WO2010013659A1 - Sealing film for solar cell and solar cell using same - Google Patents
Sealing film for solar cell and solar cell using same Download PDFInfo
- Publication number
- WO2010013659A1 WO2010013659A1 PCT/JP2009/063319 JP2009063319W WO2010013659A1 WO 2010013659 A1 WO2010013659 A1 WO 2010013659A1 JP 2009063319 W JP2009063319 W JP 2009063319W WO 2010013659 A1 WO2010013659 A1 WO 2010013659A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solar cell
- sealing film
- group
- carbon atoms
- ultraviolet absorber
- Prior art date
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- 238000007789 sealing Methods 0.000 title claims abstract description 73
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000012964 benzotriazole Substances 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 34
- 230000001681 protective effect Effects 0.000 claims description 22
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 20
- 238000004132 cross linking Methods 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- VQMHSKWEJGIXGA-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-dodecyl-4-methylphenol Chemical group CCCCCCCCCCCCC1=CC(C)=CC(N2N=C3C=CC=CC3=N2)=C1O VQMHSKWEJGIXGA-UHFFFAOYSA-N 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 abstract 3
- 239000002250 absorbent Substances 0.000 abstract 3
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 abstract 1
- 230000000903 blocking effect Effects 0.000 abstract 1
- -1 polyethylene terephthalate Polymers 0.000 description 28
- 239000000463 material Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 239000004611 light stabiliser Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 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 4
- 239000012760 heat stabilizer Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000001782 photodegradation Methods 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 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 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film 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
- 150000003839 salts Chemical class 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-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
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000002704 decyl 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])* 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000001421 myristyl 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])[H] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl 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])[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 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 2
- 238000003860 storage Methods 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- 125000002889 tridecyl 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])[H] 0.000 description 2
- 125000002948 undecyl 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])[H] 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- NLBJAOHLJABDAU-UHFFFAOYSA-N (3-methylbenzoyl) 3-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC(C(=O)OOC(=O)C=2C=C(C)C=CC=2)=C1 NLBJAOHLJABDAU-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-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
- 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
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- 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
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- YATYZLYTTAAVIF-UHFFFAOYSA-N 2-(5-chlorobenzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O YATYZLYTTAAVIF-UHFFFAOYSA-N 0.000 description 1
- SGHJOQOVLLGIGF-UHFFFAOYSA-N 2-(5-chlorobenzotriazol-2-yl)-4-methylphenol Chemical compound CC1=CC=C(O)C(N2N=C3C=C(Cl)C=CC3=N2)=C1 SGHJOQOVLLGIGF-UHFFFAOYSA-N 0.000 description 1
- FMBVJPLZYBKSIZ-UHFFFAOYSA-N 2-(5-chlorobenzotriazol-2-yl)-6-dodecyl-4-methylphenol Chemical compound CCCCCCCCCCCCC1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O FMBVJPLZYBKSIZ-UHFFFAOYSA-N 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 1
- AQROEYPMNFCJCK-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-tert-butyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=CC=CC3=N2)=C1O AQROEYPMNFCJCK-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- UBQXQCCAPASFJR-UHFFFAOYSA-N 2-[2-(2-nonanoyloxyethoxy)ethoxy]ethyl nonanoate Chemical compound CCCCCCCCC(=O)OCCOCCOCCOC(=O)CCCCCCCC UBQXQCCAPASFJR-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
- SSKNCQWPZQCABD-UHFFFAOYSA-N 2-[2-[2-(2-heptanoyloxyethoxy)ethoxy]ethoxy]ethyl heptanoate Chemical compound CCCCCCC(=O)OCCOCCOCCOCCOC(=O)CCCCCC SSKNCQWPZQCABD-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-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
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- ZLAOXGYWRBSWOY-UHFFFAOYSA-N 3-chloropropyl(methoxy)silane Chemical compound CO[SiH2]CCCCl ZLAOXGYWRBSWOY-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- OXGOEZHUKDEEKS-UHFFFAOYSA-N 3-tert-butylperoxy-1,1,5-trimethylcyclohexane Chemical compound CC1CC(OOC(C)(C)C)CC(C)(C)C1 OXGOEZHUKDEEKS-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 0 C[C@@]1N(c(cc(*)cc2*)c2O)N=C(C=C(*)C=C2)C2=*1 Chemical compound C[C@@]1N(c(cc(*)cc2*)c2O)N=C(C=C(*)C=C2)C2=*1 0.000 description 1
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- 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 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
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- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
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- 239000001530 fumaric acid Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- OJXOOFXUHZAXLO-UHFFFAOYSA-M magnesium;1-bromo-3-methanidylbenzene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C1=CC=CC(Br)=C1 OJXOOFXUHZAXLO-UHFFFAOYSA-M 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002960 margaryl 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])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- 125000001400 nonyl 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])[H] 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 125000005930 sec-butyloxycarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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 solar cell encapsulating film comprising an ethylene-polar monomer copolymer as a main component, and more particularly to a solar cell encapsulating film excellent in UV cut sustainability.
- a solar cell generally includes a light-receiving surface side transparent protective member 11 made of a glass substrate or the like, a light-receiving surface side sealing film 13A, a solar cell 14 such as a silicon power generation element, a back surface side sealing film. 13B and the back surface side protection member (back cover) 12 are laminated in this order, degassed under reduced pressure, and then heated and pressurized to crosslink and cure the light receiving surface side sealing film 13A and the back surface side sealing film 13B and adhere.
- Manufactured by integrating In a conventional solar battery, a plurality of solar battery cells 14 are connected and used in order to obtain a high electric output. Therefore, in order to ensure insulation between the solar battery cells 14, the solar battery cells are sealed using the sealing films 13A and 13B having insulation properties.
- a film made of an ethylene-polar monomer copolymer such as an ethylene vinyl acetate copolymer (EVA) film or an ethylene ethyl acrylate copolymer (EEA) film is preferable.
- EVA ethylene vinyl acetate copolymer
- ESA ethylene ethyl acrylate copolymer
- Patent Document 1 a crosslinking density such as an organic peroxide is used in the sealing film in addition to the ethylene-polar monomer copolymer to improve the crosslinking density.
- a transparent substrate such as a glass substrate is used as a light-transmitting light-receiving surface side protective material used in a conventional solar cell in order to make sunlight enter the battery as efficiently as possible and collect it on the solar cell. ing.
- the back side protective material includes a plastic film such as polyethylene terephthalate (PET) or a film in which a vapor deposition film made of silver is formed on the surface of the plastic film in order to prevent moisture from entering the battery. It is used. In addition to the conventional function of preventing the ingress of moisture by adding a colorant to the back side protective material, it improves the reflectance of incident light to increase the power generation efficiency of the battery and improve the design Is planned.
- PET polyethylene terephthalate
- a film in which a vapor deposition film made of silver is formed on the surface of the plastic film in order to prevent moisture from entering the battery. It is used.
- PET polyethylene terephthalate
- a vapor deposition film made of silver is formed on the surface of the plastic film in order to prevent moisture from entering the battery.
- the back side protective material such as a PET film may turn yellow due to the influence of light and heat. Yellowing of the back surface side protective material causes not only a decrease in power generation performance due to a decrease in the reflectance of incident light but also a decrease in design. Therefore, in the conventional solar cell, deterioration of the back surface side protective material has been prevented by adding an ultraviolet absorber to the sealing film to suppress the transmission of ultraviolet rays.
- the conventional solar cell sealing film still has a problem in that it cannot maintain sufficient UV-cutting properties.
- an object of the present invention is to provide a solar cell sealing film that can maintain excellent ultraviolet cut-off properties over a long period of time.
- the present inventor has a benzotriazole-based ultraviolet absorber represented by the following formula (1), and can maintain a high ultraviolet cutting property for a long period of time. It has been found that a sealing film can be obtained.
- the present invention is a solar cell sealing film comprising an ethylene-polar monomer copolymer, an organic peroxide, and an ultraviolet absorber,
- the ultraviolet absorber is represented by the following formula (1)
- a benzotriazole-based ultraviolet absorber represented by a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyloxycarbonyl group having 3 to 22 carbon atoms.
- R 1 represents a chlorine atom or a hydrogen atom
- R 2 and R 3 are different from each other and represent an alkyl group having 1 to 20 carbon atoms.
- the benzotriazole ultraviolet absorber is 2- (2H-1,2,3-benzotriazol-2-yl) -6-dodecyl-4-methylphenol and / or 2- (5-chloro-2H -1,2,3-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol.
- the benzotriazole-based ultraviolet absorber has little photodegradation and has excellent durability. Furthermore, the benzotriazole-based ultraviolet absorber is excellent in the ability to cut ultraviolet rays having wavelengths (about 325 nm and about 380 nm) that promote the deterioration of the back surface side protective material such as a PET film. Therefore, the solar cell sealing film containing the benzotriazole-based ultraviolet absorber can maintain the UV-cutting property for a long period of time, and can highly suppress the photodegradation of the back surface side protective material such as a PET film. It becomes possible.
- the solar cell sealing film of the present invention contains, as basic components, an ethylene-polar monomer copolymer, an organic peroxide, and an ultraviolet absorber, and the ultraviolet absorber has the following formula (1):
- R 1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms
- R 2 and R 3 are the same
- a benzotriazole-based ultraviolet absorber represented by a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyloxycarbonyl group having 3 to 22 carbon atoms.
- halogen atom for R 1 in the formula (1) examples include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom. Of these, a chlorine atom is particularly preferable.
- the alkyl group having 1 to 6 carbon atoms in R 1 of the formula (1) may be a linear or branched alkyl group.
- Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, and neopentyl.
- the haloalkyl group having 1 to 6 carbon atoms in R 1 of the above formula (1) has at least one halogen atom as a substituent in a linear or branched alkyl group.
- Examples of the alkyl group and the halogen atom are the same as those described above.
- Preferred examples of the haloalkyl group include a chloromethyl group and a chlorobutyl group.
- R 1 in the formula (1) a hydrogen atom or a chlorine atom is particularly preferable.
- Examples of the alkyl group having 1 to 20 carbon atoms in R 2 and R 3 in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.
- the alkyloxycarbonyl group having 3 to 22 carbon atoms in R 2 and R 3 in the formula (1) may be a linear or branched alkyloxycarbonyl group. Specifically, methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-hexyloxycarbonyl group, and n -Octyloxycarbonyl group and the like.
- R 2 and R 3 may be the same or different, but are preferably different from each other.
- R 2 and R 3 are preferably alkyl groups having 1 to 20 carbon atoms, particularly 1 to 15 carbon atoms.
- R 2 is preferably an alkyl group having 3 to 15 carbon atoms
- R 3 is preferably an alkyl group having 1 to 3 carbon atoms
- R 2 is a methyl group
- R 3 is A tert-butyl group, a tert-pentyl group, a decyl group, a dodecyl group, an undecyl group, a tridecyl group, a tetradecyl group, or a pentadecyl group is preferred.
- benzotriazole ultraviolet absorber represented by the formula (1) examples include 2- (2H-1,2,3-benzotriazol-2-yl) -4,6-di-tert-butylphenol; 2- (5-Chloro-2H-1,2,3-benzotriazol-2-yl) -4,6-di-tert-butylphenol; 2- (2H-1,2,3-benzotriazol-2-yl ) -4-tert-octylphenol; 2- (2H-1,2,3-benzotriazol-2-yl) -4,6-di-tert-pentylphenol; 2- (5-chloro-2H-1,2 , 3-Benzotriazol-2-yl) -4,6-di-tert-pentylphenol; 2- (2H-1,2,3-benzotriazol-2-yl) -4-tert-butylphenol; -(5-Chloro-2H-1,2,3-benzotriazol-2-yl) -4-ter
- the mass ratio (A: B) of the benzotriazole-based ultraviolet absorber (A) and the organic peroxide (B) in the solar cell sealing film of the present invention is 90:10 to 10:90, particularly 80:20. It is preferably ⁇ 20: 80.
- the functions of the crosslinking agent and the ultraviolet absorber may be deactivated by these reactions. For example, if the amount of the crosslinking agent is too large relative to the ultraviolet absorber, the UV trapping function of the ultraviolet absorber may be reduced by the generated radicals.
- the content of the benzotriazole-based ultraviolet absorber in the solar cell sealing film of the present invention is 0.1 to 1.0 part by mass, particularly 0.5 to 100 parts by mass of the ethylene-polar monomer copolymer.
- the amount is preferably 1.0 parts by mass. If it is the said content, it can be set as the sealing film which has high ultraviolet-ray cut property, without reducing transparency.
- Examples of the polar monomer of the ethylene-polar monomer copolymer used in the solar cell sealing film of the present invention include unsaturated carboxylic acid, its salt, its ester, its amide, vinyl ester, carbon monoxide and the like. Can do.
- unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, itaconic anhydride, lithium of these unsaturated carboxylic acids, sodium
- Monovalent metal salts such as potassium
- polyvalent metal salts such as magnesium, calcium and zinc
- unsaturated carboxylic acid esters such as ethyl methacrylate, isobutyl methacrylate and dimethyl maleate
- vinyl esters such as vinyl acetate and vinyl propionate.
- the ethylene-polar monomer copolymer includes ethylene-acrylic acid copolymer, ethylene-unsaturated carboxylic acid copolymer such as ethylene-methacrylic acid copolymer, and the ethylene-unsaturated carboxylic acid copolymer.
- the ethylene-polar monomer copolymer is most preferably an ethylene vinyl acetate copolymer (EVA).
- EVA ethylene vinyl acetate copolymer
- the ethylene vinyl acetate copolymer has excellent compatibility with the benzotriazole-based UV absorber represented by the above formula (1), has no yellowing caused by the addition of the benzotriazole-based UV absorber, and has excellent UV-cutting properties. It can be demonstrated.
- the content of vinyl acetate in the ethylene vinyl acetate copolymer is 20 to 35 parts by weight, more preferably 22 to 30 parts by weight, particularly 24 to 28 parts by weight, based on 100 parts by weight of the ethylene vinyl acetate copolymer. preferable. If the vinyl acetate content is less than 20 parts by mass, the sealing film obtained when crosslinked and cured at high temperatures may not have sufficient transparency. If it exceeds 35 parts by mass, carboxylic acid, alcohol, etc. are generated. There is a risk that it will be easier to do.
- the solar cell sealing film of the present invention contains an organic peroxide as a crosslinking agent. Thereby, a crosslinked cured film of an ethylene-polar monomer copolymer can be obtained, and the sealing performance of the solar cell can be improved.
- Any organic peroxide may be used as long as it decomposes at a temperature of 100 ° C. or higher to generate radicals.
- the organic peroxide is generally selected in consideration of the film formation temperature, the adjustment conditions of the composition, the curing temperature, the heat resistance of the adherend, and the storage stability. In particular, those having a decomposition temperature of 70 hours or more with a half-life of 10 hours are preferred.
- organic peroxide examples include 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-bis (t, from the viewpoint of processing temperature and storage stability of the resin.
- -Butylperoxy) hexane t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, ⁇ , ⁇ '-bis (t-butylperoxide Oxyisopropyl) benzene, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) cyclohexane 1,1-bis (t-butylperoxy) trimethylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohe
- the content of the crosslinking agent comprising an organic peroxide is preferably 0.1 to 2.0, more preferably 0.3 to 1 with respect to 100 parts by mass of the ethylene-polar monomer copolymer. 0.5 parts by mass, particularly preferably 0.6 to 1.5 parts by mass is preferred. If the content of the organic peroxide is small, the transparency of the resulting sealing film may be lowered, and if it is increased, the compatibility with the copolymer may be deteriorated.
- the composition of the present invention may contain a crosslinking aid as necessary.
- the crosslinking aid can be added to the composition in order to improve the gel fraction of the ethylene-polar monomer copolymer and improve the durability.
- a crosslinking aid compound having a radical polymerizable group as a functional group
- a trifunctional crosslinking aid such as triallyl cyanurate and triallyl isocyanurate, (meth) acrylic ester
- examples thereof include monofunctional or bifunctional crosslinking aids such as NK ester.
- triallyl cyanurate and triallyl isocyanurate are preferable, and triallyl isocyanurate is particularly preferable.
- These crosslinking aids are generally used in an amount of 10 parts by mass or less, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the ethylene-polar monomer copolymer.
- the composition is used for improving or adjusting various physical properties of the film (optical properties such as mechanical strength, adhesiveness, transparency, heat resistance, light resistance, crosslinking speed, etc.), particularly for improving mechanical strength.
- various additives such as a plasticizer, an adhesion improver, an acryloxy group-containing compound, a methacryloxy group-containing compound, and / or an epoxy group-containing compound may further be included.
- the plasticizer is not particularly limited, but polybasic acid esters and polyhydric alcohol esters are generally used. Examples thereof include dioctyl phthalate, dihexyl adipate, triethylene glycol-di-2-ethylbutyrate, butyl sebacate, tetraethylene glycol diheptanoate, and triethylene glycol dipelargonate.
- One type of plasticizer may be used, or two or more types may be used in combination.
- the plasticizer content is preferably in the range of 5 parts by mass or less with respect to 100 parts by mass of the ethylene-polar monomer copolymer.
- a silane coupling agent can be used as the adhesion improver. Thereby, it becomes possible to form the sealing film for solar cells which has the outstanding adhesive force.
- the silane coupling agent include ⁇ -chloropropylmethoxysilane, vinylethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, ⁇ -glycidoxypropyltrimethoxy.
- the content of the adhesion improver is preferably 5 parts by mass or less with respect to 100 parts by mass of the ethylene-polar monomer copolymer.
- the acryloxy group-containing compound and the methacryloxy group-containing compound are generally acrylic acid or methacrylic acid derivatives, and examples thereof include acrylic acid or methacrylic acid esters and amides.
- ester residues include linear alkyl groups such as methyl, ethyl, dodecyl, stearyl, lauryl, cyclohexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group And 3-chloro-2-hydroxypropyl group.
- Examples of amides include diacetone acrylamide.
- polyhydric alcohols such as ethylene glycol, triethylene glycol, polypropylene glycol, polyethylene glycol, trimethylolpropane, and pentaerythritol, and esters of acrylic acid or methacrylic acid can also be used.
- epoxy-containing compound examples include triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, Mention may be made of phenol (ethyleneoxy) 5 glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, glycidyl methacrylate and butyl glycidyl ether.
- the acryloxy group-containing compound, the methacryloxy group-containing compound, or the epoxy group-containing compound is generally 0.5 to 5.0 parts by mass, particularly 1.0 to 100 parts by mass of the ethylene-polar monomer copolymer, respectively. It is preferably contained in an amount of ⁇ 4.0 parts by mass.
- the solar cell sealing film of the present invention may contain a light stabilizer and / or an anti-aging agent.
- the solar cell sealing film contains a light stabilizer, the deterioration of the ethylene-polar monomer copolymer due to the influence of irradiated light or the like, and the solar cell sealing film are prevented from yellowing. be able to.
- a light stabilizer called a hindered amine type is preferably used.
- LA-52, LA-57, LA-62, LA-63LA-63p, LA-67, LA-68 (all ( ADEKA Co., Ltd.), Tinuvin 744, Tinuvin 770, Tinuvin 765, Tinuvin 144, Tinuvin 622LD, CHIMASSORB 944LD (all manufactured by Ciba Specialty Chemicals Co., Ltd.), UV-3034 (BF Goodrich) Can be mentioned.
- the light stabilizer may be used alone or in combination of two or more kinds, and the blending amount is 0.01 to 5 parts by mass with respect to 100 parts by mass of the ethylene-polar monomer copolymer. It is preferable that
- anti-aging agent examples include hindered phenol antioxidants such as N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]. , Phosphorus heat stabilizers, lactone heat stabilizers, vitamin E heat stabilizers, sulfur heat stabilizers, and the like.
- the solar cell sealing film of the present invention described above may be formed according to a known method.
- the composition containing the various components described above can be produced by a method of obtaining a sheet-like material by molding by ordinary extrusion molding, calendar molding (calendering) or the like.
- a sheet-like material can be obtained by dissolving the composition in a solvent and coating the solution on a suitable support with a suitable coating machine (coater) and drying to form a coating film.
- a suitable coating machine coater
- heating is generally in the range of 50 to 90 ° C.
- the thickness of the solar cell sealing film is not particularly limited, but may be in the range of 50 ⁇ m to 2 mm.
- the solar cell sealing film of the present invention described above contains a benzotriazole-based ultraviolet absorber that has little photodegradation and has excellent durability.
- the said benzotriazole type ultraviolet absorber is excellent in the cut property of the ultraviolet-ray which has a wavelength (about 325 nm, about 380 nm) which accelerates
- a wavelength about 325 nm, about 380 nm
- the solar cell sealing film of the present invention has a light transmittance of a wavelength of 325 nm of 0.3% or less and a light transmittance of a wavelength of 380 nm of 1.5% or less. Therefore, the solar cell sealing film can maintain an excellent ultraviolet cut property over a long period of time.
- the solar cell sealing film of the present invention is subjected to an accelerated weathering test (after irradiation with ultraviolet rays having an ultraviolet intensity of 100 mW / cm 2 at 300 to 400 nm in air at a temperature of 63 ° C. and a humidity of 50% RH for 300 hours. ),
- the YI value difference ( ⁇ YI value) is 7 or less.
- the structure of the solar cell using such a solar cell sealing film is not particularly limited, but the solar cell sealing film is interposed between the light-receiving surface side transparent protective member and the back surface side protective member.
- crosslinking integration are mentioned.
- the light receiving surface side transparent protective member 11 the light receiving surface side sealing film 13A, the solar cell 14 and the back surface side sealing.
- the film 13B and the back surface side protection member 12 may be laminated, and the sealing film may be cross-linked and cured according to a conventional method such as heat and pressure.
- the laminate is heated with a vacuum laminator at a temperature of 135 to 180 ° C., further 140 to 180 ° C., particularly 155 to 180 ° C., a degassing time of 0.1 to 5 minutes, and a press pressure of 0.1.
- Heat pressing may be performed at a pressure of ⁇ 1.5 kg / cm 2 and a press time of 5 to 15 minutes.
- the ethylene-polar monomer copolymer contained in the light receiving surface side sealing film 13A and the back surface side sealing film 13B is cross-linked, whereby the light receiving surface side sealing film 13A and the back surface side sealing film 13B.
- the solar cell 14 can be sealed by integrating the light-receiving surface-side transparent protective member 11, the back-side transparent member 12, and the solar cell 14.
- the sealing film containing the benzotriazole-based ultraviolet absorber is preferably used as at least a back surface side sealing film, and is used as both a light receiving surface side sealing film and a back surface side sealing film. Is more preferable.
- the side of the solar cell irradiated with light is referred to as “light receiving surface side”, and the side opposite to the light receiving surface of the solar cell is referred to as “back surface side”.
- the light-receiving surface side transparent protective member used for the solar cell of the present invention is usually a glass substrate such as silicate glass.
- the thickness of the glass substrate is generally from 0.1 to 10 mm, and preferably from 0.3 to 5 mm.
- the glass substrate may generally be chemically or thermally strengthened.
- the back surface side protective member used in the present invention is a plastic film such as PET.
- a fluorinated polyethylene film particularly a fluorinated polyethylene film / Al / fluorinated polyethylene film, in this order.
- a film laminated with is preferable.
- the solar cell of this invention has the characteristics in the sealing film used for a light-receiving surface side and a back surface side as mentioned above. Therefore, the members other than the sealing film such as the light-receiving surface-side transparent protective member, the back-side protective member, and the solar cell need only have the same configuration as a conventionally known solar cell, and are particularly limited. Not.
- Example 1 The materials shown in Table 1 were supplied to a roll mill and kneaded at 70 ° C., and the resulting composition was calendered at 70 ° C., allowed to cool, and then sealed for solar cells (thickness: 1.0 mm). Got.
- Examples 2 to 19 and Comparative Examples 1 to 6 As shown in Tables 1 to 4, a solar cell sealing film was prepared in the same manner as in Example 1 except that the type and / or addition amount of the ultraviolet absorber was changed.
- the integrated laminate was subjected to 300 ° C. in an air with a temperature of 63 ° C. and a humidity of 50% RH using an accelerated weathering tester (S-UV tester, manufactured by Iwasaki Electric Co., Ltd.) using a 4 KW metal halide lamp as a light source. It was taken out after being irradiated with ultraviolet rays having an ultraviolet intensity of 100 mW / cm 2 at ⁇ 400 nm for 300 hours.
- S-UV tester accelerated weathering tester
- the solar cell sealing film of the present invention can cut the transmission of light with a wavelength of 325 nm and a wavelength of 380 nm to a high level even after the accelerated weathering test,
- the degree ( ⁇ YI value) is also extremely low. That is, even after the accelerated weather resistance test, the light transmittance at a wavelength of 325 nm is 0.5% or less, the light transmittance at a wavelength of 380 nm is 2.0% or less, and the difference in YI values is 13 or less. It is. From these, it can be seen that the solar cell sealing film of the present invention is capable of maintaining excellent ultraviolet cutting property and transparency over a long period of time.
- the solar cell sealing film of the present invention it is possible to provide a solar cell capable of exhibiting excellent design and power generation performance over a long period of time.
Abstract
A sealing film for solar cells, which can maintain excellent ultraviolet light blocking properties for a long time.
The sealing film for solar cells contains an ethylene-polar monomer copolymer, an organic peroxide and an ultraviolet absorbent, and is characterized in that the ultraviolet absorbent is a benzotriazole ultraviolet absorbent represented by formula (1).
(In the formula, R1 represents a hydrogen atom, a halogen atom, an alkyl group having 1-6 carbon atoms or a haloalkyl group having 1-6 carbon atoms; and R2 and R3 may be the same or different and each represents a hydrogen atom, an alkyl group having 1-20 carbon atoms or an alkyloxycarbonyl group having 3-22 carbon atoms.)
Description
本発明は、エチレン－極性モノマー共重合体を主成分とする太陽電池用封止膜に関し、特に紫外線カット持続性に優れる太陽電池用封止膜に関する。
The present invention relates to a solar cell encapsulating film comprising an ethylene-polar monomer copolymer as a main component, and more particularly to a solar cell encapsulating film excellent in UV cut sustainability.
近年、資源の有効利用や環境汚染の防止等の面から、太陽光を電気エネルギーに直接、変換する太陽電池が広く使用され、さらなる開発が進められている。
In recent years, solar cells that directly convert sunlight into electrical energy have been widely used and further developed in terms of effective use of resources and prevention of environmental pollution.
太陽電池は、一般に、図１に示すように、ガラス基板などからなる受光面側透明保護部材１１、受光面側封止膜１３Ａ、シリコン発電素子などの太陽電池用セル１４、裏面側封止膜１３Ｂ、及び裏面側保護部材（バックカバー）１２をこの順で積層し、減圧で脱気した後、加熱加圧して受光面側封止膜１３Ａ及び裏面側封止膜１３Ｂを架橋硬化させて接着一体化することにより製造される。従来の太陽電池では、高い電気出力を得るために、複数の太陽電池用セル１４を接続して用いられている。したがって、太陽電池用セル１４間の絶縁性を確保するために、絶縁性のある封止膜１３Ａ、１３Ｂを用いて太陽電池用セルを封止している。
As shown in FIG. 1, a solar cell generally includes a light-receiving surface side transparent protective member 11 made of a glass substrate or the like, a light-receiving surface side sealing film 13A, a solar cell 14 such as a silicon power generation element, a back surface side sealing film. 13B and the back surface side protection member (back cover) 12 are laminated in this order, degassed under reduced pressure, and then heated and pressurized to crosslink and cure the light receiving surface side sealing film 13A and the back surface side sealing film 13B and adhere. Manufactured by integrating. In a conventional solar battery, a plurality of solar battery cells 14 are connected and used in order to obtain a high electric output. Therefore, in order to ensure insulation between the solar battery cells 14, the solar battery cells are sealed using the sealing films 13A and 13B having insulation properties.
受光面側および裏面側に用いられる封止膜としては、エチレン酢酸ビニル共重合体（ＥＶＡ）フィルム、エチレンエチルアクリレート共重合体（ＥＥＡ）フィルムなどのエチレン－極性モノマー共重合体からなるフィルムが好ましく用いられている（特許文献１）。また、膜強度や耐久性を向上させるために、前記封止膜にエチレン－極性モノマー共重合体の他に有機過酸化物などの架橋剤を用いて架橋密度を向上させている。
As the sealing film used on the light receiving surface side and the back surface side, a film made of an ethylene-polar monomer copolymer such as an ethylene vinyl acetate copolymer (EVA) film or an ethylene ethyl acrylate copolymer (EEA) film is preferable. (Patent Document 1). Further, in order to improve the film strength and durability, a crosslinking density such as an organic peroxide is used in the sealing film in addition to the ethylene-polar monomer copolymer to improve the crosslinking density.
従来の太陽電池に用いられる透光性の受光面側保護材には、電池内に太陽光をなるべく効率よく入射させて太陽電池セルに集光するために、ガラス基板などの透明基板が用いられている。
A transparent substrate such as a glass substrate is used as a light-transmitting light-receiving surface side protective material used in a conventional solar cell in order to make sunlight enter the battery as efficiently as possible and collect it on the solar cell. ing.
一方、裏面側保護材には、電池内部への水分侵入などを防止するために、ポリエチレンテレフタレート（ＰＥＴ）などのプラスチックフィルムや、これらのプラスチックフィルム表面に銀からなる蒸着膜が形成されたものが用いられている。裏面側保護材には、さらに着色剤を添加することにより、水分の浸入を防止する従来の機能に加えて、入射光の反射率を向上させて電池の発電効率を高めたり、意匠性の向上が図られている。
On the other hand, the back side protective material includes a plastic film such as polyethylene terephthalate (PET) or a film in which a vapor deposition film made of silver is formed on the surface of the plastic film in order to prevent moisture from entering the battery. It is used. In addition to the conventional function of preventing the ingress of moisture by adding a colorant to the back side protective material, it improves the reflectance of incident light to increase the power generation efficiency of the battery and improve the design Is planned.
しかしながら、太陽電池を屋外などで長期に亘り使用した場合に、光、熱の影響により、ＰＥＴフィルムなどの裏面側保護材が黄変する場合がある。裏面側保護材の黄変は、入射光の反射率の低下による発電性能の低下だけでなく、意匠性の低下をも招く。そこで、従来の太陽電池では、封止膜に紫外線吸収剤を添加して、紫外線の透過を抑制することにより、裏面側保護材の劣化を防止していた。
However, when the solar cell is used outdoors for a long time, the back side protective material such as a PET film may turn yellow due to the influence of light and heat. Yellowing of the back surface side protective material causes not only a decrease in power generation performance due to a decrease in the reflectance of incident light but also a decrease in design. Therefore, in the conventional solar cell, deterioration of the back surface side protective material has been prevented by adding an ultraviolet absorber to the sealing film to suppress the transmission of ultraviolet rays.
上述のように、封止膜に紫外線吸収剤を添加しても、経時的に紫外線吸収剤が劣化して、紫外線の透過量が高くなる場合があった。そのため、従来の太陽電池用封止膜では、依然として十分な紫外線カット性を維持できない問題があった。
As described above, even when an ultraviolet absorber was added to the sealing film, the ultraviolet absorber deteriorated with time, and the amount of transmitted ultraviolet light sometimes increased. For this reason, the conventional solar cell sealing film still has a problem in that it cannot maintain sufficient UV-cutting properties.
そこで、本発明は、優れた紫外線カット性を長期間に亘り維持することができる太陽電池用封止膜を提供することを目的とする。
Therefore, an object of the present invention is to provide a solar cell sealing film that can maintain excellent ultraviolet cut-off properties over a long period of time.
本発明者は、上記課題に鑑み種々の検討を行った結果、下記式（１）で示されるベンゾトリアゾール系紫外線吸収剤により、高い紫外線カット性を長期間に亘り維持することができる太陽電池用封止膜が得られることを見出した。
As a result of various studies in view of the above-mentioned problems, the present inventor has a benzotriazole-based ultraviolet absorber represented by the following formula (1), and can maintain a high ultraviolet cutting property for a long period of time. It has been found that a sealing film can be obtained.
すなわち、本発明は、エチレン－極性モノマー共重合体、有機過酸化物、及び紫外線吸収剤を含む太陽電池用封止膜であって、
前記紫外線吸収剤が、下記式（１） That is, the present invention is a solar cell sealing film comprising an ethylene-polar monomer copolymer, an organic peroxide, and an ultraviolet absorber,
The ultraviolet absorber is represented by the following formula (1)
前記紫外線吸収剤が、下記式（１） That is, the present invention is a solar cell sealing film comprising an ethylene-polar monomer copolymer, an organic peroxide, and an ultraviolet absorber,
The ultraviolet absorber is represented by the following formula (1)
（式中、Ｒ1は、水素原子、ハロゲン原子、炭素原子数１～６個のアルキル基、又は炭素原子数１～６個のハロアルキル基を表し、Ｒ2及びＲ3は、同一であっても異なっていてもよく、水素原子、炭素原子数１～２０個のアルキル基、又は炭素原子数３～２２のアルキルオキシカルボニル基を表す）で表されるベンゾトリアゾール系紫外線吸収剤であることを特徴とする太陽電池用封止膜により上記課題を解決する。
(Wherein R 1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms, and R 2 and R 3 are the same, A benzotriazole-based ultraviolet absorber represented by a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyloxycarbonyl group having 3 to 22 carbon atoms). The above-described problems are solved by the characteristic solar cell sealing film.
本発明の太陽電池用封止膜の好適な態様を以下に列記する。
Preferred embodiments of the solar cell sealing film of the present invention are listed below.
（１）前記式（１）において、Ｒ1が塩素原子又は水素原子を表し、Ｒ2及びＲ3が、相互に異なり、炭素原子数１～２０個のアルキル基を表す。
(1) In the formula (1), R 1 represents a chlorine atom or a hydrogen atom, and R 2 and R 3 are different from each other and represent an alkyl group having 1 to 20 carbon atoms.
（２）前記ベンゾトリアゾール系紫外線吸収剤が、２－（２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－６－ドデシル－４－メチルフェノール及び／又は２－（５－クロロ－２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４－メチル－６－ｔｅｒｔ－ブチルフェノールである。
(2) The benzotriazole ultraviolet absorber is 2- (2H-1,2,3-benzotriazol-2-yl) -6-dodecyl-4-methylphenol and / or 2- (5-chloro-2H -1,2,3-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol.
（３）前記ベンゾトリアゾール系紫外線吸収剤と前記有機過酸化物との質量比が、９０：１０～１０：９０である。
(3) The mass ratio of the benzotriazole ultraviolet absorber and the organic peroxide is 90:10 to 10:90.
前記ベンゾトリアゾール系紫外線吸収剤は、光劣化が少なく、優れた耐久性を有する。さらに、前記ベンゾトリアゾール系紫外線吸収剤は、ＰＥＴフィルムなど裏面側保護材の劣化を促進させる波長（約３２５ｎｍ、約３８０ｎｍ）を有する紫外線のカット性に優れる。したがって、前記ベンゾトリアゾール系紫外線吸収剤を含む太陽電池用封止膜は、紫外線カット性を長期間に亘り維持することができ、ＰＥＴフィルムなどの裏面側保護材の光劣化を高く抑制することが可能となる。
The benzotriazole-based ultraviolet absorber has little photodegradation and has excellent durability. Furthermore, the benzotriazole-based ultraviolet absorber is excellent in the ability to cut ultraviolet rays having wavelengths (about 325 nm and about 380 nm) that promote the deterioration of the back surface side protective material such as a PET film. Therefore, the solar cell sealing film containing the benzotriazole-based ultraviolet absorber can maintain the UV-cutting property for a long period of time, and can highly suppress the photodegradation of the back surface side protective material such as a PET film. It becomes possible.
本発明の太陽電池用封止膜は、基本成分として、エチレン－極性モノマー共重合体、有機過酸化物、及び紫外線吸収剤を含み、前記紫外線吸収剤として、下記式（１）
The solar cell sealing film of the present invention contains, as basic components, an ethylene-polar monomer copolymer, an organic peroxide, and an ultraviolet absorber, and the ultraviolet absorber has the following formula (1):
（式中、Ｒ1は、水素原子、ハロゲン原子、炭素原子数１～６個のアルキル基、又は炭素原子数１～６個のハロアルキル基を表し、Ｒ2及びＲ3は、同一であっても異なっていてもよく、水素原子、炭素原子数１～２０個のアルキル基、又は炭素原子数３～２２のアルキルオキシカルボニル基を表す）で表されるベンゾトリアゾール系紫外線吸収剤を用いる。
(Wherein R 1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms, and R 2 and R 3 are the same, And a benzotriazole-based ultraviolet absorber represented by a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyloxycarbonyl group having 3 to 22 carbon atoms).
前記式（１）のＲ1におけるハロゲン原子としては、フッ素原子、塩素原子、ヨウ素原子、及び臭素原子などが挙げられる。なかでも、塩素原子が特に好ましい。
Examples of the halogen atom for R 1 in the formula (1) include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom. Of these, a chlorine atom is particularly preferable.
前記式（１）のＲ1における炭素原子数１～６個のアルキル基は、直鎖状又は分岐状のアルキル基であればよい。前記アルキル基として具体的には、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｓｅｃ－ブチル基、ｎ－ペンチル基、イソペンチル基，ネオペンチル基、ｔｅｒｔ－ペンチル基、及びｎ－ヘキシル基などを挙げることができる。
The alkyl group having 1 to 6 carbon atoms in R 1 of the formula (1) may be a linear or branched alkyl group. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, and neopentyl. Group, tert-pentyl group, n-hexyl group and the like.
前記式（１）のＲ1における炭素原子数１～６個のハロアルキル基は、直鎖状又は分岐状のアルキル基に少なくとも１個のハロゲン原子を置換基として有するものである。前記アルキル基及び前記ハロゲン原子としては上述したのと同様のものが挙げられる。好ましいハロアルキル基としては、例えば、クロロメチル基、クロロブチル基などを挙げることができる。
The haloalkyl group having 1 to 6 carbon atoms in R 1 of the above formula (1) has at least one halogen atom as a substituent in a linear or branched alkyl group. Examples of the alkyl group and the halogen atom are the same as those described above. Preferred examples of the haloalkyl group include a chloromethyl group and a chlorobutyl group.
前記式（１）のＲ1として上述したもののうち、水素原子又は塩素原子が特に好ましく挙げられる。
Of those described above as R 1 in the formula (1), a hydrogen atom or a chlorine atom is particularly preferable.
前記式（１）のＲ2及びＲ3における炭素原子数１～２０個のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｓｅｃ－ブチル基、ｎ－ペンチル基、イソペンチル基，ネオペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、ノニル基、デシル基、ドデシル基、ウンデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノニデシル基、及びエイコシル基などを挙げることができる。
Examples of the alkyl group having 1 to 20 carbon atoms in R 2 and R 3 in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Group, sec-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, nonyl group, decyl group, dodecyl group, undecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group Group, heptadecyl group, octadecyl group, nonidecyl group, and eicosyl group.
前記式（１）のＲ2及びＲ3における炭素原子数３～２２のアルキルオキシカルボニル基は、直鎖状又は分岐状のアルキルオキシカルボニル基であればよい。具体的には、メトキシカルボニル基、エトキシカルボニル基、イソプロポキシカルボニル基、ｎ－ブトキシカルボニル基、イソブトキシカルボニル基、ｓｅｃ－ブトキシカルボニル基、ｔｅｒｔ－ブトキシカルボニル基、ｎ－ヘキシルオキシカルボニル基、及びｎ－オクチルオキシカルボニル基などが挙げられる。
The alkyloxycarbonyl group having 3 to 22 carbon atoms in R 2 and R 3 in the formula (1) may be a linear or branched alkyloxycarbonyl group. Specifically, methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-hexyloxycarbonyl group, and n -Octyloxycarbonyl group and the like.
前記式（１）において、Ｒ2及びＲ3は、同一であっても異なっていてもよいが、相互に異なっているのが好ましい。前記Ｒ2及びＲ3として好ましくは、炭素原子数１～２０個、特に１～１５個のアルキル基が挙げられる。なかでも、Ｒ2が炭素原子数３～１５個のアルキル基であり、Ｒ3が炭素原子数１～３個のアルキル基であるのが好ましく、特にＲ2がメチル基であり、Ｒ3がｔｅｒｔ－ブチル基、ｔｅｒｔ－ペンチル基、デシル基、ドデシル基、ウンデシル基、トリデシル基、テトラデシル基、又はペンタデシル基であるのが好ましい。
In the formula (1), R 2 and R 3 may be the same or different, but are preferably different from each other. R 2 and R 3 are preferably alkyl groups having 1 to 20 carbon atoms, particularly 1 to 15 carbon atoms. Among them, R 2 is preferably an alkyl group having 3 to 15 carbon atoms, R 3 is preferably an alkyl group having 1 to 3 carbon atoms, and particularly R 2 is a methyl group, and R 3 is A tert-butyl group, a tert-pentyl group, a decyl group, a dodecyl group, an undecyl group, a tridecyl group, a tetradecyl group, or a pentadecyl group is preferred.
前記式（１）で表されるベンゾトリアゾール系紫外線吸収剤として具体的には、２－（２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４，６－ジ－ｔｅｒｔ－ブチルフェノール；２－（５－クロロ－２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４，６－ジ－ｔｅｒｔ－ブチルフェノール；２－（２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４－ｔｅｒｔ－オクチルフェノール；２－（２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４，６－ジ－ｔｅｒｔ－ペンチルフェノール； ２－（５－クロロ－２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４，６－ジ－ｔｅｒｔ－ペンチルフェノール；２－（２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４－ｔｅｒｔ－ブチルフェノール；２－（５－クロロ－２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４－ｔｅｒｔ－ブチルフェノール；２－（２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４－メチルフェノール；２－（５－クロロ－２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４－メチルフェノール；２－（２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－６－ドデシル－４－メチルフェノール；２－（５－クロロ－２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－６－ドデシル－４－メチルフェノール；２－（２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４－メチル－６－ｔｅｒｔ－ブチルフェノール；２－（５－クロロ－２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４－メチル－６－ｔｅｒｔ－ブチルフェノールなどが挙げられる。これらは１種単独で使用してもよく、２種以上を混合して使用してもよい。
Specific examples of the benzotriazole ultraviolet absorber represented by the formula (1) include 2- (2H-1,2,3-benzotriazol-2-yl) -4,6-di-tert-butylphenol; 2- (5-Chloro-2H-1,2,3-benzotriazol-2-yl) -4,6-di-tert-butylphenol; 2- (2H-1,2,3-benzotriazol-2-yl ) -4-tert-octylphenol; 2- (2H-1,2,3-benzotriazol-2-yl) -4,6-di-tert-pentylphenol; 2- (5-chloro-2H-1,2 , 3-Benzotriazol-2-yl) -4,6-di-tert-pentylphenol; 2- (2H-1,2,3-benzotriazol-2-yl) -4-tert-butylphenol; -(5-Chloro-2H-1,2,3-benzotriazol-2-yl) -4-tert-butylphenol; 2- (2H-1,2,3-benzotriazol-2-yl) -4-methyl Phenol; 2- (5-Chloro-2H-1,2,3-benzotriazol-2-yl) -4-methylphenol; 2- (2H-1,2,3-benzotriazol-2-yl) -6 -Dodecyl-4-methylphenol; 2- (5-chloro-2H-1,2,3-benzotriazol-2-yl) -6-dodecyl-4-methylphenol; 2- (2H-1,2,3 -Benzotriazol-2-yl) -4-methyl-6-tert-butylphenol; 2- (5-chloro-2H-1,2,3-benzotriazol-2-yl) -4-methyl-6-tert- Butyl Fe Nord etc. are mentioned. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.
なかでも、前記式（１）で表されるベンゾトリアゾール系紫外線吸収剤としては、２－（２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－６－ドデシル－４－メチルフェノール、２－（５－クロロ－２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４－メチル－６－ｔｅｒｔ－ブチルフェノール、２－（２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４－ｔｅｒｔ－オクチルフェノール、及び２－（２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４，６－ジ－ｔｅｒｔ－ペンチルフェノールが好ましく挙げられる。
Among these, as the benzotriazole-based ultraviolet absorber represented by the formula (1), 2- (2H-1,2,3-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2 -(5-Chloro-2H-1,2,3-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol, 2- (2H-1,2,3-benzotriazol-2-yl) Preferred are -4-tert-octylphenol and 2- (2H-1,2,3-benzotriazol-2-yl) -4,6-di-tert-pentylphenol.
本発明の太陽電池用封止膜におけるベンゾトリアゾール系紫外線吸収剤（Ａ）と有機過酸化物（Ｂ）との質量比（Ａ：Ｂ）は、９０：１０～１０：９０、特に８０：２０～２０：８０であるのが好ましい。架橋剤及び紫外線吸収剤はこれらの反応により機能が失活する場合がある。例えば、紫外線吸収剤に対して架橋剤の量が多過ぎると、発生したラジカルにより紫外線吸収剤のＵＶ捕捉機能が低下する場合がある。また、架橋剤に対して紫外線吸収剤の量が多過ぎると、紫外線吸収剤によりラジカルの発生が抑制されて架橋反応が進行しない恐れがある。したがって、架橋剤及び紫外線吸収剤を組み合わせて使用する場合には、配合比を最適化するのが好ましく、上記範囲内とするのが好ましい。
The mass ratio (A: B) of the benzotriazole-based ultraviolet absorber (A) and the organic peroxide (B) in the solar cell sealing film of the present invention is 90:10 to 10:90, particularly 80:20. It is preferably ˜20: 80. The functions of the crosslinking agent and the ultraviolet absorber may be deactivated by these reactions. For example, if the amount of the crosslinking agent is too large relative to the ultraviolet absorber, the UV trapping function of the ultraviolet absorber may be reduced by the generated radicals. Moreover, when there is too much quantity of a ultraviolet absorber with respect to a crosslinking agent, generation | occurrence | production of a radical will be suppressed with a ultraviolet absorber, and there exists a possibility that a crosslinking reaction may not advance. Accordingly, when a combination of a crosslinking agent and an ultraviolet absorber is used, it is preferable to optimize the blending ratio, and it is preferably within the above range.
本発明の太陽電池用封止膜における前記ベンゾトリアゾール系紫外線吸収剤の含有量は、エチレン－極性モノマー共重合体１００質量部に対して、０．１～１．０質量部、特に０．５～１．０質量部であるのが好ましい。前記含有量であれば、透明性を低下させることなく高い紫外線カット性を有する封止膜とすることができる。
The content of the benzotriazole-based ultraviolet absorber in the solar cell sealing film of the present invention is 0.1 to 1.0 part by mass, particularly 0.5 to 100 parts by mass of the ethylene-polar monomer copolymer. The amount is preferably 1.0 parts by mass. If it is the said content, it can be set as the sealing film which has high ultraviolet-ray cut property, without reducing transparency.
本発明の太陽電池用封止膜に用いられるエチレン－極性モノマー共重合体の極性モノマーとしては、不飽和カルボン酸、その塩、そのエステル、そのアミド、ビニルエステル、一酸化炭素などを例示することができる。より具体的には、アクリル酸、メタクリル酸、フマル酸、イタコン酸、マレイン酸モノメチル、マレイン酸モノエチル、無水マレイン酸、無水イタコン酸等の不飽和カルボン酸、これら不飽和カルボン酸のリチウム、ナトリウム、カリウムなどの１価金属の塩やマグネシウム、カルシウム、亜鉛などの多価金属の塩、アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸イソブチル、アクリル酸ｎブチル、アクリル酸イソオクチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸イソブチル、マレイン酸ジメチル等の不飽和カルボン酸エステル、酢酸ビニル、プロピオン酸ビニルのようなビニルエステルなどの一種又は二種以上などを例示することができる。
Examples of the polar monomer of the ethylene-polar monomer copolymer used in the solar cell sealing film of the present invention include unsaturated carboxylic acid, its salt, its ester, its amide, vinyl ester, carbon monoxide and the like. Can do. More specifically, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, itaconic anhydride, lithium of these unsaturated carboxylic acids, sodium, Monovalent metal salts such as potassium, polyvalent metal salts such as magnesium, calcium and zinc, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, nbutyl acrylate, isooctyl acrylate, methyl methacrylate Examples thereof include one or more of unsaturated carboxylic acid esters such as ethyl methacrylate, isobutyl methacrylate and dimethyl maleate, and vinyl esters such as vinyl acetate and vinyl propionate.
エチレン－極性モノマー共重合体としてより具体的には、エチレン－アクリル酸共重合体、エチレン－メタクリル酸共重合体のようなエチレン－不飽和カルボン酸共重合体、前記エチレン－不飽和カルボン酸共重合体のカルボキシル基の一部又は全部が上記金属で中和されたアイオノマー、エチレン－アクリル酸メチル共重合体、エチレン－アクリル酸エチル共重合体、エチレン－メタクリル酸メチル共重合体、エチレン－アクリル酸イソブチル共重合体、エチレン－アクリル酸ｎブチル共重合体のようなエチレン－不飽和カルボン酸エステル共重合体、エチレン－アクリル酸イソブチル－メタクリル酸共重合体、エチレン－アクリル酸ｎブチル－メタクリル酸共重合体のようなエチレン－不飽和カルボン酸エステル－不飽和カルボン酸共重合体及びそのカルボキシル基の一部又は全部が上記金属で中和されたアイオノマー、エチレン－酢酸ビニル共重合体のようなエチレン－ビニルエステル共重合体などを代表例として例示することができる。
More specifically, the ethylene-polar monomer copolymer includes ethylene-acrylic acid copolymer, ethylene-unsaturated carboxylic acid copolymer such as ethylene-methacrylic acid copolymer, and the ethylene-unsaturated carboxylic acid copolymer. Ionomer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-acrylic, wherein some or all of the carboxyl groups of the polymer are neutralized with the above metals Ethylene isobutyl copolymer, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-n-butyl acrylate copolymer, ethylene-isobutyl acrylate-methacrylic acid copolymer, ethylene-n-butyl acrylate-methacrylic acid Ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer such as copolymer It can be exemplified vinyl ester copolymers and the like as a typical example - some or all of the polymer and the carboxyl group is an ionomer neutralized with the metal, ethylene - ethylene such as vinyl acetate copolymer.
なかでも、エチレン－極性モノマー共重合体として、最も好ましくは、エチレン酢酸ビニル共重合体（ＥＶＡ）が挙げられる。エチレン酢酸ビニル共重合体は、前記式（１）で表されるベンゾトリアゾール系紫外線吸収剤との相溶性に優れ、ベンゾトリアゾール系紫外線吸収剤の添加による黄変がなく、優れた紫外線カット性を発揮することができる。
Among them, the ethylene-polar monomer copolymer is most preferably an ethylene vinyl acetate copolymer (EVA). The ethylene vinyl acetate copolymer has excellent compatibility with the benzotriazole-based UV absorber represented by the above formula (1), has no yellowing caused by the addition of the benzotriazole-based UV absorber, and has excellent UV-cutting properties. It can be demonstrated.
エチレン酢酸ビニル共重合体における酢酸ビニルの含有量は、前記エチレン酢酸ビニル共重合体１００質量部に対して２０～３５質量部、さらに２２～３０質量部、特に２４～２８質量部とするのが好ましい。酢酸ビニルの含有量が、２０質量部未満であると、高温で架橋硬化させる場合に得られる封止膜の透明度が充分でない恐れがあり、３５質量部を超えると、カルボン酸、アルコール等が発生しやすくなる恐れがある。
The content of vinyl acetate in the ethylene vinyl acetate copolymer is 20 to 35 parts by weight, more preferably 22 to 30 parts by weight, particularly 24 to 28 parts by weight, based on 100 parts by weight of the ethylene vinyl acetate copolymer. preferable. If the vinyl acetate content is less than 20 parts by mass, the sealing film obtained when crosslinked and cured at high temperatures may not have sufficient transparency. If it exceeds 35 parts by mass, carboxylic acid, alcohol, etc. are generated. There is a risk that it will be easier to do.
本発明の太陽電池用封止膜は、架橋剤として有機過酸化物を含む。これにより、エチレン－極性モノマー共重合体の架橋硬化膜を得ることができ、太陽電池の封止性を高めることができる。
The solar cell sealing film of the present invention contains an organic peroxide as a crosslinking agent. Thereby, a crosslinked cured film of an ethylene-polar monomer copolymer can be obtained, and the sealing performance of the solar cell can be improved.
前記有機過酸化物としては、１００℃以上の温度で分解してラジカルを発生するものであれば、どのようなものでも使用することができる。有機過酸化物は、一般に、成膜温度、組成物の調整条件、硬化温度、被着体の耐熱性、貯蔵安定性を考慮して選択される。特に、半減期１０時間の分解温度が７０℃以上のものが好ましい。
Any organic peroxide may be used as long as it decomposes at a temperature of 100 ° C. or higher to generate radicals. The organic peroxide is generally selected in consideration of the film formation temperature, the adjustment conditions of the composition, the curing temperature, the heat resistance of the adherend, and the storage stability. In particular, those having a decomposition temperature of 70 hours or more with a half-life of 10 hours are preferred.
前記有機過酸化物としては、樹脂の加工温度・貯蔵安定性の観点から例えば、２，５－ジメチルヘキサン－２，５－ジハイドロパーオキサイド、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキサン、ｔ－ブチルクミルパーオキサイド、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、ジクミルパーオキサイド、α，α‘－ビス（ｔ－ブチルパーオキシイソプロピル）ベンゼン、ｎ－ブチル－４，４－ビス（ｔ－ブチルパーオキシ）バレレート、２，２－ビス（ｔ－ブチルパーオキシ）ブタン、１，１－ビス（ｔ－ブチルパーオキシ）シクロヘキサン、１，１－ビス（ｔ－ブチルパーオキシ）トリメチルシクロヘキサン、１，１－ビス（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、ｔ－ブチルパーオキシベンゾエート、ベンゾイルパーオキサイド、ｔ－ブチルパーオキシアセテート、メチルエチルケトンパーオキサイド、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ビス（ｔ－ブチルパーオキシ）シクロヘキサン、メチルエチルケトンパーオキサイド、２，５－ジメチルヘキシル－２，５－ビスパーオキシベンゾエート、ｔ－ブチルハイドロパーオキサイド、ｐ－メンタンハイドロパーオキサイド、ｐ－クロロベンゾイルパーオキサイド、ヒドロキシヘプチルパーオキサイド、クロロヘキサノンパーオキサイド、オクタノイルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、クミルパーオキシオクトエート、コハク酸パーオキサイド、アセチルパーオキサイド、ｔ－ブチルパーオキシ（２－エチルヘキサノエート）、ｍ－トルオイルパーオキサイド、ｔ－ブチルパーオキシイソブチレーオ及び２，４－ジクロロベンゾイルパーオキサイドを挙げることができる。有機過酸化物は一種単独で使用してもよく、二種以上を組み合わせて使用しても良い。
Examples of the organic peroxide include 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-bis (t, from the viewpoint of processing temperature and storage stability of the resin. -Butylperoxy) hexane, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, α, α'-bis (t-butylperoxide Oxyisopropyl) benzene, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) cyclohexane 1,1-bis (t-butylperoxy) trimethylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butyl peroxybenzoate, benzoyl peroxide, t-butyl peroxyacetate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5-bisperoxybenzoate, t-butyl hydroperoxide, p-menthane hydroperoxide, p- Chlorobenzoyl peroxide, hydroxyheptyl peroxide, chlorohexanone peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxy octoate, succinic acid peroxide Id, acetyl peroxide, t- butyl peroxy (2-ethylhexanoate), m-toluoyl peroxide, may be mentioned t-butyl peroxy isobutyrate Leo and 2,4-dichlorobenzoyl peroxide. An organic peroxide may be used individually by 1 type, and may be used in combination of 2 or more type.
前記組成物において、有機過酸化物からなる架橋剤の含有量は、エチレン－極性モノマー共重合体１００質量部に対して、好ましくは０．１～２．０、より好ましくは０．３～１．５質量部、特に好ましくは０．６～１．５質量部であることが好ましい。前記有機過酸化物の含有量は、少ないと得られる封止膜の透明性が低下する恐れがあり、多くなると共重合体との相溶性が悪くなる恐れがある。
In the composition, the content of the crosslinking agent comprising an organic peroxide is preferably 0.1 to 2.0, more preferably 0.3 to 1 with respect to 100 parts by mass of the ethylene-polar monomer copolymer. 0.5 parts by mass, particularly preferably 0.6 to 1.5 parts by mass is preferred. If the content of the organic peroxide is small, the transparency of the resulting sealing film may be lowered, and if it is increased, the compatibility with the copolymer may be deteriorated.
さらに、本発明の組成物は、必要に応じて、架橋助剤を含んでいてもよい。前記架橋助剤は、エチレン－極性モノマー共重合体のゲル分率を向上させ、耐久性を向上するために組成物に添加することができる。この目的に供される架橋助剤（官能基としてラジカル重合性基を有する化合物）としては、トリアリルシアヌレート、トリアリルイソシアヌレート等の３官能の架橋助剤の他、（メタ）アクリルエステル（例、ＮＫエステル等）の単官能又は２官能の架橋助剤等を挙げることができる。なかでも、トリアリルシアヌレートおよびトリアリルイソシアヌレートが好ましく、特にトリアリルイソシアヌレートが好ましい。これらの架橋助剤は、エチレン－極性モノマー共重合体１００質量部に対して、一般に１０質量部以下、好ましくは０．１～５質量部で使用される。
Furthermore, the composition of the present invention may contain a crosslinking aid as necessary. The crosslinking aid can be added to the composition in order to improve the gel fraction of the ethylene-polar monomer copolymer and improve the durability. As a crosslinking aid (compound having a radical polymerizable group as a functional group) used for this purpose, in addition to a trifunctional crosslinking aid such as triallyl cyanurate and triallyl isocyanurate, (meth) acrylic ester ( Examples thereof include monofunctional or bifunctional crosslinking aids such as NK ester. Of these, triallyl cyanurate and triallyl isocyanurate are preferable, and triallyl isocyanurate is particularly preferable. These crosslinking aids are generally used in an amount of 10 parts by mass or less, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the ethylene-polar monomer copolymer.
前記組成物は、膜の種々の物性（機械的強度、接着性、透明性等の光学的特性、耐熱性、耐光性、架橋速度等）の改良あるいは調整、特に機械的強度の改良のため、必要に応じて、可塑剤、接着向上剤、アクリロキシ基含有化合物、メタクリロキシ基含有化合物及び／又はエポキシ基含有化合物などの各種添加剤をさらに含んでいてもよい。
The composition is used for improving or adjusting various physical properties of the film (optical properties such as mechanical strength, adhesiveness, transparency, heat resistance, light resistance, crosslinking speed, etc.), particularly for improving mechanical strength. If necessary, various additives such as a plasticizer, an adhesion improver, an acryloxy group-containing compound, a methacryloxy group-containing compound, and / or an epoxy group-containing compound may further be included.
前記可塑剤としては、特に限定されるものではないが、一般に多塩基酸のエステル、多価アルコールのエステルが使用される。その例としては、ジオクチルフタレート、ジヘキシルアジペート、トリエチレングリコール－ジ－２－エチルブチレート、ブチルセバケート、テトラエチレングリコールジヘプタノエート、トリエチレングリコールジペラルゴネートを挙げることができる。可塑剤は一種用いてもよく、二種以上組み合わせて使用しても良い。可塑剤の含有量は、エチレン－極性モノマー共重合体１００質量部に対して５質量部以下の範囲が好ましい。
The plasticizer is not particularly limited, but polybasic acid esters and polyhydric alcohol esters are generally used. Examples thereof include dioctyl phthalate, dihexyl adipate, triethylene glycol-di-2-ethylbutyrate, butyl sebacate, tetraethylene glycol diheptanoate, and triethylene glycol dipelargonate. One type of plasticizer may be used, or two or more types may be used in combination. The plasticizer content is preferably in the range of 5 parts by mass or less with respect to 100 parts by mass of the ethylene-polar monomer copolymer.
前記接着向上剤は、シランカップリング剤を用いることができる。これにより、優れた接着力を有する太陽電池用封止膜を形成することが可能となる。前記シランカップリング剤としては、γ－クロロプロピルメトキシシラン、ビニルエトキシシラン、ビニルトリス（β－メトキシエトキシ）シラン、γ－メタクリロキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、ビニルトリクロロシラン、γ－メルカプトプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、Ｎ－β－（アミノエチル）－γ－アミノプロピルトリメトキシシランを挙げることができる。これらシランカップリング剤は、単独で使用しても、又は２種以上組み合わせて使用しても良い。また前記接着向上剤の含有量は、エチレン－極性モノマー共重合体１００質量部に対して５質量部以下であることが好ましい。
A silane coupling agent can be used as the adhesion improver. Thereby, it becomes possible to form the sealing film for solar cells which has the outstanding adhesive force. Examples of the silane coupling agent include γ-chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxy. Silane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β Mention may be made of-(aminoethyl) -γ-aminopropyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. The content of the adhesion improver is preferably 5 parts by mass or less with respect to 100 parts by mass of the ethylene-polar monomer copolymer.
前記アクリロキシ基含有化合物及び前記メタクリロキシ基含有化合物としては、一般にアクリル酸あるいはメタクリル酸誘導体であり、例えばアクリル酸あるいはメタクリル酸のエステルやアミドを挙げることができる。エステル残基の例としては、メチル、エチル、ドデシル、ステアリル、ラウリル等の直鎖状のアルキル基、シクロヘキシル基、テトラヒドルフルフリル基、アミノエチル基、２－ヒドロキシエチル基、３－ヒドロキシプロピル基、３－クロロ－２－ヒドロキシプオピル基を挙げることができる。アミドの例としては、ジアセトンアクリルアミドを挙げることができる。また、エチレングリコール、トリエチレングリコール、ポリプロピレングリコール、ポリエチレングリコール、トリメチロールプロパン、ペンタエリスリトール等の多価アルコールとアクリル酸あるいはメタクリル酸のエステルも挙げることができる。
The acryloxy group-containing compound and the methacryloxy group-containing compound are generally acrylic acid or methacrylic acid derivatives, and examples thereof include acrylic acid or methacrylic acid esters and amides. Examples of ester residues include linear alkyl groups such as methyl, ethyl, dodecyl, stearyl, lauryl, cyclohexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group And 3-chloro-2-hydroxypropyl group. Examples of amides include diacetone acrylamide. In addition, polyhydric alcohols such as ethylene glycol, triethylene glycol, polypropylene glycol, polyethylene glycol, trimethylolpropane, and pentaerythritol, and esters of acrylic acid or methacrylic acid can also be used.
前記エポキシ含有化合物としては、トリグリシジルトリス（２－ヒドロキシエチル）イソシアヌレート、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、アリルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル、フェノール（エチレンオキシ）5グリシジルエーテル、ｐ－ｔ－ブチルフェニルグリシジルエーテル、アジピン酸ジグリシジルエステル、フタル酸ジグリシジルエステル、グリシジルメタクリレート、ブチルグリシジルエーテルを挙げることができる。
Examples of the epoxy-containing compound include triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, Mention may be made of phenol (ethyleneoxy) 5 glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, glycidyl methacrylate and butyl glycidyl ether.
前記アクリロキシ基含有化合物、前記メタクリロキシ基含有化合物、または前記エポキシ基含有化合物は、それぞれエチレン－極性モノマー共重合体１００質量部に対してそれぞれ一般に０．５～５．０質量部、特に１．０～４．０質量部含まれていることが好ましい。
The acryloxy group-containing compound, the methacryloxy group-containing compound, or the epoxy group-containing compound is generally 0.5 to 5.0 parts by mass, particularly 1.0 to 100 parts by mass of the ethylene-polar monomer copolymer, respectively. It is preferably contained in an amount of ˜4.0 parts by mass.
さらに、本発明の太陽電池用封止膜は、光安定剤、及び／又は老化防止剤を含んでいてもよい。
Furthermore, the solar cell sealing film of the present invention may contain a light stabilizer and / or an anti-aging agent.
前記太陽電池用封止膜が光安定剤を含むことによっても、照射された光などの影響によってエチレン－極性モノマー共重合体の劣化し、太陽電池用封止膜が黄変するのを抑制することができる。前記光安定剤としてはヒンダードアミン系と呼ばれる光安定剤を用いることが好ましく、例えば、ＬＡ－５２、ＬＡ－５７、ＬＡ－６２、ＬＡ－６３ＬＡ－６３ｐ、ＬＡ－６７、ＬＡ－６８（いずれも（株）ＡＤＥＫＡ製）、Ｔｉｎｕｖｉｎ７４４、Ｔｉｎｕｖｉｎ ７７０、Ｔｉｎｕｖｉｎ ７６５、Ｔｉｎｕｖｉｎ１４４、Ｔｉｎｕｖｉｎ ６２２ＬＤ、ＣＨＩＭＡＳＳＯＲＢ ９４４ＬＤ（いずれもチバ・スペシャリティ・ケミカルズ（株）社製）、ＵＶ－３０３４（Ｂ．Ｆ．グッドリッチ社製）等を挙げることができる。なお、上記光安定剤は、単独で使用しても、２種以上組み合わせて用いてもよく、その配合量は、エチレン－極性モノマー共重合体１００質量部に対して０．０１～５質量部であることが好ましい。
Even when the solar cell sealing film contains a light stabilizer, the deterioration of the ethylene-polar monomer copolymer due to the influence of irradiated light or the like, and the solar cell sealing film are prevented from yellowing. be able to. As the light stabilizer, a light stabilizer called a hindered amine type is preferably used. For example, LA-52, LA-57, LA-62, LA-63LA-63p, LA-67, LA-68 (all ( ADEKA Co., Ltd.), Tinuvin 744, Tinuvin 770, Tinuvin 765, Tinuvin 144, Tinuvin 622LD, CHIMASSORB 944LD (all manufactured by Ciba Specialty Chemicals Co., Ltd.), UV-3034 (BF Goodrich) Can be mentioned. The light stabilizer may be used alone or in combination of two or more kinds, and the blending amount is 0.01 to 5 parts by mass with respect to 100 parts by mass of the ethylene-polar monomer copolymer. It is preferable that
前記老化防止剤としては、例えばＮ，Ｎ’－ヘキサン－１，６－ジイルビス〔３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナミド〕等のヒンダードフェノール系酸化防止剤、リン系熱安定剤、ラクトン系熱安定剤、ビタミンＥ系熱安定剤、イオウ系熱安定剤等が挙げられる。
Examples of the anti-aging agent include hindered phenol antioxidants such as N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]. , Phosphorus heat stabilizers, lactone heat stabilizers, vitamin E heat stabilizers, sulfur heat stabilizers, and the like.
上述した本発明の太陽電池用封止膜を形成するには、公知の方法に準じて行えばよい。例えば、上述した各種成分を含む組成物を、通常の押出成形、又はカレンダ成形（カレンダリング）等により成形してシート状物を得る方法により製造することができる。また、前記組成物を溶剤に溶解させ、この溶液を適当な塗布機（コーター）で適当な支持体上に塗布、乾燥して塗膜を形成することによりシート状物を得ることもできる。押出成形等を用いて加熱圧延することによって成膜する場合、加熱は一般に５０～９０℃の範囲である。
The solar cell sealing film of the present invention described above may be formed according to a known method. For example, the composition containing the various components described above can be produced by a method of obtaining a sheet-like material by molding by ordinary extrusion molding, calendar molding (calendering) or the like. Alternatively, a sheet-like material can be obtained by dissolving the composition in a solvent and coating the solution on a suitable support with a suitable coating machine (coater) and drying to form a coating film. In the case where a film is formed by heat rolling using extrusion molding or the like, heating is generally in the range of 50 to 90 ° C.
太陽電池用封止膜の厚さは、特に制限されないが、５０μｍ～２ｍｍの範囲であればよい。
The thickness of the solar cell sealing film is not particularly limited, but may be in the range of 50 μm to 2 mm.
上述した本発明の太陽電池用封止膜は、光劣化が少なく、優れた耐久性を有するベンゾトリアゾール系紫外線吸収剤を含む。前記ベンゾトリアゾール系紫外線吸収剤は、ＰＥＴフィルムなど裏面側保護材の劣化を促進させる波長（約３２５ｎｍ、約３８０ｎｍ）を有する紫外線のカット性に優れる。具体的には、実施例において後記するように、促進耐侯試験後（温度６３℃、湿度５０％ＲＨの空気中で、３００～４００ｎｍにおける紫外線強度が１００ｍＷ／ｃｍ2の紫外線を３００時間照射した後）であっても、本発明の太陽電池用封止膜は、波長３２５ｎｍの光線透過率が０．３％以下であり、波長３８０ｎｍの光線透過率が１．５％以下である。したがって、前記太陽電池用封止膜は、優れた紫外線カット性を長期間に亘り維持することが可能となる。
The solar cell sealing film of the present invention described above contains a benzotriazole-based ultraviolet absorber that has little photodegradation and has excellent durability. The said benzotriazole type ultraviolet absorber is excellent in the cut property of the ultraviolet-ray which has a wavelength (about 325 nm, about 380 nm) which accelerates | stimulates deterioration of back surface side protective materials, such as a PET film. Specifically, as will be described later in the Examples, after the accelerated weathering test (after irradiation with ultraviolet rays having an ultraviolet intensity of 100 mW / cm 2 at 300 to 400 nm in air at a temperature of 63 ° C. and a humidity of 50% RH for 300 hours. However, the solar cell sealing film of the present invention has a light transmittance of a wavelength of 325 nm of 0.3% or less and a light transmittance of a wavelength of 380 nm of 1.5% or less. Therefore, the solar cell sealing film can maintain an excellent ultraviolet cut property over a long period of time.
さらに、本発明の太陽電池用封止膜は、促進耐侯試験後（温度６３℃、湿度５０％ＲＨの空気中で、３００～４００ｎｍにおける紫外線強度が１００ｍＷ／ｃｍ2の紫外線を３００時間照射した後）であっても、ＹＩ値の差（△ＹＩ値）が７以下である。このように、前記太陽電池用封止膜は、光劣化が少ないことから黄変の発生が抑制され、優れた透明性を長期間に亘り維持することができる。
Furthermore, the solar cell sealing film of the present invention is subjected to an accelerated weathering test (after irradiation with ultraviolet rays having an ultraviolet intensity of 100 mW / cm 2 at 300 to 400 nm in air at a temperature of 63 ° C. and a humidity of 50% RH for 300 hours. ), The YI value difference (ΔYI value) is 7 or less. Thus, since the said sealing film for solar cells has little photodegradation, generation | occurrence | production of yellowing is suppressed and it can maintain the outstanding transparency over a long period of time.
このような太陽電池用封止膜を用いた太陽電池の構造は、特に制限されないが、受光面側透明保護部材と裏面側保護部材との間に、前記太陽電池用封止膜を介在させて架橋一体化させることにより太陽電池用セルを封止させた構造などが挙げられる。
The structure of the solar cell using such a solar cell sealing film is not particularly limited, but the solar cell sealing film is interposed between the light-receiving surface side transparent protective member and the back surface side protective member. The structure etc. which sealed the cell for solar cells by carrying out bridge | crosslinking integration are mentioned.
前記太陽電池において、太陽電池用セルを十分に封止するには、図１に示すように受光面側透明保護部材１１、受光面側封止膜１３Ａ、太陽電池用セル１４、裏面側封止膜１３Ｂ及び裏面側保護部材１２を積層し、加熱加圧など常法に従って、封止膜を架橋硬化させればよい。
In the solar cell, in order to sufficiently seal the solar cell, as shown in FIG. 1, the light receiving surface side transparent protective member 11, the light receiving surface side sealing film 13A, the solar cell 14 and the back surface side sealing. The film 13B and the back surface side protection member 12 may be laminated, and the sealing film may be cross-linked and cured according to a conventional method such as heat and pressure.
前記加熱加圧するには、例えば、前記積層体を、真空ラミネーターで温度１３５～１８０℃、さらに１４０～１８０℃、特に１５５～１８０℃、脱気時間０．１～５分、プレス圧力０．１～１．５ｋｇ／ｃｍ2、プレス時間５～１５分で加熱圧着すればよい。この加熱加圧時に、受光面側封止膜１３Ａおよび裏面側封止膜１３Ｂに含まれるエチレン－極性モノマー共重合体を架橋させることにより、受光面側封止膜１３Ａおよび裏面側封止膜１３Ｂを介して、受光面側透明保護部材１１、裏面側透明部材１２、および太陽電池用セル１４を一体化させて、太陽電池用セル１４を封止することができる。
For the heating and pressurization, for example, the laminate is heated with a vacuum laminator at a temperature of 135 to 180 ° C., further 140 to 180 ° C., particularly 155 to 180 ° C., a degassing time of 0.1 to 5 minutes, and a press pressure of 0.1. Heat pressing may be performed at a pressure of ˜1.5 kg / cm 2 and a press time of 5 to 15 minutes. During this heating and pressurization, the ethylene-polar monomer copolymer contained in the light receiving surface side sealing film 13A and the back surface side sealing film 13B is cross-linked, whereby the light receiving surface side sealing film 13A and the back surface side sealing film 13B. The solar cell 14 can be sealed by integrating the light-receiving surface-side transparent protective member 11, the back-side transparent member 12, and the solar cell 14.
前記太陽電池において、前記ベンゾトリアゾール系紫外線吸収剤を含む封止膜は、少なくとも裏面側封止膜として用いられるのが好ましく、受光面側封止膜及び裏面側封止膜の双方に用いられるのがより好ましい。
In the solar cell, the sealing film containing the benzotriazole-based ultraviolet absorber is preferably used as at least a back surface side sealing film, and is used as both a light receiving surface side sealing film and a back surface side sealing film. Is more preferable.
なお、本発明において、太陽電池セルの光が照射される側を「受光面側」と称し、太陽電池セルの受光面とは反対面側を「裏面側」と称する。
In the present invention, the side of the solar cell irradiated with light is referred to as “light receiving surface side”, and the side opposite to the light receiving surface of the solar cell is referred to as “back surface side”.
本発明の太陽電池に使用される受光面側透明保護部材は、通常珪酸塩ガラスなどのガラス基板であるのがよい。ガラス基板の厚さは、０．１～１０ｍｍが一般的であり、０．３～５ｍｍが好ましい。ガラス基板は、一般に、化学的に、或いは熱的に強化させたものであってもよい。
The light-receiving surface side transparent protective member used for the solar cell of the present invention is usually a glass substrate such as silicate glass. The thickness of the glass substrate is generally from 0.1 to 10 mm, and preferably from 0.3 to 5 mm. The glass substrate may generally be chemically or thermally strengthened.
本発明で使用される裏面側保護部材は、ＰＥＴなどのプラスチックフィルムであるが、耐熱性、耐湿熱性を考慮してフッ化ポリエチレンフィルム、特にフッ化ポリエチレンフィルム／Ａｌ／フッ化ポリエチレンフィルムをこの順で積層させたフィルムが好ましい。
The back surface side protective member used in the present invention is a plastic film such as PET. In consideration of heat resistance and moist heat resistance, a fluorinated polyethylene film, particularly a fluorinated polyethylene film / Al / fluorinated polyethylene film, in this order. A film laminated with is preferable.
なお、本発明の太陽電池は、上述した通り、受光面側および裏面側に用いられる封止膜に特徴を有する。したがって、受光面側透明保護部材、裏面側保護部材、および太陽電池用セルなどの前記封止膜以外の部材については、従来公知の太陽電池と同様の構成を有していればよく、特に制限されない。
In addition, the solar cell of this invention has the characteristics in the sealing film used for a light-receiving surface side and a back surface side as mentioned above. Therefore, the members other than the sealing film such as the light-receiving surface-side transparent protective member, the back-side protective member, and the solar cell need only have the same configuration as a conventionally known solar cell, and are particularly limited. Not.
以下、本発明を実施例により説明する。本発明は、以下の実施例により制限されるものではない。
Hereinafter, the present invention will be described by way of examples. The present invention is not limited by the following examples.
（実施例１）
表１に示す配合で各材料をロールミルに供給して７０℃で混練し、得られた組成物を７０℃でカレンダ成形し、放冷後、太陽電池用封止膜（厚さ１．０ｍｍ）を得た。 Example 1
The materials shown in Table 1 were supplied to a roll mill and kneaded at 70 ° C., and the resulting composition was calendered at 70 ° C., allowed to cool, and then sealed for solar cells (thickness: 1.0 mm). Got.
表１に示す配合で各材料をロールミルに供給して７０℃で混練し、得られた組成物を７０℃でカレンダ成形し、放冷後、太陽電池用封止膜（厚さ１．０ｍｍ）を得た。 Example 1
The materials shown in Table 1 were supplied to a roll mill and kneaded at 70 ° C., and the resulting composition was calendered at 70 ° C., allowed to cool, and then sealed for solar cells (thickness: 1.0 mm). Got.
（実施例２～１９、及び比較例１～６）
表１～４に示すように紫外線吸収剤の種類及び／又は添加量を変えた以外は、実施例１と同様にして太陽電池用封止膜を作製した。 (Examples 2 to 19 and Comparative Examples 1 to 6)
As shown in Tables 1 to 4, a solar cell sealing film was prepared in the same manner as in Example 1 except that the type and / or addition amount of the ultraviolet absorber was changed.
表１～４に示すように紫外線吸収剤の種類及び／又は添加量を変えた以外は、実施例１と同様にして太陽電池用封止膜を作製した。 (Examples 2 to 19 and Comparative Examples 1 to 6)
As shown in Tables 1 to 4, a solar cell sealing film was prepared in the same manner as in Example 1 except that the type and / or addition amount of the ultraviolet absorber was changed.
（評価）
１．促進耐侯試験
上記で作製した各太陽電池用封止膜を、二枚のガラス板（厚さ０．３ｍｍ）用いて、ガラス板／太陽電池用封止膜／ガラス板の順となるように積層した。得られた積層体を、真空ラミネーターで真空下、９０℃で２分間圧着した後、さらに圧力１３ｘ１０5Ｐａ、９０℃で８分間圧着した。次に、前記積層体を、オーブン中、温度１５５℃の条件で４５分間、加圧加熱した。これにより、封止膜を架橋硬化させ、ガラス板と封止膜とが一体化された積層体を得た。 (Evaluation)
1. Accelerated weather resistance test Each of the solar cell sealing films prepared above was laminated in the order of glass plate / solar cell sealing film / glass plate using two glass plates (thickness 0.3 mm). did. The obtained laminate was pressure-bonded at 90 ° C. for 2 minutes under vacuum with a vacuum laminator, and further pressure-bonded at pressure of 13 × 10 5 Pa and 90 ° C. for 8 minutes. Next, the laminate was heated under pressure in an oven at a temperature of 155 ° C. for 45 minutes. Thereby, the sealing film was crosslinked and cured, and a laminated body in which the glass plate and the sealing film were integrated was obtained.
１．促進耐侯試験
上記で作製した各太陽電池用封止膜を、二枚のガラス板（厚さ０．３ｍｍ）用いて、ガラス板／太陽電池用封止膜／ガラス板の順となるように積層した。得られた積層体を、真空ラミネーターで真空下、９０℃で２分間圧着した後、さらに圧力１３ｘ１０5Ｐａ、９０℃で８分間圧着した。次に、前記積層体を、オーブン中、温度１５５℃の条件で４５分間、加圧加熱した。これにより、封止膜を架橋硬化させ、ガラス板と封止膜とが一体化された積層体を得た。 (Evaluation)
1. Accelerated weather resistance test Each of the solar cell sealing films prepared above was laminated in the order of glass plate / solar cell sealing film / glass plate using two glass plates (thickness 0.3 mm). did. The obtained laminate was pressure-bonded at 90 ° C. for 2 minutes under vacuum with a vacuum laminator, and further pressure-bonded at pressure of 13 × 10 5 Pa and 90 ° C. for 8 minutes. Next, the laminate was heated under pressure in an oven at a temperature of 155 ° C. for 45 minutes. Thereby, the sealing film was crosslinked and cured, and a laminated body in which the glass plate and the sealing film were integrated was obtained.
次に、前記一体化積層体を、４ＫＷメタルハライドランプを光源とする促進耐侯試験機（Ｓ－ＵＶテスター、岩崎電気株式会社製）を用い、温度６３℃、湿度５０％ＲＨの空気中で、３００～４００ｎｍにおける紫外線強度が１００ｍＷ／ｃｍ2の紫外線を３００時間照射した後に取り出した。
Next, the integrated laminate was subjected to 300 ° C. in an air with a temperature of 63 ° C. and a humidity of 50% RH using an accelerated weathering tester (S-UV tester, manufactured by Iwasaki Electric Co., Ltd.) using a 4 KW metal halide lamp as a light source. It was taken out after being irradiated with ultraviolet rays having an ultraviolet intensity of 100 mW / cm 2 at ˜400 nm for 300 hours.
２．黄変性の評価
紫外線照射による黄変の程度を調査するために、全自動直読ヘイズコンピューターＨＧＭ－２ＤＰ（スガ試験機株式会社製）を用いて、前記促進耐侯試験前後、前記一体化積層体のＹＩ値の差（△ＹＩ値）を求めた。結果を表１～４に示す。 2. Evaluation of yellowing In order to investigate the degree of yellowing due to ultraviolet irradiation, a fully automatic direct reading haze computer HGM-2DP (manufactured by Suga Test Instruments Co., Ltd.) was used, before and after the accelerated weathering test, The difference in values (ΔYI value) was determined. The results are shown in Tables 1 to 4.
紫外線照射による黄変の程度を調査するために、全自動直読ヘイズコンピューターＨＧＭ－２ＤＰ（スガ試験機株式会社製）を用いて、前記促進耐侯試験前後、前記一体化積層体のＹＩ値の差（△ＹＩ値）を求めた。結果を表１～４に示す。 2. Evaluation of yellowing In order to investigate the degree of yellowing due to ultraviolet irradiation, a fully automatic direct reading haze computer HGM-2DP (manufactured by Suga Test Instruments Co., Ltd.) was used, before and after the accelerated weathering test, The difference in values (ΔYI value) was determined. The results are shown in Tables 1 to 4.
３．分光透過率の測定
前記促進耐侯試験前及び後の一体化積層体の分光透過率を、分光光度計（Ｕ－４０００、株式会社日立製作所製）を用いて測定した。波長３２５ｎｍ及び３８０ｎｍの分光透過率を表１～４に示す。 3. Measurement of Spectral Transmittance Spectral transmittance of the integrated laminate before and after the accelerated weathering test was measured using a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.). Tables 1 to 4 show spectral transmittances at wavelengths of 325 nm and 380 nm.
前記促進耐侯試験前及び後の一体化積層体の分光透過率を、分光光度計（Ｕ－４０００、株式会社日立製作所製）を用いて測定した。波長３２５ｎｍ及び３８０ｎｍの分光透過率を表１～４に示す。 3. Measurement of Spectral Transmittance Spectral transmittance of the integrated laminate before and after the accelerated weathering test was measured using a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.). Tables 1 to 4 show spectral transmittances at wavelengths of 325 nm and 380 nm.
表１～４に示すように、本発明の太陽電池用封止膜は、促進耐侯試験後であっても、波長３２５ｎｍ及び波長３８０ｎｍの光の透過を高くカットすることができ、さらに黄変の程度（△ＹＩ値）も極めて低く抑えられている。すなわち、促進耐侯試験後であっても、波長３２５ｎｍの光線透過率が０．５％以下であり、波長３８０ｎｍの光線透過率が２．０％以下であり、さらに、ＹＩ値の差が１３以下である。これらから、本発明の太陽電池用封止膜は、優れた紫外線カット性及び透明性を長期間に亘り維持することが可能であることがわかる。
As shown in Tables 1 to 4, the solar cell sealing film of the present invention can cut the transmission of light with a wavelength of 325 nm and a wavelength of 380 nm to a high level even after the accelerated weathering test, The degree (ΔYI value) is also extremely low. That is, even after the accelerated weather resistance test, the light transmittance at a wavelength of 325 nm is 0.5% or less, the light transmittance at a wavelength of 380 nm is 2.0% or less, and the difference in YI values is 13 or less. It is. From these, it can be seen that the solar cell sealing film of the present invention is capable of maintaining excellent ultraviolet cutting property and transparency over a long period of time.
本発明の太陽電池用封止膜によれば、長期間に亘り優れた意匠性及び発電性能を発揮することが可能な太陽電池を提供することができる。
According to the solar cell sealing film of the present invention, it is possible to provide a solar cell capable of exhibiting excellent design and power generation performance over a long period of time.
１１ 受光面側透明保護部材、
１２ 裏面側保護材、
１３Ａ 受光面側封止膜、
１３Ｂ 裏面側封止膜、
１４ 太陽電池セル。 11 Light-receiving surface side transparent protective member,
12 Back side protective material,
13A light-receiving surface side sealing film,
13B Back side sealing film,
14 Solar cell.
１２ 裏面側保護材、
１３Ａ 受光面側封止膜、
１３Ｂ 裏面側封止膜、
１４ 太陽電池セル。 11 Light-receiving surface side transparent protective member,
12 Back side protective material,
13A light-receiving surface side sealing film,
13B Back side sealing film,
14 Solar cell.
Claims (5)
- エチレン－極性モノマー共重合体、有機過酸化物、及び紫外線吸収剤を含む太陽電池用封止膜であって、
前記紫外線吸収剤が、下記式（１）
（式中、Ｒ1は、水素原子、ハロゲン原子、炭素原子数１～６個のアルキル基、又は炭素原子数１～６個のハロアルキル基を表し、Ｒ2及びＲ3は、同一であっても異なっていてもよく、水素原子、炭素原子数１～２０個のアルキル基、又は炭素原子数３～２２のアルキルオキシカルボニル基を表す）で表されるベンゾトリアゾール系紫外線吸収剤であることを特徴とする太陽電池用封止膜。 A sealing film for a solar cell comprising an ethylene-polar monomer copolymer, an organic peroxide, and an ultraviolet absorber,
The ultraviolet absorber is represented by the following formula (1)
(Wherein R 1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms, and R 2 and R 3 are the same, A benzotriazole-based ultraviolet absorber represented by a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyloxycarbonyl group having 3 to 22 carbon atoms). A solar cell sealing film. - 前記式（１）において、Ｒ1が塩素原子又は水素原子を表し、Ｒ2及びＲ3が、相互に異なり、炭素原子数１～２０個のアルキル基を表すことを特徴とする請求項１に記載の太陽電池用封止膜。 2. The formula (1), wherein R 1 represents a chlorine atom or a hydrogen atom, and R 2 and R 3 are different from each other and represent an alkyl group having 1 to 20 carbon atoms. The sealing film for solar cells as described.
- 前記ベンゾトリアゾール系紫外線吸収剤が、２－（２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－６－ドデシル－４－メチルフェノール及び／又は２－（５－クロロ－２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４－メチル－６－ｔｅｒｔ－ブチルフェノールであることを特徴とする請求項１又は２に記載の太陽電池用封止膜。 The benzotriazole ultraviolet absorber is 2- (2H-1,2,3-benzotriazol-2-yl) -6-dodecyl-4-methylphenol and / or 2- (5-chloro-2H-1, 3. The solar cell sealing film according to claim 1, which is 2,3-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol.
- 前記ベンゾトリアゾール系紫外線吸収剤と前記有機過酸化物との質量比が、９０：１０～１０：９０である請求項１～３のいずれか１項に記載の太陽電池用封止膜。 The solar cell sealing film according to any one of claims 1 to 3, wherein a mass ratio of the benzotriazole-based ultraviolet absorber and the organic peroxide is 90:10 to 10:90.
- 受光面側透明保護部材と裏面側保護部材との間に封止膜を介在させ、架橋一体化させることにより太陽電池用セルを封止してなる太陽電池において、
前記封止膜が、請求項１～４のいずれか１項に記載の太陽電池用封止膜であることを特徴とする太陽電池。 In a solar cell formed by sealing a solar cell by interposing a sealing film between the light-receiving surface-side transparent protective member and the back-side protective member and crosslinking and integrating them,
The solar cell, wherein the sealing film is the solar cell sealing film according to any one of claims 1 to 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-194998 | 2008-07-29 | ||
| JP2008194998A JP2011201928A (en) | 2008-07-29 | 2008-07-29 | Sealing film for solar cell, and solar cell using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2010013659A1 true WO2010013659A1 (en) | 2010-02-04 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2009/063319 WO2010013659A1 (en) | 2008-07-29 | 2009-07-27 | Sealing film for solar cell and solar cell using same |
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| Country | Link |
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| JP (1) | JP2011201928A (en) |
| WO (1) | WO2010013659A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013190940A1 (en) * | 2012-06-19 | 2013-12-27 | 三井化学東セロ株式会社 | Solar cell sealing material and solar cell module |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5819159B2 (en) * | 2011-10-21 | 2015-11-18 | 株式会社ブリヂストン | Solar cell sealing film and solar cell using the same |
| US9666739B2 (en) | 2013-06-28 | 2017-05-30 | Sunpower Corporation | Photovoltaic cell and laminate metallization |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09191116A (en) * | 1996-01-10 | 1997-07-22 | Canon Inc | Solar cell module |
| JP2002228803A (en) * | 2001-01-30 | 2002-08-14 | Konica Corp | Method for producing low reflection laminate and low reflection laminate |
| JP2006134970A (en) * | 2004-11-02 | 2006-05-25 | Mitsui Chemical Fabro Inc | Sheet for solar cell sealing |
| JP2009152543A (en) * | 2007-11-29 | 2009-07-09 | Bridgestone Corp | Sealing film for solar cell and solar battery using the sealing film |
-
2008
- 2008-07-29 JP JP2008194998A patent/JP2011201928A/en active Pending
-
2009
- 2009-07-27 WO PCT/JP2009/063319 patent/WO2010013659A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09191116A (en) * | 1996-01-10 | 1997-07-22 | Canon Inc | Solar cell module |
| JP2002228803A (en) * | 2001-01-30 | 2002-08-14 | Konica Corp | Method for producing low reflection laminate and low reflection laminate |
| JP2006134970A (en) * | 2004-11-02 | 2006-05-25 | Mitsui Chemical Fabro Inc | Sheet for solar cell sealing |
| JP2009152543A (en) * | 2007-11-29 | 2009-07-09 | Bridgestone Corp | Sealing film for solar cell and solar battery using the sealing film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013190940A1 (en) * | 2012-06-19 | 2013-12-27 | 三井化学東セロ株式会社 | Solar cell sealing material and solar cell module |
| CN104380481A (en) * | 2012-06-19 | 2015-02-25 | 三井化学东赛璐株式会社 | Solar cell sealing material and solar cell module |
| JPWO2013190940A1 (en) * | 2012-06-19 | 2016-05-26 | 三井化学東セロ株式会社 | Solar cell encapsulant and solar cell module |
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| Publication number | Publication date |
|---|---|
| JP2011201928A (en) | 2011-10-13 |
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