池モジュール - Google Patents
太陽電池用積層シート及びこれを用いた太陽電池モジュール Download PDFInfo
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- WO2009157545A1 WO2009157545A1 PCT/JP2009/061737 JP2009061737W WO2009157545A1 WO 2009157545 A1 WO2009157545 A1 WO 2009157545A1 JP 2009061737 W JP2009061737 W JP 2009061737W WO 2009157545 A1 WO2009157545 A1 WO 2009157545A1
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- WIPO (PCT)
- Prior art keywords
- ethylene
- solar cell
- copolymer
- laminated sheet
- sheet
- Prior art date
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
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- 125000005442 diisocyanate group Chemical group 0.000 description 1
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
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- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
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- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
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- JCNCSCMYYGONLU-UHFFFAOYSA-N n,n'-bis(2-methylphenyl)methanediimine Chemical group CC1=CC=CC=C1N=C=NC1=CC=CC=C1C JCNCSCMYYGONLU-UHFFFAOYSA-N 0.000 description 1
- XLDBGFGREOMWSL-UHFFFAOYSA-N n,n'-bis[2,6-di(propan-2-yl)phenyl]methanediimine Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C=NC1=C(C(C)C)C=CC=C1C(C)C XLDBGFGREOMWSL-UHFFFAOYSA-N 0.000 description 1
- CMESPBFFDMPSIY-UHFFFAOYSA-N n,n'-diphenylmethanediimine Chemical compound C1=CC=CC=C1N=C=NC1=CC=CC=C1 CMESPBFFDMPSIY-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- NQKOSCFDFJKWOX-UHFFFAOYSA-N n-[3-[diethoxy(methyl)silyl]propyl]aniline Chemical compound CCO[Si](C)(OCC)CCCNC1=CC=CC=C1 NQKOSCFDFJKWOX-UHFFFAOYSA-N 0.000 description 1
- YZPARGTXKUIJLJ-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]aniline Chemical compound CO[Si](C)(OC)CCCNC1=CC=CC=C1 YZPARGTXKUIJLJ-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000011242 organic-inorganic particle Substances 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000005394 sealing glass Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- JRQSGAVWKHXROZ-UHFFFAOYSA-N silane 3-triethoxysilylpropan-1-amine Chemical compound [SiH4].CCO[Si](OCC)(OCC)CCCN JRQSGAVWKHXROZ-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- NAQGCFBMSYBDFZ-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) propane-1,1,2,3-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(=O)OC1CC(C)(C)NC(C)(C)C1 NAQGCFBMSYBDFZ-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- OIRRCMCATRAYJG-UHFFFAOYSA-N tris(2,2,6,6-tetramethylpiperidin-4-yl) 1H-triazine-2,4,6-tricarboxylate Chemical compound CC1(NC(CC(C1)OC(=O)N1NC(=CC(=N1)C(=O)OC1CC(NC(C1)(C)C)(C)C)C(=O)OC1CC(NC(C1)(C)C)(C)C)(C)C)C OIRRCMCATRAYJG-UHFFFAOYSA-N 0.000 description 1
- DYSUTBVWFJRUKW-UHFFFAOYSA-N tris(2,2,6,6-tetramethylpiperidin-4-yl) 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)(OC(=O)C)CC(=O)OC1CC(C)(C)NC(C)(C)C1 DYSUTBVWFJRUKW-UHFFFAOYSA-N 0.000 description 1
- HBUNLJQRZABWAM-UHFFFAOYSA-N tris(2,2,6,6-tetramethylpiperidin-4-yl) 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(O)(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 HBUNLJQRZABWAM-UHFFFAOYSA-N 0.000 description 1
- HAJIOQHUJLPSAL-UHFFFAOYSA-N tris(2,2,6,6-tetramethylpiperidin-4-yl) benzene-1,3,5-tricarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC(C(=O)OC2CC(C)(C)NC(C)(C)C2)=CC(C(=O)OC2CC(C)(C)NC(C)(C)C2)=C1 HAJIOQHUJLPSAL-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
- C08L23/0876—Neutralised polymers, i.e. ionomers
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2809—Web or sheet containing structurally defined element or component and having an adhesive outermost layer including irradiated or wave energy treated component
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2857—Adhesive compositions including metal or compound thereof or natural rubber
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2887—Adhesive compositions including addition polymer from unsaturated monomer including nitrogen containing polymer [e.g., polyacrylonitrile, polymethacrylonitrile, etc.]
Definitions
- the present invention relates to a solar cell laminated sheet for fixing a solar cell element constituting a solar cell module and a solar cell module including the same.
- Solar power generation directly converts solar energy into electrical energy using a silicon cell semiconductor (solar cell element). Since the function of the solar cell element used here is reduced when it comes into direct contact with outside air, the solar cell element is generally composed of a sealing material and a transparent surface protective material (mainly glass), and a back surface protective material (polyester resin). System or a back sheet made of a fluororesin, etc., thereby preventing the entry of foreign matter and moisture with buffering. At this time, the back sheet protects the solar cell element from the external environment (rain, humidity, wind, etc.), as well as various electrical insulation, flame retardancy, heat resistance, adhesion to the sealing material, weather resistance, etc. Performance is required. Therefore, various materials and configurations have been studied in order to satisfy these performances.
- the back sheet a sheet for sealing the back surface of a solar cell using a film such as a polyester resin or a fluororesin excellent in electrical insulation is used.
- a film such as a polyester resin or a fluororesin excellent in electrical insulation.
- this polyester resin or fluororesin film is used, there is a problem that the adhesiveness to the sealing material is inferior as a demerit.
- an easy-adhesion coat layer functioning as a primer is applied on the back sheet (for example, see Patent Document 1), and a corona treatment is applied to a polyester film (for example, see Patent Document 2).
- a corona treatment is applied to a polyester film.
- Solar cells are required to be durable enough to maintain their performance for a long period of about 20 years, and the adhesiveness between the sealing material and the back sheet determines the reliability of the solar cells.
- the adhesive strength between the sealant and the back sheet is significantly reduced, and when delamination occurs due to the influence, the sealing material also permeates through the part where moisture has peeled off, resulting in a decrease in output, etc. May cause problems.
- a solar cell module when manufacturing a solar cell module, it manufactures with the following two methods. (1) A back sheet, a sealing material, a solar cell element, a sealing material, and a glass plate are stacked in this order and heated to be integrated. (2) The solar cell element forming surface on which the solar cell element is directly formed on the glass plate is stacked in the order of the sealing material and the back sheet, and is heated and integrated. In each of these methods, it is necessary to prepare a back sheet and a sealing material separately, and stack and integrate them while performing careful transportation and careful positioning simultaneously with other members including solar cell elements. In addition, a place for storing (stocking) each member is also necessary. In addition, when a module is manufactured, a manufacturing facility for supplying each member is required and a large installation place is required.
- the present invention has been made in view of the above situation. Under such circumstances, at the manufacturing site of the conventional solar cell module, the material management and the handling of the material are greatly improved, contributing to the improvement of productivity and the simplification of the manufacturing equipment, and the back sheet and the sealing. There is a need for a laminated sheet for solar cells that is excellent in interlayer adhesion strength with a material. Also, There is a need for a solar cell module with excellent durability.
- the surface of the backsheet base material using a fluororesin or polyester resin, which has been subjected to chemical treatment or physical treatment for improving adhesion, is selected from carboxylic acid groups and carboxylate-derived groups.
- Laminated sheet for solar cell in which a sealing material layer containing a copolymer of a polar monomer having a polar group and ethylene and an ethylene copolymer composition containing a dialkoxysilane having an amino group is laminated by a melt extrusion lamination method It is.
- the chemical treatment is the laminated sheet for solar cells according to ⁇ 1>, in which a two-component reaction type urethane resin anchor coating agent is applied.
- urethane resin anchor coating agent is a two-component reactive adhesive composition using a main agent containing a polyester urethane polyol and a curing agent containing an isocyanate compound. It is preferable that
- ⁇ 4> The solar cell laminated sheet according to any one of ⁇ 1> to ⁇ 3>, wherein the physical treatment is a corona treatment.
- the copolymer of the polar monomer and ethylene is at least one selected from an ionomer of an ethylene / unsaturated carboxylic acid copolymer and an ethylene / unsaturated carboxylic acid copolymer It is preferable that it is a laminated sheet for solar cells as described in any one of ⁇ 4>.
- the dialkoxysilane is at least one selected from 3-aminopropylalkyldialkoxysilane and N-2- (aminoethyl) -3-aminopropylalkyldialkoxysilane.
- ⁇ 1> to ⁇ 5 It is preferable that it is a lamination sheet for solar cells as described in any one of>.
- the content ratio of the dialkoxysilane is 15 parts by mass or less with respect to 100 parts by mass of the copolymer of the polar monomer and ethylene, according to any one of ⁇ 1> to ⁇ 6>
- a laminated sheet for solar cells is preferable.
- ⁇ 8> The solar cell according to any one of ⁇ 5> to ⁇ 7>, wherein the ethylene / unsaturated carboxylic acid copolymer is an ethylene / acrylic acid copolymer or an ethylene / methacrylic acid copolymer. Laminated sheet for use.
- ⁇ 9> The solar cell laminate sheet according to any one of ⁇ 5> to ⁇ 8>, wherein the ionomer is a zinc ionomer of an ethylene / unsaturated carboxylic acid copolymer.
- ⁇ 11> The ⁇ 5> to ⁇ 10>, wherein the ethylene / unsaturated carboxylic acid copolymer has a proportion of constituent units derived from the unsaturated carboxylic acid of 20% by mass or less based on the total mass of the copolymer. It is a laminated sheet for solar cells as described in any one of these.
- the content of the dialkoxysilane is 0.03 to 12 parts by mass with respect to 100 parts by mass of the ethylene / polar monomer copolymer, and any one of ⁇ 1> to ⁇ 11> It is a laminated sheet for solar cells as described in above.
- the fluororesin is tetrafluoroethylene / ethylene copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, polychlorotrifluoroethylene, chlorotrifluoroethylene.
- the laminated sheet for solar cells according to any one of ⁇ 1> to ⁇ 12>, which is at least one selected from an ethylene copolymer, polyvinyl fluoride, and polyvinylidene fluoride.
- the polyester resin is at least one selected from polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polycyclohexanedimethanol-terephthalate (PCT). It is preferable that it is a laminated sheet for solar cells according to any one of the above ⁇ 13>.
- a solar cell module comprising a substrate on which sunlight is incident, a solar cell element, and the laminated sheet for solar cell according to any one of ⁇ 1> to ⁇ 14>.
- the member management and the handling of the member are greatly improved, contributing to the improvement of productivity and the simplification of the manufacturing equipment, and the back sheet and the sealing material
- the laminated sheet for solar cells excellent in interlayer adhesive strength is provided.
- ADVANTAGE OF THE INVENTION According to this invention, the solar cell module excellent in durability is provided.
- the laminated sheet for a solar cell of the present invention has a carboxylic acid group and a carboxylic acid on the surface of a backsheet base material using a fluororesin or a polyester resin, which has been subjected to chemical treatment or physical treatment for improving adhesion.
- a sealing material layer comprising a copolymer of a polar monomer having a polar group selected from a salt-derived group and ethylene and an ethylene copolymer composition containing a dialkoxysilane having an amino group is melt-extruded and laminated. It is configured in a laminated structure using the method.
- the present invention can provide a laminated sheet for solar cells in which a back sheet and a sealing material are integrated.
- this laminated sheet for solar cells significantly improves the member management and the handling of the members at the manufacturing site of the conventional solar cell module. That is, it is not necessary to manage the back sheet and the sealing material separately.
- the method (2) for producing the solar cell module described above can provide innovative productivity in the production of a thin film type solar cell module.
- the present invention enables high-speed integral molding of the backsheet and the sealing material by a melt lamination method, and exhibits strong interlaminar adhesion strength, so that it has excellent long-term durability.
- the present invention strongly adheres to an inorganic material such as glass, a solar cell module having excellent durability can be provided.
- a copolymer of a specific polar monomer and ethylene (hereinafter referred to as an ethylene / polar monomer copolymer) is applied to the surface of the backsheet substrate that has been subjected to chemical treatment or physical treatment described later.
- a composition for an encapsulant comprising an ethylene copolymer composition containing a specific alkoxysilane compound can be laminated and integrated at a high speed by a melt lamination method.
- the resulting laminated sheet has moisture and water resistance, flexibility, and moldability during module production.
- the adhesion of the back sheet in a laminated structure including a substrate / solar cell element / back sheet on which sunlight is incident specifically, a sealing material is provided between the solar cell element and the back sheet.
- a sealing material is provided between the solar cell element and the back sheet.
- the ethylene / polar monomer copolymer in the present invention is a polymer obtained by copolymerizing ethylene and a polar monomer as at least a copolymerization component, and other monomers may be copolymerized as necessary.
- the polar monomer is an unsaturated monomer having an unsaturated group and at least one polar group selected from a group derived from a carboxylic acid group and a carboxylate group, and is used alone or in combination of two or more. Also good.
- the unsaturated group is preferably an addition polymerizable group, more preferably a group containing an ethylenically unsaturated bond.
- Carboxylic acid groups and carboxylate-derived groups are preferred in terms of adhesiveness compared to other polar groups other than these.
- polar monomers having a carboxylic acid group and a carboxylate-derived group include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid, Maleic acid monoesters (monomethyl maleate, monoethyl maleate, etc.), etc., and salts of these monovalent metals (eg, lithium, potassium, sodium, etc.) or salts of polyvalent metals (eg, magnesium, calcium, zinc, etc.) Etc.
- acrylic acid and methacrylic acid are preferred in terms of the reactivity of the carboxylic acid group.
- an ethylene / acrylic acid copolymer and an ethylene / methacrylic acid copolymer are particularly preferable in terms of adhesiveness.
- the polar monomer is a metal salt of an unsaturated carboxylic acid
- this ethylene / polar monomer copolymer is known as an ionomer.
- the ethylene / unsaturated carboxylic acid copolymer used as the base of the ionomer of the ethylene / unsaturated carboxylic acid copolymer the same copolymer as described above can be used.
- the metal species include alkali metals such as lithium and sodium, and polyvalent metals such as calcium, magnesium, zinc and aluminum. The advantage of using such an ionomer is transparency and high storage modulus at high temperatures.
- the degree of neutralization for example, 80% or less is desirable, but in view of adhesiveness and the like, those having a very high degree of neutralization are not desirable.
- the ionomer preferably has, for example, a neutralization degree of 60% or less, particularly 30% or less.
- the lower limit of the degree of neutralization is preferably 5%.
- ethylene / polar monomer copolymer used as the base of the ionomer an ethylene / acrylic acid copolymer and an ethylene / methacrylic acid copolymer are preferable.
- metal species zinc is particularly preferably used.
- Zinc ionomers contain zinc ions as metal ions, so they are particularly superior in weather resistance compared to ionomers containing other metal ions such as Na, and the generation of gels and foams during sheet preparation is greatly suppressed. This improves stability during sheet production.
- the ratio of the “structural unit derived from the polar monomer” in the ethylene / polar monomer copolymer is 1% by mass or more based on the total mass of the copolymer. When the proportion is 1% by mass or more, it is positively contained. When the proportion is less than 1% by mass, the adhesiveness of the resulting copolymer is lowered, and the durability of the solar cell is lowered. This is particularly suitable in the case of an ethylene / unsaturated carboxylic acid copolymer or its ionomer, and the proportion of structural units derived from the unsaturated carboxylic acid is 1% by mass or more based on the total mass of the copolymer. It is preferable.
- the ratio of the structural unit derived from unsaturated carboxylic acid is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total mass of the copolymer.
- the melting point of the ethylene / polar monomer copolymer is preferably 55 ° C. or higher, more preferably 60 ° C. or higher, and particularly preferably 70 ° C. or higher.
- the melting point of the ethylene / polar monomer copolymer or its ionomer is 55 ° C. or higher, the heat resistance is good, and when used as a sealing material for sealing solar cell elements, the temperature rises when using solar cells. Deformation can be prevented, and problems such as generation of burrs due to the sealing material flowing out more than necessary when the solar cell module is manufactured by the thermocompression bonding method can be avoided.
- the ethylene / polar monomer copolymer in the present invention has a melt flow rate (MFR) of 1 to 100 g in JIS K7210-1999 (190 ° C., 2160 g load) in consideration of molding processability and mechanical strength. / 10 minutes are preferable, and those of 5 to 50 g / 10 minutes are particularly preferable.
- MFR melt flow rate
- the ethylene / polar monomer copolymer may have a structural unit derived from other monomers than ethylene and “polar monomer having a polar group selected from a carboxylic acid group and a group derived from a carboxylate”.
- Another monomer may be a copolymer obtained by copolymerizing, for example, vinyl ester or alkyl ester of (meth) acrylic acid, and the effect of imparting flexibility can be obtained.
- the proportion of other monomers in the copolymer may be appropriately selected within a range not impairing the effects of the present invention.
- the ethylene / polar monomer copolymer can be obtained by radical copolymerization under high temperature and high pressure.
- An ionomer of an ethylene / polar monomer copolymer can be obtained by reacting an ethylene / polar monomer copolymer with a metal compound.
- Examples of the “dialkoxysilane having an amino group” blended in the ethylene copolymer composition in the present invention include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (amino 3) such as N-2- (aminoethyl) -3-aminopropylalkyldialkoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane such as ethyl) -3-aminopropylmethyldiethoxysilane -Aminopropylalkyldialkoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldiethoxysilane and the like.
- dialkoxysilane N-2- (aminoethyl) -3-aminopropylalkyldialkoxysilane (more preferably, the alkyl moiety has 1 to 3 carbon atoms) or 3-aminopropylalkyldialkoxysilane (More preferably, the alkyl moiety has 1 to 3 carbon atoms).
- N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyl Methyldiethoxysilane is preferred.
- N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane is preferably used because it is easily available industrially.
- dialkoxysilane as a silane coupling agent as in the invention, thickening and gelation in the lamination process are suppressed and stable, and adhesion is maintained with the back sheet while maintaining adhesion. You can do it.
- the dialkoxysilane having an amino group is effective in improving the adhesiveness with a base material (a substrate such as glass on the side on which sunlight is incident as well as a back sheet) sandwiching a solar cell element, and a gel at the time of forming a sheet, for example From the standpoint of stability such as suppression of occurrence of a state-like material, the amount is preferably 15 parts by mass or less, more preferably 0.03 to 12 parts by mass with respect to 100 parts by mass of the ethylene / polar monomer copolymer in the present invention, Particularly preferably, it is blended at a ratio of 0.05 to 12 parts by mass.
- the amount of dialkoxysilane having an amino group is 15 parts by mass or less, good adhesiveness can be obtained, and the formation of a gel-like material can be suppressed and sheet forming can be stably performed.
- the ethylene copolymer composition of the present invention may contain at least one weathering stabilizer such as an antioxidant, a light stabilizer, and an ultraviolet absorber, so that the sealing material based on ultraviolet rays in sunlight is used. This is effective in preventing deterioration.
- at least one weathering stabilizer such as an antioxidant, a light stabilizer, and an ultraviolet absorber
- Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2-carboxybenzophenone, 2-hydroxy-4-n.
- Benzophenone series such as octoxybenzophenone, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) benzotriazole, 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- Benzotriazoles such as (2′-hydroxy-5-tert-octylphenyl) benzotriazole and salicylic acid esters such as phenyl salicylate and p-octylphenyl salicylate can be preferably used.
- antioxidants and phosphites can be preferably used.
- the hindered phenol antioxidant include 2,6-di-t-butyl-p-cresol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2 , 6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4′-methylenebis (2,6-di-t-butylphenol), 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol], bis [3,3-bis (4-hydroxy) -3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-t-butyl-m-cresol), 2,2′-ethylidene
- phosphite antioxidants include 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate dimethyl ester, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid) Examples thereof include ethyl and tris (2,4-di-t-butylphenyl) phosphinate.
- a hindered amine-based one can be preferably used as the light stabilizer.
- specific examples include hindered amine light stabilizers such as 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyl.
- the above-mentioned weather stabilizer is preferably in the range of 5 parts by mass or less, particularly in the range of 0.1 to 3 parts by mass, with respect to 100 parts by mass of the ethylene / polar monomer copolymer.
- any other additive can be blended within the range not impairing the object of the present invention.
- various known additives can be used. For example, pigments, dyes, lubricants, anti-discoloring agents, anti-blocking agents, foaming agents, foaming aids, crosslinking agents, crosslinking aids, inorganic A filler, a flame retardant, etc. can be mentioned.
- the discoloration preventing agent metal fatty acid salts such as cadmium and barium can be used.
- pigments, dyes, inorganic fillers, and the like can be blended for the purpose of coloring and improving power generation efficiency. Examples thereof include white pigments such as titanium oxide and calcium carbonate, blue pigments such as ultramarine, black pigments such as carbon black, and glass beads and light diffusing agents.
- an inorganic pigment such as titanium oxide together with an ethylene / polar monomer copolymer, because it is excellent in the effect of preventing a decrease in insulation resistance.
- the preferred blending amount of these (especially inorganic pigments) is preferably 100 parts by weight or less, more preferably 100 parts by weight of ethylene / polar monomer copolymer. Is 0.5 to 50 parts by mass, particularly preferably 4 to 50 parts by mass.
- the surface on which the sealing material layer is laminated is subjected to a chemical treatment or a physical treatment to improve adhesion.
- the Examples of the physical treatment applied to the substrate surface of the polyester resin or fluororesin constituting the back sheet include corona treatment, plasma treatment, flame treatment, and ozone treatment.
- An example of the chemical treatment is anchor coating treatment.
- the amount of anchor coating agent used in the anchor coat treatment, from the viewpoint of obtaining good adhesion is preferably in the range of 1 ⁇ 300g / m 2, and more preferably a range of 3 ⁇ 200g / m 2.
- the anchor coat agent is an adhesive or an adhesion aid for enhancing the adhesion of the substrate, and may be appropriately selected from known materials, and either a solvent type or an aqueous type can be selected.
- a two-component reaction type urethane resin-based adhesive is preferable from the viewpoint of obtaining good adhesive strength between the substrate and the ethylene / polar monomer copolymer.
- the two-component reaction type urethane resin adhesive has excellent hydrolysis resistance.
- an adhesive composition obtained by blending a curing agent with either a polyester polyol or a polyester urethane polyol chain-extended with a bifunctional or higher isocyanate compound or a mixture thereof.
- an adhesive composition obtained by further blending 1 to 50 parts by mass of at least one compound selected from a carbodiimide compound, an oxazoline compound, and an epoxy compound with 100 parts by mass of the adhesive composition. .
- the polyester polyol is an aliphatic type such as succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, brassylic acid, and aromatic type such as isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid.
- the hydroxyl groups at both ends of the polyester polyol are, for example, 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, methylene diisocyanate, isopropylene diisocyanate, lysine diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isopropylidene dicyclohexyl-4,4 '-Isocyanate compound selected from diisocyanate and the like, or at least one selected from these isocyanate compounds
- Adducts consisting of biuret body, such as a polyester urethane polyol chain extension with isocyanurate
- polystyrene-based material examples include polyether polyol, polycarbonate polyol, acrylic polyol, and the like, and those containing these components as main components can be used. Of these, polycarbonate polyol and acrylic polyol are preferred in view of heat resistance and the like.
- An isocyanate compound can be used as the curing agent for crosslinking these.
- the present invention is not limited to this, and any type can be used as long as it is a curing agent reactive with active hydrogen groups.
- Examples of the oxazoline compound expected to have the same action include 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 2,4- Monooxazoline compounds such as diphenyl-2-oxazoline, 2,2 '-(1,3-phenylene) -bis (2-oxazoline), 2,2'-(1,2-ethylene) -bis (2-oxazoline) And dioxazoline compounds such as 2,2 ′-(1,4-butylene) -bis (2-oxazoline) and 2,2 ′-(1,4-phenylene) -bis (2-oxazoline).
- Examples of the epoxy compound expected to have the same action include diglycidyl ethers of aliphatic diols such as 1,6-hexanediol, neopentyl glycol, polyalkylene glycol, sorbitol, sorbitan, polyglycerol, penta Polyglycidyl ethers of aliphatic polyols such as erythritol, diglycerol, glycerol, trimethylolpropane, polyglycidyl ethers of alicyclic polyols such as cyclohexanedimethanol, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, adipic acid Diglycidyl esters or polyglycidyl esters of aliphatic and aromatic polycarboxylic acids such as sebacic acid, resorcinol, bis- (p-hydroxyphenyl) methane, 2,2- Digly
- the two-component reactive urethane resin anchor coating agent is preferably an adhesive composition using a main agent containing a polyester urethane polyol and a curing agent containing an isocyanate compound.
- ozone treatment, plasma treatment, corona discharge treatment, flame treatment, etc. are performed in advance on the welding surface of the sealing material layer of the backsheet substrate. You may give it.
- corona discharge treatment is preferably used from the viewpoints of convenience on manufacturing equipment, improvement in adhesion, and sustainability.
- the ethylene copolymer composition is an extruder such as an extrusion laminator or a lateral T-die extruder. It can be performed by a method of heating and melting and extruding and laminating on a surface on which a physical treatment or a chemical treatment has been performed on a backsheet substrate.
- the back sheet is subjected to corona treatment in advance and then laminated.
- the heating and melting should be performed so as to satisfy the desired temperature and viscosity in consideration of various properties such as fluidity, film formability, film thickness adjustment and film thickness uniformity of the ethylene copolymer composition of the present invention. Can do.
- a temperature at which the ethylene copolymer composition is in a molten state can be selected. Specifically, the temperature is preferably in the range of 100 to 300 ° C, more preferably in the range of 120 to 200 ° C.
- the “molten state” in the present invention refers to a state in which the resin is softened and exhibits spreadability. When supplied in this state, it is welded to the backsheet substrate. “Welding” means that adhesion occurs between the back sheet base material.
- Heat melting is preferably performed so that the viscosity of the ethylene copolymer composition at the time of melting is in the range of 50 to 500 Pa ⁇ s at 160 ° C.
- the heat melting is more preferably performed at 160 ° C. so as to have a viscosity in the range of 100 to 450 Pa ⁇ s.
- the viscosity is a value measured at 160 ° C. using a capillary rheometer.
- the melt viscosity is measured by detecting the shear rate and the shear stress when a molten sample in a cylinder at a constant temperature is extruded from a capillary die by a piston.
- extrusion molding such as single screw extrusion, twin screw extrusion, co-extrusion (eg, T-die extrusion method), calendar method, etc. Etc. can be performed. Specifically, it can be supplied using an extruder such as an extrusion laminator or a lateral T-die extruder.
- the thickness of the encapsulant layer containing the ethylene copolymer composition provided on the back sheet is not particularly limited, but is usually about 0.01 to 1.0 mm.
- the back sheet of the present invention is configured using a base material using a fluororesin or a polyester resin.
- a fluororesin or a polyester resin is suitable in terms of weather resistance, heat resistance, and insulation.
- As the substrate a fluororesin substrate mainly composed of a fluororesin and a polyester resin substrate mainly composed of a polyester resin are preferable.
- “mainly” means that the content ratio of the fluororesin or polyester resin in the resin substrate is 80% by mass or more.
- tetrafluoroethylene / ethylene copolymer PTFE
- tetrafluoroethylene / hexafluoropropylene copolymer FEP
- tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer PFA
- PCTFE polychlorotrifluoroethylene
- PCTFEE chlorotrifluoroethylene / ethylene copolymer
- PVDF polyvinyl fluoride
- PVDF polyvinylidene fluoride
- polyester resin a polyester base material selected from polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polycyclohexanedimethanol-terephthalate (PCT) is preferable for the same reason as above. Can be mentioned.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PBT polybutylene terephthalate
- PCT polycyclohexanedimethanol-terephthalate
- polyester base material a base material obtained using a polybasic acid or an ester-forming derivative thereof and a polyol or an ester-forming derivative thereof can be used.
- Polybasic acid components include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, dimer Acid components such as acid, maleic acid and itaconic acid, and polyol components include ethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, trimethylol Propane, pentaerythritol, xylene glycol, dimethylolpropane, poly (ethylene oxide) glycol, poly (tetramethylene oxide
- polyesters obtained from two or more of the polybasic acid components and one or more of the polyol components are preferably mentioned, and particularly, in terms of weather resistance and heat resistance, Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polycyclohexanedimethanol-terephthalate (PCT) are preferred.
- PET Polyethylene terephthalate
- PEN polyethylene naphthalate
- PBT polybutylene terephthalate
- PCT polycyclohexanedimethanol-terephthalate
- polyester resin base materials are materials that may be hydrolyzed. Therefore, when using a polyester-based substrate such as polyethylene terephthalate, the number average molecular weight is in the range of 18,000 to 40,000, the cyclic oligomer content is 1.5% by mass or less, and the intrinsic viscosity is 0.5 dl / g or more.
- a polyester base material having decomposability is preferable.
- the molecular terminal is a carboxylic acid group, it acts as heat, water, and further as an acid catalyst, and is most affected by hydrolysis.
- a solid phase polymerization method that can increase the number average molecular weight without increasing the amount of terminal carboxylic acid, or seal the terminal carboxylic acid group with a carbodiimide compound, oxazoline compound, or epoxy compound. You can also In addition, when there is a concern about the effect of shrinkage due to heat when manufacturing a solar cell module, a polyester base material having a heat shrinkage rate of 1% or less, preferably 0.5% or less by performing an annealing treatment is used. It is possible to use.
- UV absorbers such as benzophenone, benzotriazole, and triazine, hindered phenol-based, phosphorus-based, sulfur-based, tocopherol-based antioxidants, and hindered amine-based light stabilizers are also appropriately used. It is possible to mix.
- the back sheet used in the present invention is not only a fluororesin and a polyester resin, but also a polycarbonate resin, an acrylic resin, a polyolefin resin, a polyamide resin, a polyarylate resin, and the like, which are used for heat resistance, strength properties, You may adjust electrical insulation.
- the polyester resin substrate When a polyester resin substrate is used as the substrate constituting the back sheet of the present invention, the polyester resin substrate may be transparent, but from the viewpoint of improving weather resistance and appearance, it is white or black.
- a polyester film is preferred.
- the white polyester film is a “pigment dispersion type” added with white additives such as titanium oxide, silica, alumina, calcium carbonate, barium sulfate, or a polymer or fine particles incompatible with polyester, It is possible to use a “fine foaming type” or the like that is whitened by forming voids at the blend interface during biaxial stretching.
- the “polyester incompatible with polyester” is preferably a polyolefin resin such as polyethylene, polypropylene, polybutene, polymethylpentene. If necessary, it is possible to use polyalkylene glycol or a copolymer thereof as a compatibilizing agent.
- the fine particles include organic particles and inorganic particles, such as silicon particles, polyimide particles, crosslinked styrene-divinylbenzene copolymer particles, crosslinked polyester particles, and fluorine-based particles.
- the inorganic particles include calcium carbonate, silicon dioxide, barium sulfate and the like.
- a “pigment dispersion type” to which a black additive such as carbon black is added is used.
- a fluororesin or a polyester resin may be laminated in any form, and the fluororesin or the polyester resin is present on the side in contact with the ethylene copolymer composition of the present invention. If it is. In general, the following configurations can be adopted, but the present invention is not limited to these examples.
- the base material is composed of fluororesin / polyester resin / fluororesin, fluororesin / aluminum foil / fluororesin, polyester resin / aluminum foil / polyester resin, polyester resin / white polyester resin / polyester resin, silica-deposited polyester resin / white Examples include polyester resin, silica-deposited polyester resin / polyester resin / white polyester resin, and the like.
- the above-described laminated sheet for solar cell of the present invention, a solar cell element, and a transparent protective material such as glass are arranged so as to sandwich the solar cell element, and fixed by heating and / or pressure bonding.
- a solar cell module can be produced.
- the solar cell element is encapsulated from both sides thereof, such as the upper transparent protective substrate / sealing material / solar cell element / the laminated sheet for solar cell of the present invention described above on the side where sunlight enters.
- a solar cell module having a laminated structure sandwiched between the two.
- an amorphous solar cell element is formed on a glass substrate by sputtering or the like, and the laminated sheet for solar cell of the present invention described above so that the sealing material layer faces the solar cell element.
- the thing of the structure which piled up can be mentioned.
- the laminated sheet for a solar cell of the present invention can be formed as described above as long as the ethylene copolymer composition layer (encapsulant layer) has a sufficient thickness to exhibit performance as an encapsulant.
- No sealing material is required when manufacturing the battery module.
- the layer of the ethylene copolymer composition is thin, it is also possible to prepare a sealing material separately and manufacture a solar cell module by a normal method. In that case, it is preferable from the surface of durable adhesive that the sealing material prepared separately is the same kind as the ethylene copolymer composition of this invention.
- solar cell elements examples include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and III-V and II-VI compound semiconductor systems such as gallium-arsenic, copper-indium-selenium, and cadmium-tellurium.
- silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon
- III-V and II-VI compound semiconductor systems such as gallium-arsenic, copper-indium-selenium, and cadmium-tellurium.
- Various solar cell elements can be used.
- the laminated sheet for solar cells of the present invention described above is particularly useful from the viewpoint of sealing an amorphous solar cell element, for example, amorphous silicon, in terms of durable adhesiveness with a sealing material.
- Examples of the upper protective base material constituting the solar cell module include glass, acrylic resin, polycarbonate, polyester, fluorine-containing resin, and the like from the viewpoint of an incident surface on which sunlight is incident.
- the upper protective substrate is an acrylic resin, polycarbonate, polyester, fluorine-containing resin or the like
- the laminated sheet for solar cell of the present invention can be used as it is.
- Metal- indicates a copolymerization ratio of repeating structural units derived from methacrylic acid
- MFR is a mel flow rate value measured at 190 ° C. under a load of 2160 g in accordance with JIS K7210-1999.
- Resin Resin (a): Zn ionomer of ethylene / methacrylic acid copolymer (methacrylic acid content: 15% by mass, MFR: 5 g / 10 min, degree of neutralization: 23%, melting point: 91 ° C.)
- Silane coupling agent Silane coupling agent (a): N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane Silane coupling agent (b): N-2- (aminoethyl) -3-aminopropyltrimethoxysilane Silane coupling agent (c): 3-aminopropyltriethoxysilane Silane coupling agent (d): 3-glycidoxypropyltrimethoxysilane Silane coupling agent (e): 3-glycidoxypropylmethyl Diethoxysilane
- Antioxidant Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by Ciba Specialty Chemicals)
- UV absorber 2-hydroxy-4-n-octoxybenzophenone (Chimassorb 81, manufactured by Ciba Specialty Chemicals)
- Light stabilizer bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin 770DF, manufactured by Ciba Specialty Chemicals)
- Base material The following four types were prepared for the substrate.
- ⁇ Blue plate glass thickness 3.2 mm, size 7.5 cm ⁇ 12 cm (manufactured by Asahi Glass Co., Ltd., blue plate reinforced float glass)
- White plate glass thickness 3.2 mm, size 7.5 cm ⁇ 12 cm (Asahi Glass Co., Ltd., white plate tempered glass)
- Back sheet (2) PET (12 ⁇ m polyethylene terephthalate) / white PET (50 ⁇ m white polyethylene terephthalate) laminated substrate [polyester resin substrate; Toyo Aluminum manufactured by Toyo Aluminum Co., Ltd.] The back sheet (2) was subjected to corona treatment on both side surfaces and the surface wetting tension was 50 mN / m or more.
- sealing sheet 5000 g of the resin (a), 25 g of the silane coupling agent (a), 1 g of the antioxidant, 10 g of the ultraviolet absorber, and 3.5 g of the light stabilizer were weighed and mixed to obtain impregnated pellets.
- the molten resin was laminated on the anchor coat surface of the back sheet (2) arranged so that the anchor coat surface was opposed to the molten resin to form a resin layer (sealing material layer). Then, it aged at 40 degreeC for 48 hours. In this way, a laminated sheet A for solar cells was produced, and a solar cell module was produced.
- Adhesiveness between the anchor coat-treated surface of the back sheet and the resin layer (1) Each of the bonded samples that finished each evaluation item during the evaluation of durability was cut out to a width of 10 mm and obtained.
- the adhesion strength [N] between the anchor coat surface of the back sheet and the resin layer was measured at a tensile speed of 50 mm / min by peeling the back sheet and the resin layer from the sample piece. Adhesive strength of 2N or more is acceptable.
- Example 2 5000 g of the resin (b), 25 g of the silane coupling agent (a), 1 g of the antioxidant, 10 g of the ultraviolet absorber, and 3.5 g of the light stabilizer were blended to obtain impregnated pellets.
- L / D 26, full flight screw, compression ratio 2.6
- Example 3 In Example 2, the impregnated pellets were replaced with the following two types of mixture, and three layers were extrusion coated on the corona-treated surface of the backsheet (2) to form a three-layered resin layer (sealing material layer).
- a laminated sheet C for solar cell was produced and evaluated in the same manner as in Example 2 except that it was formed into a laminated sheet. At this time, the thicknesses of the outer layer 1, the intermediate layer, and the outer layer 2 were 50 ⁇ m, 100 ⁇ m, and 50 ⁇ m, respectively. Moreover, it carried out similarly to Example 2, and it laminated
- stacked like white sheet glass / solar cell element / laminated sheet C for solar cells ( sealing material layer / back sheet (2)), and produced the solar cell module.
- Example 4 5000 g of the resin (b), 25 g of the silane coupling agent (a), 1 g of the antioxidant, 10 g of the ultraviolet absorber, and 3.5 g of the light stabilizer were blended to obtain impregnated pellets.
- the molten resin was laminated on the corona-treated surface of the backsheet (1) to the pre-corona-treated backsheet (1) to form a resin layer (sealing material layer).
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Abstract
Description
(1)バックシートと封止材と太陽電池素子と封止材とガラスプレートとをこの順番に積み重ね、加熱して一体化する。
(2)ガラスプレート上に直接太陽電池素子が形成された太陽電池素子形成面に対して封止材、バックシートの順番で積み重ね、加熱して一体化する。
これらの方法は、いずれもバックシート、封止材を別々に用意して、太陽電池素子を含む他の部材と同時に慎重なる運搬と慎重なる位置決めを行いながら積み重ね、一体化する必要がある。
また、それぞれの部材を保管(ストック)する場所も必要である。また別には、モジュール製造時には、それぞれの部材を供給する製造設備が必要となるうえ、大きな設置場所が必要である。
耐久性に優れた太陽電池モジュールが必要とされている。
<1> フッ素樹脂又はポリエステル樹脂を用いたバックシート基材の、接着性改良のための化学的処理又は物理的処理が施された面に、カルボン酸基及びカルボン酸塩由来の基から選ばれる極性基を有する極性モノマーとエチレンとの共重合体及びアミノ基を有するジアルコキシシランを含有するエチレン共重合体組成物を含む封止材層が溶融押出しラミネーション法により積層された太陽電池用積層シートである。
本発明によれば、耐久性に優れた太陽電池モジュールが提供される。
また、本発明は、バックシートと封止材とを溶融ラミネーション法で高速一体成形できるうえ、強い層間接着強度を示すので長期耐久性に優れる。
さらに、本発明は、ガラスなどの無機物に対しても強固に接着するので、耐久性に優れた太陽電池モジュールを提供できる。
その結果、得られる積層シートは、耐湿・耐水性、柔軟性、及びモジュール製造時の成形性を有する。また、太陽光が入射する基板/太陽電池素子/バックシートを含む積層構造でのバックシートの接着性、具体的には、特に太陽電池素子とバックシートとの間に封止材を配設して基板/太陽電池素子/封止材/バックシートを含む構造としたときの積層シートの封止材面と接触する部材との接着性が高められ、さらに耐熱性の向上効果も相俟ってより良好な接着性が得られる。これにより、バックシートと封止材との層間、封止材と他の部材例えばガラスや太陽電池素子との層間の剥離に伴なう外気や異物・水分等の侵入を回避することができ、電池機能の低下が抑えられ、太陽電池の長期での耐久性能が向上する。
これらのうち、カルボン酸基の反応性の点で、アクリル酸、メタクリル酸が好ましい。
エチレン・不飽和カルボン酸共重合体のアイオノマーのベースとなるエチレン・不飽和カルボン酸共重合体は前述と同様の共重合体が使用できる。その金属種としては、リチウム、ナトリウムなどのアルカリ金属、カルシウム、マグネシウム、亜鉛、アルミニウムなどの多価金属などを例示することができる。このようなアイオノマーを使用する利点は、透明性、高温における貯蔵弾性率が高いことである。その中和度としては、例えば80%以下のものが望ましいが、接着性等を考慮するとあまり中和度の高いものは望ましくない。アイオノマーは、例えば中和度が60%以下、特に30%以下のものが好ましい。中和度の下限値は5%が望ましい。
また、不飽和カルボン酸に由来の構成単位の共重合体中における割合が大きくなると、透明性に関してはより優れたものが得られるが、融点が低くなったり、吸湿性が増すなどの問題を生じやすくなるため、不飽和カルボン酸に由来の構成単位の割合は、共重合体全質量に対して、20質量%以下が好ましく、より好ましくは15質量%以下が望ましい。
これらの中でも、ジアルコキシシランとしては、N-2-(アミノエチル)-3-アミノプロピルアルキルジアルコキシシラン(より好ましくはアルキル部位の炭素数が1~3)又は3-アミノプロピルアルキルジアルコキシシラン(より好ましくはアルキル部位の炭素数が1~3)が好ましい。中でも特に、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルメチルジエトキシシラン、3-アミノプロピルメチルジメトキシシラン、3-アミノプロピルメチルジエトキシシランが好ましい。特に、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシランは、工業的に入手しやすいので好ましく使用される。
アミノ基を有するジアルコキシシランの量が15質量部以下であると、良好な接着性が得られ、ゲル状物等の発生を抑えてシート成形を安定に行なえる。
また、本発明の太陽電池用積層シートにおいて、透明性は要求されない場合に、着色、発電効率向上などの目的で、顔料、染料、無機充填剤などを配合することができる。例えば、酸化チタン、炭酸カルシウムなどの白色顔料、ウルトラマリンなどの青色顔料、カーボンブラックのような黒色顔料などのほか、ガラスビーズや光拡散剤などを例示することができる。本発明においては、エチレン・極性モノマー共重合体と共に、特に酸化チタンのような無機顔料を配合すると、絶縁抵抗低下の防止効果に優れる点で好ましい。顔料、染料、無機充填剤などを配合する場合、これら(特に無機顔料)の好適な配合量としては、エチレン・極性モノマー共重合体100質量部に対して、100質量部以下が好ましく、より好ましくは0.5~50質量部であり、特に好ましくは4~50質量部である。
バックシートを構成するポリエステル樹脂やフッ素樹脂の基材面に施す物理的処理としては、コロナ処理、プラズマ処理、火炎処理、オゾン処理が例示できる。
また、化学的処理としては、アンカーコート処理が例示できる。アンカーコート処理に用いるアンカーコート剤の量は、良好な接着性を得る観点から、1~300g/m2の範囲が好ましく、3~200g/m2の範囲がより好ましい。
なお、粘度は、キャピラリー式レオメーターを用いて160℃で測定される値である。具体的には、一定温度のシリンダー内の溶融試料をピストンによりキャピラリーダイから押し出したときの剪断速度と剪断応力を検出し、溶融粘度を測定したものである。
このようなポリエステル樹脂基材は、上述のポリオールと同様に、分子末端がカルボン酸基の場合、熱、水、更には酸触媒としての作用が働き、加水分解に最も影響を受ける。そのため、この末端カルボン酸量を上昇させることなく数平均分子量を増加させることが可能な固相重合法を用いたり、あるいは末端カルボン酸基をカルボジイミド系化合物、オキサゾリン系化合物、エポキシ系化合物により封止することもできる。また、太陽電池モジュールを製造する際の熱で収縮の影響が懸念される場合には、アニール処理を施すことによって熱収縮率を1%以下、好ましくは0.5%以下にしたポリエステル基材を用いることが可能である。また、耐候性が要求される場合には、ベンゾフェノン、ベンゾトリアゾール、トリアジンなどの紫外線吸収剤、ヒンダードフェノール系、リン系、硫黄系、トコフェロール系の酸化防止剤、ヒンダードアミン系の光安定剤も適宜配合することが可能である。
黒色系のポリエステルフィルムは、カーボンブラック等の黒色添加物を添加した「顔料分散タイプ」を用いる。
基材の構成としては、フッ素樹脂/ポリエステル樹脂/フッ素樹脂、フッ素樹脂/アルミ箔/フッ素樹脂、ポリエステル樹脂/アルミ箔/ポリエステル樹脂、ポリエステル樹脂/白色ポリエステル樹脂/ポリエステル樹脂、シリカ蒸着ポリエステル樹脂/白色ポリエステル樹脂、シリカ蒸着ポリエステル樹脂/ポリエステル樹脂/白色ポリエステル樹脂などが挙げられる。
また、別タイプの太陽電池モジュールとして、ガラス基板上にアモルファス太陽電池素子をスパッタリング等で形成した上に、封止材層が太陽電池素子と向き合うように既述の本発明の太陽電池用積層シートを重ねた構成のもの等を挙げることができる。
また、上部保護基材がアクリル樹脂、ポリカーボネート、ポリエステル、フッ素含有樹脂などの場合には、本発明の太陽電池用積層シートをそのまま利用することが可能である。
以下に示す実施例及び比較例の実施にあたり、下記の材料を準備した。なお、「メタクリル酸含量」はメタクリル酸由来の繰り返し構成単位の共重合比率を示し、MFRは、JIS K7210-1999に準拠し、190℃、荷重2160gにて測定したメルフローレート値である。
・樹脂(a):エチレン・メタクリル酸共重合体のZnアイオノマー
(メタクリル酸含量:15質量%、MFR:5g/10分、中和度:23%、融点:91℃)
・樹脂(b):エチレン・メタクリル酸共重合体のZnアイオノマー
(メタクリル酸含量:8.7質量%、MFR:5.5g/10分、中和度:17%、融点:98℃)
・樹脂(c):エチレン・メタクリル酸共重合体
(メタクリル酸含量:15質量%、MFR:25g/10分、融点:93℃)
・樹脂(d):エチレン・メタクリル酸共重合体
(メタクリル酸含量:20質量%、MFR:60g/10分、融点:87℃)
・樹脂(e):エチレン・メタクリル酸共重合体のNaアイオノマー
(メタクリル酸含量:15質量%、MFR:2.8g/10分、中和度:30%、融点:92℃)
・シランカップリング剤(a):N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン
・シランカップリング剤(b):N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン
・シランカップリング剤(c):3-アミノプロピルトリエトキシシラン
・シランカップリング剤(d):3-グリシドキシプロピルトリメトキシシラン
・シランカップリング剤(e):3-グリシドキシプロピルメチルジエトキシシラン
(4)紫外線吸収剤:2-ヒドロキシ-4-n-オクトキシベンゾフェノン(Chimassorb 81、チバ・スペシャルティ・ケミカルズ社製)
(5)光安定剤:ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート(Tinuvin 770DF、チバ・スペシャルティ・ケミカルズ社製)
〔セイカダイン2810C(主剤)/セイカダイン2710A(硬化剤)/酢酸エチル=5/5/50(質量比)〕
基材には、下記の4種を用意した。
・青板ガラス:厚み3.2mm、サイズ7.5cm×12cm(旭硝子社製、青板強化フロートガラス)
・白板ガラス:厚み3.2mm、サイズ7.5cm×12cm(旭ガラス社製、白板強化ガラス)
・バックシート(1):PVF(38μm厚ポリフッ化ビニル)/PET(75μm厚ポリエチレンテレフタレート)/PVF(38μm厚ポリフッ化ビニル)の積層基材
〔エムエーパッケージング(株)製のPTD75(フッ素樹脂基材);PVF:デュポン社製のテドラー(登録商標)〕
バックシート(1)は、PVF面にコロナ処理を施して表面の濡れ張力を50mN/m以上として用いた。
・バックシート(2):PET(12μmのポリエチレンテレフタレート)/白PET(50μmの白色ポリエチレンテレフタレート)の積層基材〔ポリエステル樹脂基材;東洋アルミニウム(株)製のトーヤルソーラー〕
バックシート(2)は、両側表面にコロナ処理を施し表面の濡れ張力を50mN/m以上として用いた。
・PHOTOWATT社製の多結晶シリコンタイプPWP1CP3
上記の樹脂(a)5000g、シランカップリング剤(a)25g、酸化防止剤1g、紫外線吸収剤10g、及び光安定剤3.5gをそれぞれ秤量して混合し、含浸ペレットとした。得られた含浸ペレットを、押出機(L/D=26、フルフライトスクリュー、圧縮比2.6)を用いて加工温度180℃にて混練し、シート状に溶融押出しすることにより、シート厚が0.4mmの封止用シートを作製した。
下記表1に示す樹脂70gと同じく下記表1に示すシランカップリング剤0.7gとをそれぞれ秤量し、ラボプラストミル混練機(東洋精機社製、ツインスクリュー)にて150℃、回転数30rpmで15分間混合した。このとき、トルク[N・m]の変化を観察し、溶融押出しラミネーション法により成形可能かどうかを評価した。このとき、シランカップリング剤は、樹脂投入後の樹脂トルクが安定してから添加した。
ΔN[%]=(Nmax/Nmin)×100 ・・・式
以上の結果から、樹脂(a)~(b)とシランカップリング剤(a)とを用いた例を実施例として示す。なお、予備実験3~10の組成では、積層シートの形成は困難である。
-アンカーコート剤の塗布-
前記バックシート(2)を用い、その白PETの表面にバーコーターNo8を選択して前記アンカーコート剤を塗布後、100℃で5分間乾燥した。このとき、乾燥後の塗布厚は1μm以下であった。この基材を用いて、以下のようにして太陽電池用積層シートを作製した。
上記の樹脂(a)5000g、シランカップリング剤(a)25g、酸化防止剤1g、紫外線吸収剤10g、光安定剤3.5g、白色顔料(酸化チタン、デュポン社製のR103)100g(濃度60質量%)を秤量し、混合して含浸ペレットとした。得られた含浸ペレットを、押出機(L/D=26、フルフライトスクリュー、圧縮比2.6)を用いて加工温度180℃にて混練し、溶融押出しされた樹脂の厚みが0.1mmになるようにして溶融樹脂を、アンカーコート面が溶融樹脂と対向するように配置されたバックシート(2)のアンカーコート面にラミネートし、樹脂層(封止材層)を形成した。その後、40℃で48時間エージングした。このようにして太陽電池用積層シートAを作製し、太陽電池モジュールを作製した。
上記より得られた太陽電池用積層シートAに対し、下記評価を行なった。評価結果は、下記表2に示す。
下記の条件で貼合サンプルを作成し、カラーコンピューターSM-T(スガ試験機(株)製)を用いて初期の黄色度YIを測定した。
<条件>
・貼り合わせ装置:NPC製のLM-50x50S
・サンプル構成 :青色ガラス/上記の封止用シート/太陽電池用積層シートA
・貼り合わせ条件:150℃×10分間にて貼り合わせ
次に、Ci-4000(アトラス社製)により、評価項目に合わせて下記の環境条件下でそれぞれエージングを行なった後、再び上記同様にYIを測定し、初期のYIと対比して黄変度を評価した。エージングの前後でYIの変化が小さい方が耐久性に優れることを示す。
・耐熱性:85℃×1000時間
・耐湿性:85℃×90%RH×1000時間
・耐候性:83℃×180W/m2×50%RH×1000時間
前記(1)耐久性の評価中の各評価項目を終了した各々の貼合サンプルを10mm幅に切り出し、得られた各サンプル片に対してバックシートと樹脂層との間を剥離することによって、引張速度50mm/minでバックシートのアンカーコート面と、樹脂層との間の接着強度[N]を測定した。接着強度は、2N以上が許容範囲である。
前記(1)耐久性と同様にして貼合サンプルを作成し、この貼合サンプルを10mm幅に切り出し、得られたサンプル片に対して封止用シート及びガラス間を剥離することすることによって、引張速度50mm/minでサンプルの青板ガラスと封止用シートとの間の接着強度[N]を測定した。接着強度は、10N以上が許容範囲である。
得られた太陽電池用積層シートAを用い、これをその樹脂層が溶融するように加熱し、青板ガラス/封止用シート/太陽電池素子/太陽電池用積層シートA(=封止材層/バックシート(2))の積層順に重ねて圧着することにより、太陽電池モジュールを作製した。
上記樹脂(b)5000g、シランカップリング剤(a)25g、酸化防止剤1g、紫外線吸収剤10g、光安定剤3.5gを配合し、含浸ペレットとした。得られた含浸ペレットを、押出機(L/D=26、フルフライトスクリュー、圧縮比2.6)を用いて加工温度180℃にて混練し、溶融押出しされた樹脂の厚みが0.2mmになるようにして、予めコロナ処理されたバックシート(2)に対して、溶融樹脂をバックシート(2)コロナ処理面にラミネートし、樹脂層(封止材層)を形成した。このようにして太陽電池用積層シートBを作製し、白板ガラス/太陽電池素子/太陽電池用積層シートB(=封止材層/バックシート(2))のように重ねて太陽電池モジュールを作製した。評価結果は、下記表2に示す。
実施例2において、含浸ペレットを下記のような2種の混合物に代え、バックシート(2)のコロナ処理面に3層重ねて押出コーティングし、3層構造の樹脂層(封止材層)を形成して積層シートとしたこと以外は、実施例2と同様にして、太陽電池用積層シートCを作製し、評価を行なった。このとき、外層1、中間層、外層2の厚みをそれぞれ50μm、100μm、50μmとした。また、実施例2と同様にして、白板ガラス/太陽電池素子/太陽電池用積層シートC(=封止材層/バックシート(2))のように重ねて太陽電池モジュールを作製した。評価結果は、下記表2に示す。
<外層1>
実施例2と同様に調製した含浸ペレット
<中間層>
実施例2の含浸ペレットからシランカップリング剤を除いた以外、同様にして調製した含浸ペレット
<外層2>
実施例1と同様に調製した含浸ペレット
上記樹脂(b)5000g、シランカップリング剤(a)25g、酸化防止剤1g、紫外線吸収剤10g、光安定剤3.5gを配合し、含浸ペレットとした。得られた含浸ペレットを、押出機(L/D=26、フルフライトスクリュー、圧縮比2.6)を用いて加工温度180℃にて混練し、溶融押出しされた樹脂の厚みが0.2mmになるようにして、予めコロナ処理されたバックシート(1)に対して、溶融樹脂をバックシート(1)のコロナ処理面にラミネートし、樹脂層(封止材層)を形成した。このようにして太陽電池用積層シートDを作製し、白板ガラス/太陽電池素子/太陽電池用積層シートD(=封止材層/バックシート(1))のように重ねて太陽電池モジュールを作製した。評価結果は、下記表2に示す。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (15)
- フッ素樹脂又はポリエステル樹脂を用いたバックシート基材の、接着性改良のための化学的処理又は物理的処理が施された面に、カルボン酸基及びカルボン酸塩由来の基から選ばれる極性基を有する極性モノマーとエチレンとの共重合体及びアミノ基を有するジアルコキシシランを含有するエチレン共重合体組成物を含む封止材層が溶融押出しラミネーション法により積層された太陽電池用積層シート。
- 前記化学的処理が、2液反応型のウレタン樹脂系アンカーコート剤を塗布する処理である請求項1に記載の太陽電池用積層シート。
- 前記ウレタン樹脂系アンカーコート剤が、ポリエステルウレタンポリオールを含む主剤とイソシアネート化合物を含む硬化剤とを用いた2液反応型接着組成物である請求項2に記載の太陽電池用積層シート。
- 前記物理的処理が、コロナ処理である請求項1に記載の太陽電池用積層シート。
- 前記極性モノマーとエチレンとの共重合体が、エチレン・不飽和カルボン酸共重合体及びエチレン・不飽和カルボン酸共重合体のアイオノマーから選ばれる少なくとも1種である請求項1に記載の太陽電池用積層シート。
- 前記ジアルコキシシランが、3-アミノプロピルアルキルジアルコキシシラン及びN-2-(アミノエチル)-3-アミノプロピルアルキルジアルコキシシランから選ばれる少なくとも1種である請求項1に記載の太陽電池用積層シート。
- 前記ジアルコキシシランの含有割合が、前記極性モノマーとエチレンとの共重合体100質量部に対して15質量部以下である請求項1に記載の太陽電池用積層シート。
- 前記エチレン・不飽和カルボン酸共重合体が、エチレン・アクリル酸共重合体又はエチレン・メタクリル酸共重合体である請求項5に記載の太陽電池用積層シート。
- 前記アイオノマーが、エチレン・不飽和カルボン酸共重合体の亜鉛アイオノマーである請求項5に記載の太陽電池用積層シート。
- 前記アイオノマーは、エチレン・不飽和カルボン酸共重合体中の酸基の中和度が60%以下である請求項5に記載の太陽電池用積層シート。
- 前記エチレン・不飽和カルボン酸共重合体は、不飽和カルボン酸に由来の構成単位の割合が共重合体全質量に対して20質量%以下である請求項5に記載の太陽電池用積層シート。
- 前記ジアルコキシシランの含有量が、前記エチレン・極性モノマー共重合体100質量部に対して、0.03~12質量部である請求項1に記載の太陽電池用積層シート。
- 前記フッ素樹脂が、テトラフルオロエチレン・エチレン共重合体、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体、ポリクロロトリフルオロエチレン、クロロトリフルオロエチレン・エチレン共重合体、ポリフッ化ビニル、及びポリフッ化ビニリデンから選ばれる少なくとも1種である請求項1に記載の太陽電池用積層シート。
- 前記ポリエステル樹脂が、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリブチレンテレフタレート(PBT)、及びポリシクロヘキサンジメタノール-テレフタレート(PCT)から選ばれる少なくとも1種である請求項1に記載の太陽電池用積層シート。
- 太陽光が入射する基板と、太陽電池素子と、請求項1に記載の太陽電池用積層シートとを備えた太陽電池モジュール。
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- 2009-06-26 CN CN2009801240315A patent/CN102067328A/zh active Pending
- 2009-06-26 JP JP2010518078A patent/JP5280443B2/ja active Active
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US8962971B2 (en) | 2009-03-03 | 2015-02-24 | E I Du Pont De Nemours And Company | Laminated polymer film and solar module made thereof |
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Also Published As
Publication number | Publication date |
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DE112009001575T5 (de) | 2011-05-05 |
JPWO2009157545A1 (ja) | 2011-12-15 |
JP5280443B2 (ja) | 2013-09-04 |
DE112009001575B4 (de) | 2022-10-06 |
CN102067328A (zh) | 2011-05-18 |
KR101358364B1 (ko) | 2014-02-05 |
US20110108094A1 (en) | 2011-05-12 |
KR20110019436A (ko) | 2011-02-25 |
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