WO2014203740A1 - Sealing material composition for solar cells, sealing material layer for solar cells, and solar cell module using same - Google Patents
Sealing material composition for solar cells, sealing material layer for solar cells, and solar cell module using same Download PDFInfo
- Publication number
- WO2014203740A1 WO2014203740A1 PCT/JP2014/064944 JP2014064944W WO2014203740A1 WO 2014203740 A1 WO2014203740 A1 WO 2014203740A1 JP 2014064944 W JP2014064944 W JP 2014064944W WO 2014203740 A1 WO2014203740 A1 WO 2014203740A1
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- WO
- WIPO (PCT)
- Prior art keywords
- solar cell
- cell encapsulant
- sealing material
- weight
- hindered amine
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000003566 sealing material Substances 0.000 title abstract description 29
- -1 amine compound Chemical class 0.000 claims abstract description 79
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims abstract description 41
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims abstract description 32
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008393 encapsulating agent Substances 0.000 claims description 81
- 229920005989 resin Polymers 0.000 claims description 57
- 239000011347 resin Substances 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 52
- 239000011159 matrix material Substances 0.000 claims description 41
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 18
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 16
- 229920001038 ethylene copolymer Polymers 0.000 claims description 9
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 4
- 230000006866 deterioration Effects 0.000 abstract description 16
- 238000003475 lamination Methods 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 22
- 230000000694 effects Effects 0.000 description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000012965 benzophenone Substances 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 239000007850 fluorescent dye Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 230000003405 preventing effect Effects 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004383 yellowing Methods 0.000 description 7
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 6
- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
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- 229940113165 trimethylolpropane Drugs 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 238000001782 photodegradation Methods 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- 150000003613 toluenes Chemical class 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
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- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 description 2
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 2
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 2
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
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- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- ONTODYXHFBKCDK-UHFFFAOYSA-N 2-(2,4-dimethylphenyl)-1,3,5-triazine Chemical compound CC1=CC(C)=CC=C1C1=NC=NC=N1 ONTODYXHFBKCDK-UHFFFAOYSA-N 0.000 description 1
- DQUGQTFARHTZHG-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(2-hydroxyethoxy)phenol Chemical compound OC1=CC(OCCO)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 DQUGQTFARHTZHG-UHFFFAOYSA-N 0.000 description 1
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- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- OSIVCXJNIBEGCL-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-octoxypiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(OCCCCCCCC)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(OCCCCCCCC)C(C)(C)C1 OSIVCXJNIBEGCL-UHFFFAOYSA-N 0.000 description 1
- VYCDFODYRFOXDA-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-undecoxypiperidin-4-yl) carbonate Chemical compound C1C(C)(C)N(OCCCCCCCCCCC)C(C)(C)CC1OC(=O)OC1CC(C)(C)N(OCCCCCCCCCCC)C(C)(C)C1 VYCDFODYRFOXDA-UHFFFAOYSA-N 0.000 description 1
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 description 1
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 description 1
- UBCOMSHPFLPDJL-UHFFFAOYSA-N bis[2-hydroxy-3-(2-hydroxyethyl)-5-methoxyphenyl]methanone Chemical compound COC1=CC(CCO)=C(O)C(C(=O)C=2C(=C(CCO)C=C(OC)C=2)O)=C1 UBCOMSHPFLPDJL-UHFFFAOYSA-N 0.000 description 1
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- WLYPWANJUSYTQP-UHFFFAOYSA-N bis[2-hydroxy-4-(hydroxymethyl)phenyl]methanone Chemical compound OC1=CC(CO)=CC=C1C(=O)C1=CC=C(CO)C=C1O WLYPWANJUSYTQP-UHFFFAOYSA-N 0.000 description 1
- FMQXEBBPQWSWHF-UHFFFAOYSA-N bis[2-hydroxy-5-(2-hydroxyethyl)-3-methoxyphenyl]methanone Chemical compound COC1=CC(CCO)=CC(C(=O)C=2C(=C(OC)C=C(CCO)C=2)O)=C1O FMQXEBBPQWSWHF-UHFFFAOYSA-N 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 239000012943 hotmelt Substances 0.000 description 1
- HUVCZKYUWFGVLS-UHFFFAOYSA-N imidazo[4,5-e]thiazine Chemical compound C1=NSC2=NC=NC2=C1 HUVCZKYUWFGVLS-UHFFFAOYSA-N 0.000 description 1
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- 238000010030 laminating Methods 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
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- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
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- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
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- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
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- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
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- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
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- 239000011669 selenium Substances 0.000 description 1
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- WUPCFMITFBVJMS-UHFFFAOYSA-N tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 WUPCFMITFBVJMS-UHFFFAOYSA-N 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- 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
-
- 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 sealing material layer composition for solar cells, a sealing material layer for solar cells, and a solar cell module using the same.
- Non-Patent Document 1 More details regarding these devices can be found in the literature (see, for example, Non-Patent Document 1). However, there is still room for improvement in the durability and light stability of these devices including encapsulants, and it is an ongoing challenge for many researchers to develop technology to improve this efficiency. It is.
- Existing sealing material layers for solar cells contain various additives in order to prevent oxidative degradation, light degradation, etc. of the resin.
- a method is used in which an antioxidant or a light stabilizer is added to prevent discoloration such as white turbidity or yellowing caused by deterioration of a resin or additive due to long-term use (for example, see Patent Document 1). .
- the sealing material layer for solar cells also has a role of maintaining the shape of the solar cell module made of members such as cells, glass, and a back sheet, and has sufficient crosslinkability. Is also sought.
- the addition of a large amount of an antioxidant or a light stabilizer in the above method significantly reduces the crosslinkability of the matrix resin of the encapsulant layer, resulting in a problem that the characteristics as the encapsulant layer are lost. is there.
- the addition amount of organic peroxide or the like is increased in order to maintain the crosslinkability, the organic peroxide remaining in the encapsulant layer after the crosslinking reaction and the decomposition product thereof may cause deterioration of different matrix resins. turn into.
- phenolic antioxidants often used as antioxidants are discolored in the antioxidant mechanism and can cause yellowing when added in a large amount to the encapsulant layer.
- the present invention is for a solar cell capable of forming a solar cell encapsulant layer that can be sufficiently crosslinked and cured at the time of module lamination, and that is prevented from being deteriorated even when exposed to ultraviolet rays for a long time.
- An object is to provide a composition.
- the present invention also provides a solar cell encapsulant layer that can be sufficiently crosslinked and cured at the time of module lamination, and that is prevented from being deteriorated even when exposed to ultraviolet rays for a long time, and a solar cell module using the same.
- the purpose is to do.
- the present inventors have achieved the above object by using the following solar cell encapsulant composition, solar cell encapsulant layer, and solar cell module using the same. The inventors have found that this can be achieved and have completed the present invention.
- the solar cell encapsulant composition of the present invention is characterized by comprising a dibutylhydroxytoluene (BHT) derivative and a hindered amine compound having a phenol skeleton in the molecule.
- BHT dibutylhydroxytoluene
- a solar cell encapsulant layer that can be sufficiently crosslinked and cured at the time of module lamination and that has been prevented from being deteriorated even when exposed to ultraviolet rays for a long time is easily obtained. Can be formed.
- the expression of the above-described effects is presumed to be due to the mechanism described below, but it is not specified that the following mechanism is essential.
- BHT dibutylhydroxytoluene
- the hindered amine compound has a higher molecular weight, reduces the possibility of bleeding out, and is easy to maintain long-term functional expression.
- the solar cell encapsulant composition of the present invention can prevent oxidative degradation over a long period of time without inhibiting crosslinking, and suppresses photodegradation. It becomes possible.
- dibutylhydroxytoluene means 2,6-di-tert-butyl-4-methylphenol.
- the dibutylhydroxytoluene (BHT) derivative means a compound obtained by chemically modifying the dibutylhydroxytoluene.
- the hindered amine in the present invention generally directly captures radicals generated in the system by light irradiation and the like, and radicals are chain-reacted by stabilization of radical species by their own steric hindrance structure or conjugated (resonance) structure. It means an amine compound having the property of stopping (suppressing) the process of being carried out.
- the hindered amine compound preferably has a dibutylhydroxytoluene skeleton.
- the hindered amine compound itself can be further provided with a function as an antioxidant.
- the solar cell encapsulant layer formed of the composition can more effectively exhibit an oxidation deterioration preventing effect and a light deterioration suppressing effect over a long period of time.
- the hindered amine compound preferably has a 2,2,6,6-tetramethyl-4-piperidyl structure.
- the sealing material layer for solar cells formed with the said composition becomes easy to express the oxidation deterioration prevention effect and the light deterioration suppression effect more reliably over a long period of time.
- the hindered amine compound preferably has a molecular weight of 400 to 4000.
- the hindered amine compound itself can be more effectively suppressed from bleeding out.
- the solar cell encapsulant layer formed from the composition can more reliably exhibit an oxidation deterioration preventing effect and a light deterioration suppressing effect over a long period of time.
- the solar cell encapsulant composition of the present invention preferably further contains a hindered amine compound having no phenol skeleton in the molecule.
- the solar cell encapsulant layer formed of the composition may easily exhibit the above-described oxidation deterioration preventing effect and light deterioration suppressing effect over a long period of time.
- the matrix resin of the solar cell encapsulant composition contains an ethylene copolymer as a main component, and the dibutylhydroxy is added to 100 parts by weight of the matrix resin. It is preferable to contain 0.001 to 0.2 parts by weight of a toluene derivative and 0.001 to 0.3 parts by weight of the hindered amine compound. By setting it as the said compounding quantity, the bridge
- the said main component shall mean the case where the said matrix resin is a mixture of several resin, and contains 50 weight% or more by weight ratio.
- the weight ratio is more preferably 70% by weight or more, and still more preferably 90% by weight.
- the solar cell encapsulant composition of the present invention preferably further contains an ultraviolet absorbing compound.
- an ultraviolet absorbing compound By using the ultraviolet absorbing compound, it is possible to further suppress ultraviolet deterioration, impart a wavelength conversion function, and the like, and to make the solar cell sealing material layer formed of the composition more multifunctional.
- the matrix resin preferably contains an ethylene-vinyl acetate copolymer as a main component.
- an ethylene-vinyl acetate copolymer as a main component as the matrix resin, a solar cell encapsulant layer having more excellent light transmittance and durability can be obtained.
- the solar cell encapsulant layer of the present invention is characterized by being formed using the solar cell encapsulant composition.
- the solar cell encapsulant composition By forming using the above composition, it becomes a solar cell encapsulant layer that can be sufficiently crosslinked and cured at the time of module laminating and that is prevented from being deteriorated even when exposed to ultraviolet rays for a long time.
- the solar cell module of the present invention is characterized by including a solar cell encapsulant layer formed using the solar cell encapsulant composition. Since the solar cell module has the solar cell encapsulant layer, the solar cell module can be sufficiently crosslinked and cured at the time of module lamination, and is a solar cell module in which deterioration is suppressed even when exposed to ultraviolet rays for a long time.
- the solar cell is preferably a crystalline silicon solar cell.
- the said solar cell module can improve photoelectric conversion efficiency more effectively by using it for the solar cell module which laminates
- the example of the solar cell module using the sealing material layer for solar cells of this invention is shown.
- the example of the solar cell module using the sealing material layer for solar cells of this invention is shown.
- the sealing material composition for solar cells of the present invention is characterized by comprising a dibutylhydroxytoluene (BHT) derivative and a hindered amine compound having a phenol skeleton in the molecule.
- the solar cell encapsulant composition may be formed by dispersing at least a dibutylhydroxytoluene (BHT) derivative and a hindered amine compound having a phenol skeleton in the molecule in an optically transparent matrix resin. it can.
- the solar cell encapsulant composition of the present invention contains the dibutylhydroxytoluene (BHT) derivative and the hindered amine compound so that the crosslinkable resin has sufficient crosslinkability even at the time of module lamination.
- dibutylhydroxytoluene (BHT) derivative in the present invention examples include dibutylhydroxytoluene (BHT) and compounds obtained by chemically modifying a part or a plurality of portions of the dibutylhydroxytoluene (BHT).
- dibutylhydroxytoluene (BHT) derivative examples include neutral salts such as sodium salt and potassium salt of dibutylhydroxytoluene, derivatives on the benzene ring or partially substituted alkyl groups, and the like. Of these, dibutylhydroxytoluene (BHT) is preferably used.
- the molecular weight of the dibutylhydroxytoluene (BHT) is 220, but when the dibutylhydroxytoluene (BHT) derivative is used, the molecular weight of the derivative is preferably 220 to 500, and preferably 220 to 400. More preferably, it is 220 to 300.
- molecular weight measurement shall be based on MS spectrum.
- hindered amine compound having a phenol skeleton in the molecule of the present invention has a phenol skeleton in the molecule and directly captures radicals generated in the system by light irradiation or the like, and is conjugated with its own steric hindrance structure.
- An amine compound having the property of stopping (suppressing) the chain reaction of radicals by stabilizing radical species is used.
- the hindered amine compound preferably does not substantially exhibit an absorption maximum at an ultraviolet wavelength (300 to 400 nm).
- the hindered amine compound preferably has a 2,2,6,6-tetramethyl-4-piperidyl structure.
- an amine compound having a bulky substituent such as a t-butyl group so that other molecules are not easily accessible (sterically hindered) to the adjacent portion (o-position, etc.) of the hydroxyl group of the phenol skeleton. Etc.
- hindered amine compound examples include bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl. Malonate (molecular weight: 685), 1- [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine (molecular weight: 722). These compounds may be used alone or in combination of two or more.
- hindered amine compounds examples include Tinuvin 144 (molecular weight: 685, manufactured by BASF) and the like, all of which have a phenol skeleton in the molecule. These compounds may be used alone or in combination of two or more.
- the hindered amine compound preferably has a molecular weight of 400 to 4000, more preferably 500 to 2000, and even more preferably 600 to 1000.
- the molecular weight is less than 400, the hindered amine compound itself tends to bleed out.
- the molecular weight is 4000 or more, problems such as compatibility with the matrix resin may occur.
- molecular weight measurement shall be based on MS spectrum.
- the matrix resin of the solar cell encapsulant composition contains an ethylene copolymer as a main component, and the dibutylhydroxy is added to 100 parts by weight of the matrix resin.
- the toluene derivative is preferably 0.001 to 0.2 parts by weight, more preferably 0.01 to 0.15 parts by weight, and further preferably 0.02 to 0.1 parts by weight.
- the matrix resin of the solar cell encapsulant composition contains an ethylene copolymer as a main component, and the hindered amine system is used with respect to 100 parts by weight of the matrix resin.
- the amount of the compound is preferably 0.001 to 0.3 parts by weight, more preferably 0.005 to 0.1 parts by weight, and still more preferably 0.01 to 0.05 parts by weight.
- the matrix resin of the solar cell encapsulant composition contains an ethylene copolymer as a main component, and the dibutylhydroxy is added to 100 parts by weight of the matrix resin. It is preferable to contain 0.001 to 0.2 parts by weight of a toluene derivative and 0.001 to 0.3 parts by weight of the hindered amine compound. Further, 0.001 to 0.2 part by weight of the dibutylhydroxytoluene derivative and 0.005 to 0.1 part by weight of the hindered amine compound can be contained. 001 to 0.2 parts by weight and 0.01 to 0.05 parts by weight of the hindered amine compound can be included.
- the dibutylhydroxytoluene derivative can be contained in an amount of 0.01 to 0.15 parts by weight, and the hindered amine compound can be contained in an amount of 0.001 to 0.3 parts by weight. 01 to 0.15 parts by weight, and 0.005 to 0.1 parts by weight of the hindered amine compound, 0.01 to 0.15 parts by weight of the dibutylhydroxytoluene derivative, and The hindered amine compound can be contained in an amount of 0.01 to 0.05 parts by weight.
- the dibutylhydroxytoluene derivative can be contained in an amount of 0.02 to 0.1 parts by weight, and the hindered amine compound can be contained in an amount of 0.001 to 0.3 parts by weight.
- the solar cell encapsulant layer formed of the composition can exhibit the effect of preventing oxidative degradation and suppressing light degradation over a long period of time without more reliably inhibiting crosslinking.
- the above-described effects are not limited to a mere total effect, but a synergistic effect can be obtained.
- the solar cell encapsulant composition preferably further includes a hindered amine compound having no phenol skeleton in the molecule.
- the solar cell encapsulant layer formed of the composition may easily exhibit the above-described oxidation deterioration preventing effect and light deterioration suppressing effect over a long period of time.
- hindered amine compounds having no phenol skeleton in the molecule examples include, for example, bis- (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin 123, manufactured by BASF, molecular weight 737).
- the matrix resin of the solar cell encapsulant composition contains an ethylene copolymer as a main component, and the intramolecular amount relative to 100 parts by weight of the matrix resin.
- the hindered amine compound having no phenol skeleton is preferably 0.001 to 0.3 parts by weight, more preferably 0.005 to 0.1 parts by weight, and 0.01 to 0.05 parts by weight. More preferably, it is a part.
- an optically transparent matrix resin as the solar cell encapsulant composition.
- the matrix resin include polyolefins such as polyethylene terephthalate, poly (meth) acrylate, polyvinyl acetate, polyethylene tetrafluoroethylene, polyimide, amorphous polycarbonate, siloxane sol-gel, polyurethane, polystyrene, polyethersulfone, poly Examples include arylate, epoxy resin, and silicone resin. These matrix resins may be used alone or in admixture of two or more.
- the poly (meth) acrylate includes polyacrylate and polymethacrylate, and examples thereof include (meth) acrylic ester resin.
- examples of the polyolefin resin include polyethylene, polypropylene, and polybutadiene.
- examples of the polyvinyl acetate include polyvinyl formal, polyvinyl butyral (PVB resin), and modified PVB.
- Examples of the constituent monomer of the (meth) acrylic ester resin include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate.
- (Meth) acrylic acid alkyl esters such as cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate, and benzyl methacrylate.
- (meth) acrylic acid alkyl ester in which the alkyl group is substituted with a hydroxyl group, an epoxy group, a halogen group, or the like can be given. These compounds may be used alone or in combination of two or more.
- the alkyl group in the ester moiety preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
- (meth) acrylic ester resin in addition to (meth) acrylic ester, an unsaturated monomer copolymerizable with these may be used as a copolymer.
- unsaturated monomer examples include unsaturated organic acids such as methacrylic acid and acrylic acid, styrene, ⁇ -methylstyrene, acrylamide, diacetone acrylamide, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, cyclohexylmaleimide, and the like. I can give you. These unsaturated monomers may be used alone or in admixture of two or more.
- (meth) acrylic acid esters among others, methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, It is preferable to use 2-ethylhexyl methacrylate and its functional group-substituted (meth) acrylic acid alkyl ester. From the viewpoint of durability and versatility, methyl methacrylate is a more preferred example.
- Examples of the copolymer of the (meth) acrylic acid ester and the unsaturated monomer include (meth) acrylic acid ester-styrene copolymer, ethylene-vinyl acetate copolymer, and the like. Of these, ethylene copolymers are preferred from the viewpoint of moisture resistance, versatility, and cost, and ethylene-vinyl acetate copolymers are more preferred, and from the viewpoint of durability and surface hardness, ) Acrylic acid esters are preferred. Further, the combined use of an ethylene-vinyl acetate copolymer and a (meth) acrylic acid ester is preferable from the above viewpoints.
- the ethylene-vinyl acetate copolymer preferably has a vinyl acetate monomer unit content of 20 to 40 parts by weight, preferably 25 to 35 parts by weight, based on 100 parts by weight of the ethylene-vinyl acetate copolymer. More preferably, the above content is preferable from the viewpoint of uniform dispersibility in a matrix resin such as a rare earth complex.
- ethylene-vinyl acetate copolymer When using the ethylene-vinyl acetate copolymer as an optically transparent matrix resin, commercially available products can be used as appropriate.
- commercially available ethylene-vinyl acetate copolymers include Ultrasen (manufactured by Tosoh Corporation), Everflex (manufactured by Mitsui DuPont Polychemical Co., Ltd.), Suntec EVA (manufactured by Asahi Kasei Chemicals Corporation), UBE EVA copolymer ( Ube Maruzen Polyethylene Co., Ltd.), Evertate (Sumitomo Chemical Co., Ltd.), Novatec EVA (Nihon Polyethylene Co., Ltd.) and the like. These may be used singly or in combination of two or more.
- a crosslinkable monomer may be added to form a resin having a crosslinked structure.
- crosslinkable monomer examples include compounds obtained by reacting ⁇ , ⁇ -unsaturated carboxylic acid with dicyclopentenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, and polyhydric alcohol (for example, polyethylene glycol di (meth) acrylate (having 2 to 14 ethylene groups), trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, Trimethylolpropane propoxy tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate (pro Having 2 to 14 pyrene groups), dipentaerythritol penta (
- crosslinkable monomers may be used alone or in admixture of two or more.
- trimethylolpropane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and bisphenol A polyoxyethylene dimethacrylate are preferred as the crosslinkable monomer.
- a thermal polymerization initiator or a photopolymerization initiator can be added to the crosslinkable monomer, and polymerized and crosslinked by heating or light irradiation to form a crosslinked structure.
- thermoplastic resin polymerization initiator examples include 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, Di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, ⁇ , ⁇ '-bis (t-butylperoxy) Isopropyl) benzene, n-butyl-4,4-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, t-butyl
- the blending amount of the thermal polymerization initiator may be 0.1 to 5 parts by weight with respect to 100 parts by weight of the matrix resin, for example.
- the photopolymerization initiator a known photoinitiator that generates a free radical by ultraviolet light or visible light can be appropriately used.
- the photopolymerization initiator include benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzoin phenyl ether, benzophenone, N, N′-tetramethyl-4,4′-diamino Benzophenones (Michler's ketone), benzophenones such as N, N′-tetraethyl-4,4′-diaminobenzophenone, benzyl ketals such as benzyldimethyl ketal (manufactured by Ciba Japan Chemicals, Irgacure 651), benzyl diethyl ketal, Acetophenones such as 2,2-dimethoxy-2-phenylacetophenone,
- photopolymerization initiator examples include a combination of 2,4,5-triallylimidazole dimer and 2-mercaptobenzoxazole, leucocrystal violet, tris (4-diethylamino-2-methylphenyl) methane, and the like. Etc. Further, for example, known additives may be used as appropriate, such as tertiary amines such as triethanolamine for benzophenone.
- the blending amount of the photopolymerization initiator can be 0.1 to 5 parts by weight with respect to 100 parts by weight of the matrix resin, for example.
- the refractive index of the matrix resin is, for example, in the range of 1.4 to 1.7, in the range of 1.45 to 1.65, or in the range of 1.45 to 1.55. In some embodiments, the refractive index of the polymer matrix material is 1.5.
- the solar cell encapsulant composition of the present invention preferably further contains an ultraviolet absorbing compound.
- an ultraviolet absorbing compound that suppresses the suppression of UV degradation, as well as the wavelength conversion function
- An ultraviolet absorbing compound that can be used can be used.
- the ultraviolet absorbing compound known compounds can be appropriately used.
- the ultraviolet absorbing compound include benzophenone, benzotriazole, triazine, salicylic acid, and cyanoacrylate. These compounds may be used alone or in combination of two or more.
- benzophenone-based ultraviolet absorbing compound examples include 2,2′-dihydroxy-4,4′-di (hydroxymethyl) benzophenone and 2,2′-dihydroxy-4,4′-di (2-hydroxyethyl) benzophenone.
- benzotriazole ultraviolet absorbing compound examples include 2- [2′-hydroxy-5 ′-(hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(2-hydroxy). Ethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(3-hydroxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-methyl-5' -(Hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-methyl-5 '-(2-hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy -3'-methyl-5 '-(3-hydroxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy -3'-methyl-5 '-(3-hydroxypropyl) phenyl] -2H-benzotri
- Examples of the triazine-based ultraviolet absorbing compound include 2- (2-hydroxy-4-hydroxymethylphenyl) -4,6-diphenyl-s-triazine and 2- (2-hydroxy-4-hydroxymethylphenyl) -4. , 6-bis (2,4-dimethylphenyl) -s-triazine, 2- [2-hydroxy-4- (2-hydroxyethyl) phenyl] -4,6-diphenyl-s-triazine, 2- [2- Hydroxy-4- (2-hydroxyethyl) phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -4 , 6-Diphenyl-s-triazine, 2- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -4,6-bis (2,4-dimethyl) Phenyl) -s-triazine, 2- [2-hydroxy-4- (3-
- salicylic acid-based ultraviolet absorbing compound examples include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.
- Examples of the cyanoacrylate-based ultraviolet absorbing compound include 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, ethyl-2-cyano-3,3′-diphenyl acrylate, and the like.
- examples of the ultraviolet absorbing compound include fluorescent compounds that absorb light in a wavelength region of 350 to 400 nm more than light in a wavelength region exceeding 400 nm. be able to.
- examples of the fluorescent compound include organic fluorescent compounds and inorganic fluorescent compounds.
- organic fluorescent compound known organic pigment compounds (such as organic fluorescent dyes) can be used.
- organic fluorescent compound include naphthalimide, perylene, anthraquinone, coumarin, benzocoumarin, xanthene, phenoxazine, benzo [a] phenoxazine, benzo [b] phenoxazine, benzo [c] phenoxazine, and naphthalimide.
- inorganic fluorescent compound examples include complex compounds having europium or samarium as the emission center. These compounds may be used alone or in combination of two or more.
- the absorbance of the fluorescent compound is, for example, preferably from 0.1 to 6, more preferably from 0.5 to 4, and further preferably from 0.8 to 3.
- the ultraviolet absorbing compound preferably has a maximum absorption wavelength in the range of 200 to 400 nm, particularly 280 to 380 nm.
- a maximum absorption wavelength of the said ultraviolet absorption compound can be measured using a commercially available ultraviolet ray measuring apparatus etc. using a well-known method.
- a benzophenone ultraviolet absorbing compound from the viewpoint of preventing photodegradation of the ethylene-vinyl acetate copolymer, and the benzophenone ultraviolet absorbing containing two or less hydroxyl groups in one molecule. It is particularly preferred to use a compound.
- the ultraviolet absorbing compound include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-n-octoxy-benzophenone.
- the above compound has a maximum absorption wavelength in the range of 320 to 350 nm, and can more effectively suppress the photodegradation of the ethylene-vinyl acetate copolymer.
- the content of the ultraviolet absorbing compound is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.8 part by weight, based on 100 parts by weight of the matrix resin. More preferably, it is 0.5 parts by weight.
- the components are mixed and dispersed in the matrix resin.
- the solar cell encapsulant composition may contain a known additive as long as the desired performance is not impaired.
- the additive include thermoplastic polymers, antioxidants, UV inhibitors, light stabilizers, organic peroxides, fillers, plasticizers, silane coupling agents, acid acceptors, and clays. These may be used singly or in combination of two or more.
- the solar cell encapsulant layer of the present invention is formed using the above solar cell encapsulant composition.
- the solar cell encapsulant layer may be produced according to a known method.
- a composition obtained by mixing the above-described solar cell encapsulant composition (or each material thereof) with a known method using heat kneading, a super mixer (high-speed fluidized mixer), a roll mill, a plast mill, etc. It can be suitably manufactured by a method of forming a sheet by molding by extrusion molding, calendar molding (calendering), vacuum hot pressing or the like.
- after forming the said layer on PET film etc. it can manufacture by the method of transcribe
- the solar cell encapsulant composition containing the matrix resin, the dibutylhydroxytoluene derivative, the hindered amine compound, and the like may be applied and formed as it is on a surface protective layer or a separator.
- the above material may be applied and formed as a mixed composition with other materials.
- the matrix resin When applied as the solar cell encapsulant composition, the matrix resin preferably has a melting point of 50 to 120 ° C., more preferably 50 to 100 ° C., in consideration of processability. More preferably, it is -80 ° C.
- the melting point of the solar cell encapsulant composition is 50 to 120 ° C.
- the kneading and melting and coating temperature of the composition are preferably performed at a temperature obtained by adding 30 to 100 ° C. to the melting point.
- the solar cell encapsulant layer is manufactured into a thin film structure by the following steps: (i) The polymer (matrix resin) powder is a solvent (eg, tetrachloroethylene (TCE) in a predetermined ratio. ), Preparing a polymer solution dissolved in cyclopentanone, dioxane, etc.) (ii) mixing a luminescent dye (fluorescent compound) containing the polymer mixture with the luminescent dye in a predetermined weight ratio Preparing a dye-containing polymer solution, (iii) pouring the dye / polymer thin film directly onto the glass substrate, after which the substrate is allowed to rise from room temperature up to 100 ° C.
- a solvent eg, tetrachloroethylene (TCE) in a predetermined ratio.
- TCE tetrachloroethylene
- the thickness of the solar cell encapsulant layer is preferably 20 to 2000 ⁇ m, more preferably 50 to 1000 ⁇ m, and even more preferably 100 to 800 ⁇ m.
- the thickness is less than 20 ⁇ m, the sealing material function is hardly exhibited.
- the thickness of a solar cell module will become large and it will be disadvantageous also in cost.
- the solar cell encapsulant layer is usually used for encapsulating solar cells, but is laminated so as to appropriately seal interconnector materials, electrodes, and the like as necessary. As long as the function of the solar cell encapsulant layer is not impaired, other layers such as each layer may be interposed as required.
- the solar cell module 1 of the present invention includes a surface protective layer 10, the solar cell sealing material layer 20, and solar cells 30. 1 and 2 show simple schematic diagrams as an example, but the present invention is not limited to these. Moreover, the sealing material layer 40 and the back sheet
- the solar cell for example, a cadmium sulfide / cadmium telluride solar cell, a copper indium gallium diselenide solar cell, an amorphous silicon solar cell, a microcrystalline silicon solar cell, or a crystalline silicon solar cell can be used.
- the solar battery cell is preferably a crystalline silicon solar battery.
- the solar cell encapsulant layer may be transferred to the solar cell or the like, or may be directly coated on the solar cell. Moreover, you may form the said sealing material layer for solar cells, and another layer simultaneously.
- each sealing material layer (sealing sheet and backside sealing sheet) was produced by the following method, based on the compounds shown in Table 1.
- Example / Comparative Example 100 parts by weight of EVA resin (Smitate KA-30) and each compound were weighed, dry blended, melt-kneaded using a single screw extruder, and pellets of an ethylene copolymer composition. Got. A sealing material layer resin sheet (thickness: about 400 ⁇ m) was produced from the pellets using a press molding machine.
- the obtained encapsulant layer resin sheet (thickness: 400 ⁇ m) was sandwiched between glass and a back sheet, and bonded at 80 ° C. and 100 kN, and stored in a drying oven at 150 ° C. for 20 minutes. Thereafter, UV light (365 nm) of 1 W / cm 2 was irradiated for a predetermined time (180 minutes) using a UV irradiator (Panasonic Electric Works Control Co., UJ35) and a lens (Panasonic Electric Works Control Co., ANUJ6426).
- the reflection spectrum of the sample before and after UV light irradiation was measured by MCPD (manufactured by Otsuka Electronics Co., Ltd.).
- the yellowing degree (YI: Yellow Index, ASTM D 1925) was calculated from the obtained reflection spectrum information, and yellowing evaluation was performed.
- the evaluation criteria were as follows. -When the average value of the measured values at the four points at the end is less than 7.5: When the average value of the measured values at the four points at the end is 7.5 or more and less than 10: ⁇ When the average value of the measured values at the four points at the end is 10 or more: ⁇
- the obtained encapsulant layer resin sheet (thickness: 400 ⁇ m) is sandwiched between glass and a PET release film and bonded at 80 ° C. and 100 kN, and stored in a drying oven at 150 ° C. for 20 minutes. did. Thereafter, the release film is peeled off, and using a UV irradiator (Panasonic Electric Works Control Co., UJ35) and a lens (Panasonic Electric Works Control Co., ANUJ6426), 1 W / cm 2 of UV light (365 nm) is given from both sides of the sheet. Irradiated for a time (120 minutes).
- the absorption spectrum of the sample before and after light irradiation was measured with a spectrophotometer (manufactured by JASCO Corporation, V560). From the obtained spectral information, the change in absorbance of the organic substance was evaluated. The evaluation criteria were as follows. ⁇ If the change in absorbance after UV irradiation is -0.8 or more: ⁇ ⁇ If the change in absorbance after UV irradiation is -0.9 or more and less than -0.8: ⁇ ⁇ If the change in absorbance after UV irradiation is less than -0.9: ⁇
- Table 1 below shows each measurement result when the obtained sealing material layer resin sheet was used.
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Abstract
Description
本発明の太陽電池用封止材組成物は、ジブチルヒドロキシトルエン(BHT)誘導体および分子内にフェノール骨格を有するヒンダードアミン系化合物を含むことを特徴とする。上記太陽電池用封止材組成物は、光学的に透明なマトリックス樹脂中に、少なくともジブチルヒドロキシトルエン(BHT)誘導体および分子内にフェノール骨格を有するヒンダードアミン系化合物を分散させること等により形成することができる。本発明の太陽電池用封止材組成物は、上記ジブチルヒドロキシトルエン(BHT)誘導体および上記ヒンダードアミン系化合物を含むことにより、モジュールラミネートの時点においても架橋性樹脂が十分な架橋性を有し、長期間紫外線に曝されても紫外線吸収化合物のUVカット性が維持され、かつマトリックス樹脂等の変色が起こりにくい太陽電池用封止材層を形成することができる。 (Encapsulant composition for solar cell)
The sealing material composition for solar cells of the present invention is characterized by comprising a dibutylhydroxytoluene (BHT) derivative and a hindered amine compound having a phenol skeleton in the molecule. The solar cell encapsulant composition may be formed by dispersing at least a dibutylhydroxytoluene (BHT) derivative and a hindered amine compound having a phenol skeleton in the molecule in an optically transparent matrix resin. it can. The solar cell encapsulant composition of the present invention contains the dibutylhydroxytoluene (BHT) derivative and the hindered amine compound so that the crosslinkable resin has sufficient crosslinkability even at the time of module lamination. Even if it is exposed to ultraviolet rays for a period of time, the UV-cutting property of the ultraviolet absorbing compound is maintained, and a sealing material layer for a solar cell, such as a matrix resin, that hardly undergoes discoloration can be formed.
一方、本発明の太陽電池用封止材層は、上記太陽電池用封止材組成物を用いて形成されたことを特徴とする。 (Sealant layer for solar cells)
On the other hand, the solar cell encapsulant layer of the present invention is formed using the above solar cell encapsulant composition.
本発明の太陽電池モジュール1は、表面保護層10、上記太陽電池用封止材層20および太陽電池セル30を含むことを特徴とする。一例として図1、2に簡易な模式図を示すが、本発明がこれらに限定されるものではない。また、太陽電池セルの背面側にさらに封止材層40、バックシート50を適宜備えることもできる。また、これらの各層間に、上記太陽電池用封止材層の上記機能を損なわない限り、接着材層、粘着剤層などの他の層を適宜介在してもよい。また、上記背面用の封止材層として、適宜、本発明の太陽電池用封止材層を用いてもよい。 (Solar cell module)
The solar cell module 1 of the present invention includes a surface protective layer 10, the solar cell sealing material layer 20, and solar cells 30. 1 and 2 show simple schematic diagrams as an example, but the present invention is not limited to these. Moreover, the sealing material layer 40 and the back sheet | seat 50 can also be further suitably provided in the back side of a photovoltaic cell. Moreover, as long as the said function of the said solar cell sealing material layer is not impaired between these each layers, you may interpose other layers, such as an adhesive material layer and an adhesive layer, suitably. Moreover, you may use the sealing material layer for solar cells of this invention suitably as said sealing material layer for back surfaces.
実施例・比較例では、以下の化合物を用いた。
・マトリックス樹脂:スミテートKA-30、エチレンビニルアセテート樹脂(住友化学社製)
・有機化合物A:4,7-ビス(4-イソブチルオキシフェニル)-2-イソブチル-2H-ベンゾトリアゾール
・過酸化物:t-ブチルパーオキシ-2-エチルヘキシルモノカルボネート(日油社製、パーブチルE)
・架橋助剤:トリアリルイソシアネート(日本化成社製、TAIC)
・BHT:ジブチルヒドロキシトルエン(東京化成社製)
・Tinuvin 144:ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)[[3,5-ビス(1,1-ジメチルエチル)-4-ヒドロキシフェニル]メチル]ブチルマロネート(BASF社製、分子量685)
・Tinuvin 770DF:ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート(BASF社製、分子量481)
・KBM503:3-メタクリロキシプロピルトリメトキシシラン(信越シリコーン社製) (Compounds in the table)
In the examples and comparative examples, the following compounds were used.
・ Matrix resin: Summitate KA-30, ethylene vinyl acetate resin (Sumitomo Chemical Co., Ltd.)
Organic compound A: 4,7-bis (4-isobutyloxyphenyl) -2-isobutyl-2H-benzotriazolePeroxide: t-butylperoxy-2-ethylhexyl monocarbonate (manufactured by NOF Corporation, perbutyl E)
・ Crosslinking aid: triallyl isocyanate (manufactured by Nippon Kasei Co., Ltd., TAIC)
・ BHT: Dibutylhydroxytoluene (manufactured by Tokyo Chemical Industry Co., Ltd.)
Tinuvin 144: bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate (BASF) (Made in Japan, molecular weight 685)
Tinuvin 770DF: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (BASF, molecular weight 481)
KBM503: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone)
実施例・比較例において、各化合物を表1の配合に基づき、各封止材層(封止シートおよび裏面用封止シート)を下記方法により製造した。 (Production of resin sheet)
In Examples and Comparative Examples, each sealing material layer (sealing sheet and backside sealing sheet) was produced by the following method, based on the compounds shown in Table 1.
得られた封止材層樹脂シート(厚さ:400μm)の両面にPET系離型フィルムを貼り付けた試料を、ガラスおよびバックシートに挟み、80℃、100kNの条件でプレスし、150℃の条件で乾燥オーブンに20分間保管した。その後、W1g切り取り精秤し、キシレン100ccに浸漬した(110℃、24時間)。その後、ろ過残渣の乾燥後(80℃、6時間)の重量W2gを精秤し、(W2/W1)×100として計算される値をゲル分率(重量%)とした。評価基準は以下のように行った。
・ゲル分率の平均値(測定個数2個)値が80%以上であった場合:○
・ゲル分率の平均値(測定個数2個)値が80%未満であった場合:× (Measurement of gel fraction)
A sample in which a PET release film was attached to both sides of the obtained encapsulant layer resin sheet (thickness: 400 μm) was sandwiched between glass and a back sheet, pressed under conditions of 80 ° C. and 100 kN, and 150 ° C. The conditions were stored in a drying oven for 20 minutes. Thereafter, W 1 g was cut and precisely weighed and immersed in 100 cc of xylene (110 ° C., 24 hours). Thereafter, the weight W 2 g after drying (80 ° C., 6 hours) of the filtration residue was precisely weighed, and the value calculated as (W 2 / W 1 ) × 100 was taken as the gel fraction (% by weight). The evaluation criteria were as follows.
When the average value of gel fraction (measured number 2) is 80% or more: ○
When the average value of gel fraction (measured number is 2) is less than 80%: ×
得られた封止材層樹脂シート(厚さ:400μm)を、ガラスおよびバックシートに挟んだ状態で、80℃、100kNの条件で貼り合わせ、150℃の条件で乾燥オーブンに20分間保管した。その後、UV照射器(パナソニック電工制御社製、UJ35)およびレンズ(パナソニック電工制御社製、ANUJ6426)を用い、1W/cm2のUV光(365nm)を所定の時間(180分)照射した。UV光照射前後のサンプルの反射スペクトルをMCPD(大塚電子社製)によって測定した。得られた反射スペクトル情報から、黄変度(YI:Yellow Index、ASTM D 1925)を算出し、黄変評価を実施した。評価基準は以下のように行った。
・端部の4点の測定値の平均値が7.5未満であった場合:○
・端部の4点の測定値の平均値が7.5以上10未満であった場合:△
・端部の4点の測定値の平均値が10以上であった場合:× (Evaluation of initial yellowing)
The obtained encapsulant layer resin sheet (thickness: 400 μm) was sandwiched between glass and a back sheet, and bonded at 80 ° C. and 100 kN, and stored in a drying oven at 150 ° C. for 20 minutes. Thereafter, UV light (365 nm) of 1 W / cm 2 was irradiated for a predetermined time (180 minutes) using a UV irradiator (Panasonic Electric Works Control Co., UJ35) and a lens (Panasonic Electric Works Control Co., ANUJ6426). The reflection spectrum of the sample before and after UV light irradiation was measured by MCPD (manufactured by Otsuka Electronics Co., Ltd.). The yellowing degree (YI: Yellow Index, ASTM D 1925) was calculated from the obtained reflection spectrum information, and yellowing evaluation was performed. The evaluation criteria were as follows.
-When the average value of the measured values at the four points at the end is less than 7.5:
When the average value of the measured values at the four points at the end is 7.5 or more and less than 10: Δ
When the average value of the measured values at the four points at the end is 10 or more: ×
得られた封止材層樹脂シート(厚さ:400μm)を、ガラスおよびPET離型フィルムに挟んだ状態で、80℃、100kNの条件で貼り合わせ、150℃の条件で乾燥オーブンに20分間保管した。その後、離型フィルムを剥がし、UV照射器(パナソニック電工制御社製、UJ35)およびレンズ(パナソニック電工制御社製、ANUJ6426)を用い、1W/cm2のUV光(365nm)をシート両側から所定の時間(120分)照射した。光照射前後のサンプルの吸収スペクトルを分光光度計(日本分光社製、V560)によって測定した。得られたスペクトル情報から、有機物の吸光度変化を評価した。評価基準は以下のように行った。
・紫外線照射した後の吸光度変化が-0.8以上であった場合:○
・紫外線照射した後の吸光度変化が-0.9以上-0.8未満であった場合:△
・紫外線照射した後の吸光度変化が-0.9未満であった場合:× (Light stability test)
The obtained encapsulant layer resin sheet (thickness: 400 μm) is sandwiched between glass and a PET release film and bonded at 80 ° C. and 100 kN, and stored in a drying oven at 150 ° C. for 20 minutes. did. Thereafter, the release film is peeled off, and using a UV irradiator (Panasonic Electric Works Control Co., UJ35) and a lens (Panasonic Electric Works Control Co., ANUJ6426), 1 W / cm 2 of UV light (365 nm) is given from both sides of the sheet. Irradiated for a time (120 minutes). The absorption spectrum of the sample before and after light irradiation was measured with a spectrophotometer (manufactured by JASCO Corporation, V560). From the obtained spectral information, the change in absorbance of the organic substance was evaluated. The evaluation criteria were as follows.
・ If the change in absorbance after UV irradiation is -0.8 or more: ○
・ If the change in absorbance after UV irradiation is -0.9 or more and less than -0.8: △
・ If the change in absorbance after UV irradiation is less than -0.9: ×
10 表面保護層
20 太陽電池用封止材層
30 太陽電池セル
40 裏面用封止材層
50 バックシート DESCRIPTION OF SYMBOLS 1 Solar cell module 10 Surface protective layer 20 Solar cell sealing material layer 30 Solar cell 40 Back surface sealing material layer 50 Back sheet
Claims (11)
- ジブチルヒドロキシトルエン(BHT)誘導体および分子内にフェノール骨格を有するヒンダードアミン系化合物を含むことを特徴とする、太陽電池用封止材組成物。 A solar cell encapsulant composition comprising a dibutylhydroxytoluene (BHT) derivative and a hindered amine compound having a phenol skeleton in the molecule.
- 前記ヒンダードアミン系化合物がジブチルヒドロキシトルエン骨格を有する、請求項1に記載の太陽電池用封止材組成物。 The solar cell encapsulant composition according to claim 1, wherein the hindered amine compound has a dibutylhydroxytoluene skeleton.
- 前記ヒンダードアミン系化合物の分子量が400~4000である、請求項1または2に記載の太陽電池用封止材組成物。 The solar cell encapsulant composition according to claim 1 or 2, wherein the hindered amine compound has a molecular weight of 400 to 4000.
- 前記ヒンダードアミン系化合物が2,2,6,6-テトラメチル-4-ピペリジル構造を有する、請求項1~3のいずれかに記載の太陽電池用封止材組成物。 The solar cell encapsulant composition according to any one of claims 1 to 3, wherein the hindered amine compound has a 2,2,6,6-tetramethyl-4-piperidyl structure.
- さらに、分子内にフェノール骨格を有さないヒンダードアミン系化合物を含むことを特徴とする、請求項1~4のいずれかに記載の太陽電池用封止材組成物。 The solar cell encapsulant composition according to claim 1, further comprising a hindered amine compound having no phenol skeleton in the molecule.
- 前記太陽電池用封止材組成物のマトリックス樹脂がエチレン系共重合体を主成分とし、前記マトリックス樹脂100重量部に対し、前記ジブチルヒドロキシトルエン誘導体を0.001~0.2重量部、および、前記ヒンダードアミン系化合物を0.001~0.3重量部含む、請求項1~5のいずれかに記載の太陽電池用封止材組成物。 The matrix resin of the solar cell encapsulant composition has an ethylene copolymer as a main component, and 0.001 to 0.2 parts by weight of the dibutylhydroxytoluene derivative with respect to 100 parts by weight of the matrix resin; and 6. The solar cell encapsulant composition according to claim 1, comprising 0.001 to 0.3 parts by weight of the hindered amine compound.
- さらに紫外線吸収化合物を含む、請求項1~6のいずれかに記載の太陽電池用封止材組成物。 The solar cell encapsulant composition according to claim 1, further comprising an ultraviolet absorbing compound.
- 前記マトリックス樹脂が、エチレン-酢酸ビニル共重合体を主成分とする、請求項1~7のいずれかに記載の太陽電池用封止材組成物。 The solar cell encapsulant composition according to any one of claims 1 to 7, wherein the matrix resin contains an ethylene-vinyl acetate copolymer as a main component.
- 請求項1~8のいずれかに記載の太陽電池用封止材組成物を用いて形成された太陽電池用封止材層。 A solar cell encapsulant layer formed using the solar cell encapsulant composition according to any one of claims 1 to 8.
- 請求項1~8のいずれかに記載の太陽電池用封止材組成物を用いて形成された太陽電池用封止材層を含む太陽電池モジュール。 A solar cell module comprising a solar cell encapsulant layer formed using the solar cell encapsulant composition according to any one of claims 1 to 8.
- 太陽電池セルが、結晶シリコン太陽電池である、請求項10に記載の太陽電池モジュール。
The solar cell module according to claim 10, wherein the solar cell is a crystalline silicon solar cell.
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CN201480035152.3A CN105324853A (en) | 2013-06-20 | 2014-06-05 | Sealing material composition for solar cells, sealing material layer for solar cells, and solar cell module using same |
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JPH06169099A (en) * | 1992-08-03 | 1994-06-14 | Siemens Solar Ind Internatl Inc | Composition and method for sealing of solar cell as well as hardened transparent sealing agent |
JP2009191182A (en) * | 2008-02-15 | 2009-08-27 | Denki Kagaku Kogyo Kk | Chloroprene-based polymer composition, adhesive composition and method for producing the chloroprene-based polymer composition |
WO2011071022A1 (en) * | 2009-12-11 | 2011-06-16 | 株式会社Adeka | Sealing film for solar cell |
JP2011238719A (en) * | 2010-05-10 | 2011-11-24 | Bridgestone Corp | Solar cell-sealing film and solar cell using the same |
CN102559080A (en) * | 2012-02-16 | 2012-07-11 | 太阳能光伏北京市工程研究中心有限公司 | Ethylene-vinylacetate adhesive film |
JP2013077705A (en) * | 2011-09-30 | 2013-04-25 | Hitachi Chemical Co Ltd | Wavelength conversion solar cell module and method of manufacturing the same |
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JP2003243682A (en) | 2002-02-19 | 2003-08-29 | Sumitomo Bakelite Co Ltd | Solar cell |
JP2008069210A (en) * | 2006-09-12 | 2008-03-27 | Shin Etsu Chem Co Ltd | Polycyclic hydrocarbon group-containing silicone-based curable composition |
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JPH06169099A (en) * | 1992-08-03 | 1994-06-14 | Siemens Solar Ind Internatl Inc | Composition and method for sealing of solar cell as well as hardened transparent sealing agent |
JP2009191182A (en) * | 2008-02-15 | 2009-08-27 | Denki Kagaku Kogyo Kk | Chloroprene-based polymer composition, adhesive composition and method for producing the chloroprene-based polymer composition |
WO2011071022A1 (en) * | 2009-12-11 | 2011-06-16 | 株式会社Adeka | Sealing film for solar cell |
JP2011238719A (en) * | 2010-05-10 | 2011-11-24 | Bridgestone Corp | Solar cell-sealing film and solar cell using the same |
JP2013077705A (en) * | 2011-09-30 | 2013-04-25 | Hitachi Chemical Co Ltd | Wavelength conversion solar cell module and method of manufacturing the same |
CN102559080A (en) * | 2012-02-16 | 2012-07-11 | 太阳能光伏北京市工程研究中心有限公司 | Ethylene-vinylacetate adhesive film |
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