TWI525111B - A solar cell sealing film and a solar battery using the same - Google Patents
A solar cell sealing film and a solar battery using the same Download PDFInfo
- Publication number
- TWI525111B TWI525111B TW101107814A TW101107814A TWI525111B TW I525111 B TWI525111 B TW I525111B TW 101107814 A TW101107814 A TW 101107814A TW 101107814 A TW101107814 A TW 101107814A TW I525111 B TWI525111 B TW I525111B
- Authority
- TW
- Taiwan
- Prior art keywords
- solar cell
- sealing film
- mass
- ethylene
- methyl methacrylate
- Prior art date
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- 238000007789 sealing Methods 0.000 title claims description 84
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 40
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 claims description 32
- 239000007822 coupling agent Substances 0.000 claims description 24
- 239000003431 cross linking reagent Substances 0.000 claims description 23
- 150000001451 organic peroxides Chemical group 0.000 claims description 13
- 150000002978 peroxides Chemical class 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- PHCUKGVEZRZQFY-UHFFFAOYSA-N CCCCCCCCCCC(=O)OC(=O)C(C)=C Chemical group CCCCCCCCCCC(=O)OC(=O)C(C)=C PHCUKGVEZRZQFY-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 description 89
- 210000004027 cell Anatomy 0.000 description 79
- -1 peroxide compound Chemical class 0.000 description 32
- 230000001681 protective effect Effects 0.000 description 23
- 238000004132 cross linking Methods 0.000 description 18
- 239000011521 glass Substances 0.000 description 13
- 238000005187 foaming Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 description 10
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000003999 initiator Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 229920005601 base polymer Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 210000003850 cellular structure Anatomy 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 4
- 229940067157 phenylhydrazine Drugs 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000155 melt Substances 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
- 150000003254 radicals Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
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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 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- QHJSCTNRFWNYID-UHFFFAOYSA-N CCC=COCCCC(C(OC)(OC)OC)CCCCCCCC Chemical compound CCC=COCCCC(C(OC)(OC)OC)CCCCCCCC QHJSCTNRFWNYID-UHFFFAOYSA-N 0.000 description 2
- KOIGTNYADMQQMS-UHFFFAOYSA-N CCC=COCCCC(C(OCC)(OCC)C)CCCCCCCC Chemical compound CCC=COCCCC(C(OCC)(OCC)C)CCCCCCCC KOIGTNYADMQQMS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- BXQMXWRVSBULNN-SNAWJCMRSA-N (E)-2-tert-butylperoxybut-2-enediamide Chemical compound C(C)(C)(C)OO/C(/C(=O)N)=C/C(=O)N BXQMXWRVSBULNN-SNAWJCMRSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- OTMBZPVYOQYPBE-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclododecane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCCCCCCCC1 OTMBZPVYOQYPBE-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
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- YZQCRYHZKMFKDE-UHFFFAOYSA-N 1-octadecylperoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOOCCCCCCCCCCCCCCCCCC YZQCRYHZKMFKDE-UHFFFAOYSA-N 0.000 description 1
- LWRXNMLZNDYFAW-UHFFFAOYSA-N 1-octylperoxyoctane Chemical compound CCCCCCCCOOCCCCCCCC LWRXNMLZNDYFAW-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- QNLVSEVOEORLBH-UHFFFAOYSA-N 2,5-bis(2-ethylhexylperoxy)-2,5-dimethylhexane Chemical compound CCCCC(CC)COOC(C)(C)CCC(C)(C)OOCC(CC)CCCC QNLVSEVOEORLBH-UHFFFAOYSA-N 0.000 description 1
- CHKCPIUYSMYEEW-UHFFFAOYSA-N 2-(2-cyclohexylpropan-2-ylperoxy)-2-ethylhexanoic acid Chemical compound CCCCC(CC)(C(O)=O)OOC(C)(C)C1CCCCC1 CHKCPIUYSMYEEW-UHFFFAOYSA-N 0.000 description 1
- 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 1
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- KMALEIUFUYPZSD-UHFFFAOYSA-N 2-[2-[2-(2-butanoyloxyethoxy)ethoxy]ethoxy]ethyl butanoate Chemical compound CCCC(=O)OCCOCCOCCOCCOC(=O)CCC KMALEIUFUYPZSD-UHFFFAOYSA-N 0.000 description 1
- JEYLQCXBYFQJRO-UHFFFAOYSA-N 2-[2-[2-(2-ethylbutanoyloxy)ethoxy]ethoxy]ethyl 2-ethylbutanoate Chemical compound CCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CC JEYLQCXBYFQJRO-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
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- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
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- GFMVOUPWTMLVTK-UHFFFAOYSA-N icosan-10-yl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCC(OC(=O)C(C)=C)CCCCCCCCC GFMVOUPWTMLVTK-UHFFFAOYSA-N 0.000 description 1
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- 229920000831 ionic polymer Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- 239000005368 silicate glass Substances 0.000 description 1
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- 230000003595 spectral effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- 239000011709 vitamin E Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H01L31/042—PV modules or arrays of single PV cells
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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Description
本發明係關於一種接著性高、於高溫高濕條件下之耐久性優異之太陽電池用密封膜以及使用其之太陽電池。
近年來,基於資源之有效利用、環境污染之防止等觀點,將太陽光直接變換為電能之太陽電池被廣為使用,進而基於生產性、耐久性之觀點而被持續開發中。
太陽電池係例如圖1所示般,依序積層由玻璃基板等所構成之表面側透明保護構件11、表面側密封膜13A、矽發電元件等太陽電池用元件14、背面側密封膜13B、以及背面側保護構件12,以減壓脫氣後,進行加熱加壓使得表面側密封膜13A以及背面側密封膜13B產生交聯硬化而接著一體化來製造。以往之太陽電池,為了得到高電氣輸出,係將複數太陽電池用元件14加以連接使用。從而,為了確保太陽電池用元件14間之絕緣性,乃使用具有絕緣性之密封膜13A、13B來密封太陽電池用元件。
以密封膜13A、13B而言,基於價廉且具有高透明性以及接著性之考量,以往係使用乙烯-乙酸乙烯酯共聚物(EVA)膜(例如專利文獻1)。此外,基於確保太陽電池元件之機械耐久性、防止濕氣或是水滲透導
致內部導線或電極生鏽,係使用交聯劑使得EVA膜產生交聯,藉以在高密合性以及接著強度下來將各構件接著一體化。
但是,EVA由於其構成成分包含乙酸乙烯酯,故設置時之高溫下的濕氣會隨時間經過而容易發生水解產生乙酸,此乙酸若和內部導線、電極接觸恐怕會促成生鏽。基於此理由,已開發出使用EVA以外之樹脂所製造之太陽電池用密封膜。在使用EVA以外之樹脂的太陽電池用密封膜方面,專利文獻2中揭示了使用乙烯-不飽和羧酸共聚物或是其離子聚合物之太陽電池用密封膜,此外,於專利文獻3係揭示了一種以乙烯-甲基丙烯酸甲酯共聚物與EVA之混合物做為基礎聚合物來使用之太陽電池用密封膜。
先前技術文獻
專利文獻1 日本特開2008-153520
專利文獻2 日本特開2000-186114
專利文獻3 日本特開2005-126708
但是,專利文獻2所記載之密封膜雖生產性優異,但由於未進行交聯,故有和其他構件(保護構件以及太陽電池用元件)之接著性不充分之問題。另一方面,於專利文獻3所記載之密封膜雖為受交聯之密封膜,但由於是乙烯-甲基丙烯酸甲酯共聚物與EVA所混合而成之密封膜,故仍然會從EVA產生乙酸,且受
到交聯劑之影響而產生發泡造成接著力降低,此為問題所在。
本發明係鑑於上述情事所得者,其目的在於提供一種太陽電池用密封膜,可防止酸所致腐蝕、抑制發泡的產生、接著性高、其高接著性即便於高溫高濕下之嚴苛條件下也能被維持。此外,藉由使用此太陽電池用密封膜,可提供一種發電效率提高、耐久性優異之太陽電池。
發泡係起因於密封目的之交聯製程中包含在密封膜的交聯劑受熱分解而產生之氣體。亦即,伴隨交聯劑之熱分解所產生之氣體會停留在太陽電池內部之背面側保護構件、背面側密封膜、太陽電池用元件、表面側密封膜以及表面側透明保護構件之各界面,從而於太陽電池內部產生發泡。另一方面,若不進行交聯則不僅無法得到充分的接著力,於高溫高濕條件下之耐久性也不充分。是以,本發明者發現到若基礎聚合物使用不會產生酸的聚合物,並以既定量摻配所需最低限度量的交聯劑與提升接著性之矽烷耦合劑,便可解決上述課題。
亦即,上述目的可藉由下述太陽電池用密封膜來達成:含有乙烯-甲基丙烯酸甲酯共聚物、交聯劑以及矽烷耦合劑;其特徵在於:該交聯劑之含有量相對於該乙烯-甲基丙烯酸甲酯共聚物100質量份為0.05~0.7質量份,該矽烷耦合劑之含有量相對於該乙烯-甲基丙烯酸甲酯共聚物100質量份為0.1~0.7質量
份;該乙烯-甲基丙烯酸甲酯共聚物中之甲基丙烯酸甲酯之含有率為25~35質量%。
本發明之較佳樣態如下。
(1)前述交聯劑相對於前述矽烷耦合劑之質量比為0.2~0.5。只要在此範圍內,尤其可一面抑制發泡、一面提高接著力,即便於濕熱環境下也可維持高水準之接著力。
(2)前述交聯劑為有機過氧化物。
(3)有機過氧化物為二烷基過氧化物系化合物。
(4)矽烷耦合劑為甲基丙烯醯氧基系矽烷耦合劑。
此外,本目的也可藉由使用有上述太陽電池用密封膜之太陽電池來達成。
本發明之太陽電池用密封膜具有優異之接著性以及耐久性。從而,依據本發明之太陽電池用密封膜可提供一種太陽電池,可抑制於密封膜與保護構件之界面發生發泡或剝離,可從發電開始初期歷經長期間維持高發電性能。
如上述般,本發明之太陽電池用密封膜在基礎聚合物方面使用乙烯-甲基丙烯酸甲酯共聚物,交聯劑相對於乙烯-甲基丙烯酸甲酯共聚物100質量份含有0.05~0.7質量份,矽烷耦合劑相對於該乙烯-甲基丙烯酸甲酯共聚物100質量份含有0.1~0.7質量份。此外,上述乙烯-甲基丙烯酸甲酯係使用甲基丙烯酸甲
酯之含有率為25~35質量%者。使用所需最低限度之交聯劑進行交聯,且併用矽烷耦合劑,可抑制發泡的產生而得到高接著性,且可提高高溫高濕條件下之耐久性。此外,在密封膜之基礎聚合物方面,藉由使用乙烯-甲基丙烯酸甲酯共聚物,可防止產生酸,可防止電極等之腐蝕、接著力之降低。乙烯-甲基丙烯酸甲酯共聚物之光線穿透性高,可使得太陽光充分入射於太陽電池用元件,故適合做為太陽電池用密封膜之基礎聚合物。
以下,針對各材料詳細說明。
〔乙烯-甲基丙烯酸甲酯共聚物〕
乙烯-甲基丙烯酸甲酯共聚物(EMMA)乃使用乙烯以及甲基丙烯酸甲酯(MMA)做為單體所得之共聚物,於本發明中,乙烯-甲基丙烯酸甲酯共聚物中之甲基丙烯酸甲酯之含有率為25~35質量%,較佳為25~30質量%。若低於25質量%有時透明性會降低,若高於35質量%有時加工性會降低。
乙烯-甲基丙烯酸甲酯共聚物以使用由JIS K7210所規定之熔流速率在35g/10分鐘以下、尤其7~20g/10分鐘者為佳。使用具有如此熔流速率之乙烯-甲基丙烯酸甲酯共聚物所得之太陽電池用密封膜,於太陽電池製作時之密封製程中加熱加壓之際,可抑制密封膜發生熔融或位偏而從基板端部滲出,可得到高密封性能。此外,於本發明中,熔流速率(MFR)之值係依照JIS K7210,以190℃、荷重21.18N之條件
所測定者。
本發明之太陽電池用密封膜除了乙烯-甲基丙烯酸甲酯共聚物亦可進而附加使用聚乙烯縮醛系樹脂(例如聚乙烯縮甲醛、聚乙烯縮丁醛(PVB樹脂)、變性PVB)、氯乙烯樹脂。此時,尤其以PVB為佳。
〔交聯劑〕
本發明中交聯劑可形成乙烯-甲基丙烯酸甲酯共聚物之交聯構造。交聯劑以使用有機過氧化物或是光聚合起始劑為佳。基於得到在接著力、耐濕性、耐貫通性之溫度依存性獲得改善之密封膜的考量,當中又以使用有機過氧化物為佳。
前述有機過氧化物只要是於100℃以上之溫度分解而產生自由基者即可,可使用任意物質。有機過氧化物一般係考慮成膜溫度、組成物之調整條件、硬化溫度、受附物之耐熱性、儲存安定性來選擇。尤其,以半衰期10小時之分解溫度為70℃以上者為佳。
在前述有機過氧化物方面,基於樹脂之加工溫度、儲存安定性之觀點可舉出例如苯醯過氧化物系硬化劑、第三己基過氧化三甲基乙酸酯、第三丁基過氧化三甲基乙酸酯、3,5,5-三甲基己醯基過氧化物、二-正辛醯基過氧化物、月桂醯基過氧化物、硬脂醯基過氧化物、1,1,3,3-四甲基丁基過氧化-2-乙基己醯酯、琥珀醯胺過氧化物、α,α’-雙(第三丁基過氧化異丙基)苯、二枯基過氧化物、二-第三己基過氧化物、2,5-二甲基-2,5-二(第三丁基過氧化)己烷、第三丁
基枯基過氧化物、二-第三丁基過氧化物、2,5-二甲基-2,5-二(2-乙基己醯基過氧化)己烷、1-環己基-1-甲基乙基過氧化-2-乙基己酸酯、第三己基過氧化-2-乙基己酸酯、4-甲基苯醯過氧化物、第三丁基過氧化-2-乙基己酸酯,間甲苯甲醯基+苯醯過氧化物、苯醯過氧化物、1,1-雙(第三丁基過氧化)-2-甲基環己醯酯、1,1-雙(第三己基過氧化)-3,3,5-三甲基環己醯酯、1,1-雙(第三己基過氧化)環己醯酯、1,1-雙(第三丁基過氧化)-3,3,5-三甲基環己烷、1,1-雙(第三丁基過氧化)環己烷、2,2-雙(4,4-二第三丁基過氧化環己基)丙烷、1,1-雙(第三丁基過氧化)環十二烷、第三己基過氧化異丙基單碳酸酯、第三丁基過氧化馬來醯胺、第三丁基過氧化-3,3,5-三甲基己烷、第三丁基過氧化月桂酯、2,5-二甲基-2,5-二(甲基苯醯過氧化)己烷、第三丁基過氧化異丙基單碳酸酯、第三丁基過氧化-2-乙基己基單碳酸酯、第三己基過氧化苯甲酸酯、2,5-二甲基-2,5-二(苯醯過氧化)己烷等。
在苯醯過氧化物系硬化劑方面只要於70℃以上之溫度能分解產生自由基者即皆可使用,以半衰期10小時之分解溫度為50℃以上者為佳,可考慮調製條件、成膜溫度、硬化(貼合)溫度、受附物之耐熱性、儲存安定性來適宜選擇。可使用之苯醯過氧化物系硬化劑可舉出例如苯醯過氧化物、2,5-二甲基己基-2,5-雙過氧化苯甲酸酯、對氯苯醯過氧化物、間甲苯甲
醯基過氧化物、2,4-二氯苯醯過氧化物、第三丁基過氧化苯甲酸酯等。苯醯過氧化物系硬化劑可使用1種或將2種以上組合使用。
此等有機過氧化物當中,以二烷基過氧化物系有機過氧化物之α,α’-雙(第三丁基過氧化異丙基)苯、二枯基過氧化物、二-第三己基過氧化物、2,5-二甲基-2,5-二(第三丁基過氧化)己烷、第三丁基枯基過氧化物以及二-第三丁基過氧化物為佳。藉此,將不易產生分解生成氣體,且可充分提高乙烯-甲基丙烯酸甲酯共聚物之交聯密度,所得之太陽電池用密封膜之耐久性可更為提高。
前述有機過氧化物之含有量相對於乙烯-甲基丙烯酸甲酯共聚物100質量份為0.05~0.7質量份,較佳為0.1~0.3質量份。若少於0.05質量份則交聯反應變慢,有時無法得到充分的接著力,若多於0.7質量份則發泡可能性變高。
此外,在光聚合起始劑方面可使用公知之任意光聚合起始劑,但以摻配後之儲存安定性良好者為所希望者。做為如此之光聚合起始劑可使用例如2-羥基-2-甲基-1-苯基丙烷-1-酮、1-羥基環己基苯酮、2-甲基-1-(4-(甲硫基)苯基)-2-嗎啉丙烷-1等苯乙酮系、苄基二甲基縮酮等安息香系、苯酮、4-苯基苯酮、羥基苯酮等苯酮系、異丙基噻噸酮、2,4-二乙基噻噸酮等噻噸酮系,在其他特殊物方面可使用甲基苯基乙醛酸酯等。尤其較佳為2-羥基-2-甲
基-1-苯基丙烷-1-酮、1-羥基環己基苯酮、2-甲基-1-(4-(甲硫基)苯基)-2-嗎啉丙烷-1、苯酮等。此等光聚合起始劑可依必要性將諸如4-二甲基胺基安息香酸之安息香酸系或是3級胺系等公知慣用的光聚合促進劑之1種或是2種以上以任意比例混合使用。此外,亦可使用光聚合起始劑單獨1種或是將2種以上混合使用。
前述光聚合起始劑之含有量相對於乙烯-甲基丙烯酸甲酯共聚物100質量份為0.05~0.7質量份,較佳為0.1~0.3質量份。若少於0.05質量份則交聯反應變慢,有時無法得到充分接著力,若多於0.7質量份則發泡可能性變高。
〔矽烷耦合劑〕
本發明所使用之矽烷耦合劑可舉出γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基三乙氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、γ-氯丙基甲氧基矽烷、乙烯基乙氧基矽烷、乙烯基三(β-甲氧基乙氧基)矽烷、乙烯基三乙醯氧基矽烷、γ-環氧丙氧丙基三甲氧基矽烷、γ-環氧丙氧丙基三乙氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、乙烯基三氯矽烷、γ-巰基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷等。
當中尤其以屬甲基丙烯醯氧基系矽烷耦合劑(意
指含有甲基丙烯醯氧基之矽烷耦合劑)之γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基三乙氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷為佳,當中又以γ-甲基丙烯醯氧基丙基三甲氧基矽烷為特佳。此等矽烷耦合劑可單獨使用或是組合2種以上使用。
本發明之太陽電池用密封膜中之矽烷耦合劑之含有量相對於乙烯-甲基丙烯酸甲酯共聚物100質量份為0.1~0.7質量份,較佳為0.3~0.65質量份。若少於0.1質量份則有時無法得到充分的接著性。若多於0.7質量份有時會發生滲出。
此處,於本發明中,交聯劑對矽烷耦合劑之質量比(交聯劑/矽烷耦合劑)以0.2~0.5為佳。藉由一方面儘量減少所使用之交聯劑的量、另一方面相對增加矽烷耦合劑之量,可確實抑制發泡並提高接著力。
〔其他〕
交聯硬化前之太陽電池用密封膜亦可進一步含有交聯助劑。前述交聯助劑可提高乙烯-甲基丙烯酸甲酯共聚物之交聯密度,進而提高密封膜之接著性以及耐久性。
前述交聯助劑相對於乙烯-甲基丙烯酸甲酯共聚物100質量份較佳為0.1~3.0質量份、更佳為0.1~2.5質量份。採用如此之交聯助劑之含有量,不會因添加交聯助劑而產生氣體,可提高乙烯-甲基丙烯酸甲酯
共聚物之交聯密度。
做為前述交聯助劑(具有自由基聚合性基做為官能基之化合物),除了三聚氰酸三烯丙酯、異三聚氰酸三烯丙酯等3官能之交聯助劑以外,也可舉出(甲基)丙烯酸酯(例如NK酯等)之單官能或是2官能交聯助劑等。當中又以三聚氰酸三烯丙酯以及異三聚氰酸三烯丙酯為佳,尤其以異三聚氰酸三烯丙酯為佳。
本發明之太陽電池用密封膜為了改良或是調整膜之各種物性(機械強度、透明性等光學特性、耐熱性、耐光性、交聯速度等)、尤其為了改良機械強度,亦可視必要性再含有可塑劑、含丙烯醯氧基之化合物、含甲基丙烯醯氧基之化合物以及/或是含環氧基之化合物等各種添加劑。
前述可塑劑並無特別限定,一般可舉出多元酸之酯、多元醇之酯。其例可舉出鄰苯二甲酸二辛酯、己二酸二己酯、三乙二醇-二-2-乙基丁酸酯、癸二酸丁酯、四乙二醇二丁酸酯、三乙二醇二壬酸酯。可塑劑可使用一種亦可組合二種以上使用。可塑劑之含有量相對於乙烯-甲基丙烯酸甲酯共聚物100質量份以5質量份以下之範圍為佳。
前述含丙烯醯氧基之化合物以及前述含甲基丙烯醯氧基之化合物,一般為丙烯酸或是甲基丙烯酸衍生物,可舉出例如丙烯酸或是甲基丙烯酸之酯或醯胺。在酯殘基之例子方面可舉出甲基、乙基、十二烷基、硬脂基、月桂基等直鏈狀烷基、環己基、四氫糠基、
胺基乙基、2-羥基乙基、3-羥基丙基、3-氯-2-羥基丙基。在醯胺例子方面可舉出二丙酮丙烯醯胺。此外,也可舉出乙二醇、三乙二醇、聚丙二醇、聚乙二醇、三羥甲基丙烷、季戊四醇等多元醇與丙烯酸或是甲基丙烯酸所成之酯。
在前述含環氧基之化合物方面,可舉出三環氧丙基三(2-羥基乙基)異三聚氰酸、新戊二醇二環氧丙醚、1,6-己二醇二環氧丙醚、烯丙基環氧丙醚、2-乙基己基環氧丙醚、苯基環氧丙醚、苯酚(氧化乙烯)5環氧丙醚、對第三丁基苯基環氧丙醚、己二酸二環氧丙酯、鄰苯二甲酸二環氧丙酯、甲基丙烯酸環氧丙酯、丁基環氧丙醚。
前述含丙烯醯氧基之化合物、前述含甲基丙烯醯氧基之化合物、或是前述含環氧基之化合物分別相對於乙烯-甲基丙烯酸甲酯共聚物100質量份一般為0.5~5.0質量份,尤以1.0~4.0質量份為佳。
再者,本發明之太陽電池用密封膜亦可含有抗老化劑。在抗老化劑方面可舉出例如N,N’-己烷-1,6-二基雙〔3-(3,5-二-第三丁基-4-羥基苯基)丙醯胺〕等受阻苯酚系抗氧化劑、磷系熱安定劑、內酯系熱安定劑、維他命E系熱安定劑、硫系熱安定劑等。
〔太陽電池用密封膜之製造〕
當要形成上述本發明之太陽電池用密封膜之情況,只要依據公知方法來進行即可。例如,可藉由將含有上述各成分之組成物以通常之擠出成形或是軋光
成形(軋光)等來成形得到片狀物之方法來製造。此外,也可將前述組成物溶解於溶劑,將此溶液以適當的塗布機(coater)來塗布於適當的支撐體上並乾燥以形成塗膜,藉以得到片狀物。此外,製膜時之加熱溫度以交聯劑不致反應或是幾乎不反應之溫度為佳。例如50~90℃、尤其以40~80℃為佳。本發明之太陽電池用密封膜之厚度並無特別限制,可為0.05~2mm。
〔太陽電池〕
本發明之太陽電池之構造只要使用本發明之太陽電池用密封膜即可並無特別限制。例如,可舉出於表面側透明保護構件與背面側保護構件之間介設本發明之太陽電池用密封膜來交聯一體化之密封有太陽電池用元件之構造等。此外,於本發明中,將太陽電池元件受光照射之側(受光面側)稱為「表面側」,將太陽電池元件受光面之相反面側稱為「背面側」。
前述太陽電池,為了充分密封太陽電池用元件,可例如圖1所示般積層表面側透明保護構件11、表面側密封膜13A、太陽電池用元件14、背面側密封膜13B以及背面側保護構件12,依照加熱加壓等通常方法來使得密封膜交聯硬化即可。
為了進行前述加熱加壓,只要例如將前述積層體以真空層合機在溫度135~180℃(較佳為140~180℃、更佳為155~180℃)、脫氣時間0.1~5分鐘、加壓壓力0.1~1.5kg/cm2、加壓時間5~15分鐘來進行加熱壓接即可。於加熱加壓時,藉由使得表面側密封膜13A以及
背面側密封膜13B所含乙烯-甲基丙烯酸甲酯共聚物進行交聯,可經由表面側密封膜13A以及背面側密封膜13B來使得表面側透明保護構件11、背面側透明構件12、以及太陽電池用元件14一體化來密封太陽電池用元件14。
此外,本發明之太陽電池用密封膜,不光是圖1所示之使用單晶或是多晶矽結晶系的太陽電池元件而得之太陽電池,也可使用於薄膜矽系、薄膜非晶矽系太陽電池、硒化銅銦(CIS)系太陽電池等薄膜太陽電池之密封膜。於此情況,尚可舉出例如:在玻璃基板、聚醯亞胺基板、氟樹脂系透明基板等表面側透明保護構件之表面上以化學氣相蒸鍍法等形成有薄膜太陽電池元件層上積層本發明之太陽電池用密封膜、背面側保護構件而接著一體化之構造;於背面側保護構件表面上所形成之太陽電池元件上積層本發明之太陽電池用密封膜、表面側透明保護構件而接著一體化之構造;或是依序積層表面側透明保護構件、表面側密封膜、薄膜太陽電池元件、背面側密封膜、以及背面側保護構件而接著一體化之構造等。
本發明之太陽電池所使用之表面側透明保護構件11以通常矽酸鹽玻璃等玻璃基板為佳。玻璃基板之厚度一般為0.1~10mm,以0.3~5mm為佳。玻璃基板一般亦可經過化學性或是熱性強化者。
本發明所使用之背面側保護構件12較佳可使用聚對苯二甲酸乙二醇酯(PET)、聚醯胺等塑膠膜。此
外,考慮耐熱性、耐濕熱性,亦可為氟化聚乙烯膜、尤其是依序積層氟化聚乙烯膜/Al/氟化聚乙烯膜所得之膜。
此外,本發明之太陽電池(包含薄膜太陽電池)係於表面側以及/或是背面側所使用之密封膜。從而,關於表面側透明保護構件、背面側保護構件、以及太陽電池用元件等前述密封膜以外的構件,只要具有和以往公知之太陽電池為同樣構成即可,並無特別限制。
【實施例】
以下,依據實施例說明本發明。
〔實施例1~20、比較例1~22〕
以表1~5所示摻配將各材料供給於輥磨機,於70℃進行混練來調製太陽電池用密封膜組成物。將前述太陽電池用密封膜組成物於70℃進行軋光成形,放置冷卻後,製作太陽電池用密封膜。
<評價方法>
(1)初期玻璃接著力
於3mm之浮動玻璃上載置上述太陽電池用密封膜(厚度0.6mm),以設定為100℃之真空層合機加壓10分鐘進行暫時壓接後,使得此積層體於設定在155℃之爐交聯45分鐘。針對此積層體,依照JIS K 6854,如圖2所示般,將玻璃板21與太陽電池用密封膜23之間之一部分加以剝離,將太陽電池用密封膜23彎折180°並使用拉伸試驗機(島津製作所公司製,AUTOGRAPH)以拉伸速度100mm/分鐘時之剝除力做
為玻璃接著力(N/cm)來測定。
(2)耐濕熱性試驗後之玻璃接著力
將和(1)同樣製作之積層體於設定在85℃、85%之環境的濕熱爐內靜置4000小時後,和(1)同樣來測定玻璃接著力。
(3)發泡試驗
將上述太陽電池用密封膜(厚度0.6mm)以玻璃(表面側保護構件)/太陽電池用密封膜/太陽電池元件/太陽電池用密封膜/背面側保護構件(聚醯胺樹脂製背片:ISOVOLTA公司製,ICOSOLAR3554)之順序來積層,於設定在100℃之真空層合機加壓10分鐘來暫時壓接得到積層體,將此積層體放入設定在155℃之爐中,測量直到發生隆起之時間。
(4)光線穿透率
將以2片離型PET(厚度100μm)夾持著太陽電池用密封膜(厚度0.6mm)之積層體以90℃條件在真空層合機以真空2分鐘、加壓8分鐘來經過暫時壓接製程,於設定在155℃之爐交聯45分鐘。針對此積層體,以分光光度計(U-4100:日立製作所製)實施300~1200nm之光譜測定,以其平均值做為光線穿透率。
結果如表1~5所示。
<評價結果>
如表1以及2所示般,實施例1~20之太陽電池用密封膜相較於比較例,發泡受到抑制、初期接著力高、於耐濕熱性條件下之接著力的降低小。尤其,交聯劑/矽烷耦合劑之質量比為0.2~0.5之實施例3、8、9、14、19以及20之密封膜的發泡被顯著抑制,接著力特別高。此外,表中交聯劑/矽烷耦合劑之質量比之值為將小數點第2位四捨五入之值。此外,實施例1~20之太陽電池用密封膜之光線穿透率相較於使用以往所用之EVA的密封膜(比較例1~8)具有同等值,顯示其適合做為密封膜使用。
依據本發明,可提供一種從發電開始初期歷經長期間維持高發電性能之太陽電池。
11‧‧‧表面側透明保護構件
12‧‧‧背面側保護構件
13A‧‧‧表面側密封膜
13B‧‧‧背面側密封膜
14‧‧‧太陽電池用元件
21‧‧‧玻璃板
23‧‧‧太陽電池用密封膜
圖1係一般太陽電池之概略截面圖。
圖2係用以說明接著力評價之180°剝離試驗法之概略圖。
11‧‧‧表面側透明保護構件
12‧‧‧背面側保護構件
13A‧‧‧表面側密封膜
13B‧‧‧背面側密封膜
14‧‧‧太陽電池用元件
Claims (4)
- 一種太陽電池用密封膜,係含有乙烯-甲基丙烯酸甲酯共聚物、交聯劑以及矽烷耦合劑;其特徵在於:該交聯劑之含有量相對於該乙烯-甲基丙烯酸甲酯共聚物100質量份為0.1~0.3質量份,該矽烷耦合劑之含有量相對於該乙烯-甲基丙烯酸甲酯共聚物100質量份為0.3~0.65質量份;該乙烯-甲基丙烯酸甲酯共聚物中之甲基丙烯酸甲酯之含有率為25~35質量%;該交聯劑相對於該矽烷耦合劑之質量比為0.2~0.5;該矽烷耦合劑係甲基丙烯醯氧基系矽烷耦合劑。
- 如申請專利範圍第1項之太陽電池用密封膜,其中該交聯劑係有機過氧化物。
- 如申請專利範圍第2項之太陽電池用密封膜,其中該有機過氧化物為二烷基過氧化物系有機過氧化物。
- 一種太陽電池,係使用有如申請專利範圍第1至3項中任一項之太陽電池用密封膜。
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JP3454585B2 (ja) * | 1994-11-15 | 2003-10-06 | 積水化学工業株式会社 | 太陽電池用封止材 |
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