WO2016171080A1 - Sealing sheet and solar cell module - Google Patents
Sealing sheet and solar cell module Download PDFInfo
- Publication number
- WO2016171080A1 WO2016171080A1 PCT/JP2016/062119 JP2016062119W WO2016171080A1 WO 2016171080 A1 WO2016171080 A1 WO 2016171080A1 JP 2016062119 W JP2016062119 W JP 2016062119W WO 2016171080 A1 WO2016171080 A1 WO 2016171080A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sealing sheet
- ethylene
- mass
- solar cell
- compounds
- Prior art date
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- 238000007789 sealing Methods 0.000 title claims abstract description 108
- 229920001577 copolymer Polymers 0.000 claims abstract description 69
- -1 divinyl aromatic compounds Chemical class 0.000 claims abstract description 53
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 6
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000007973 cyanuric acids Chemical class 0.000 claims abstract description 4
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 claims abstract 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 72
- 239000005977 Ethylene Substances 0.000 claims description 72
- 230000001681 protective effect Effects 0.000 claims description 23
- 235000011187 glycerol Nutrition 0.000 claims description 18
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 12
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
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- 239000010410 layer Substances 0.000 description 18
- 239000003963 antioxidant agent Substances 0.000 description 13
- 239000006087 Silane Coupling Agent Substances 0.000 description 11
- 230000003078 antioxidant effect Effects 0.000 description 10
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- 238000004519 manufacturing process Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
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- 239000000654 additive Substances 0.000 description 6
- 239000004611 light stabiliser Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
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- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 2
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 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 2
- 230000015556 catabolic process Effects 0.000 description 2
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- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
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- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
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- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
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- VMJIDDGLSSJEFK-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylbutan-2-ylperoxy)cyclohexane Chemical compound CCC(C)(C)OOC1(OOC(C)(C)CC)CC(C)CC(C)(C)C1 VMJIDDGLSSJEFK-UHFFFAOYSA-N 0.000 description 1
- ABFCPWCUXLLRSC-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C ABFCPWCUXLLRSC-UHFFFAOYSA-N 0.000 description 1
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- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- RPPBZEBXAAZZJH-UHFFFAOYSA-N cadmium telluride Chemical compound [Te]=[Cd] RPPBZEBXAAZZJH-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- BLANBUKUVIWWGZ-UHFFFAOYSA-N ethenyl 2-hydroxyacetate Chemical compound OCC(=O)OC=C BLANBUKUVIWWGZ-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- HARQWLDROVMFJE-UHFFFAOYSA-N ethyl 3,3-bis(tert-butylperoxy)butanoate Chemical compound CCOC(=O)CC(C)(OOC(C)(C)C)OOC(C)(C)C HARQWLDROVMFJE-UHFFFAOYSA-N 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229920002631 room-temperature vulcanizate silicone Polymers 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- ZUSDEBDNDIJDMZ-UHFFFAOYSA-N tert-butyl 7-methyloctaneperoxoate Chemical compound CC(C)CCCCCC(=O)OOC(C)(C)C ZUSDEBDNDIJDMZ-UHFFFAOYSA-N 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
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-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
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to a sealing sheet and a solar cell module.
- the solar cell module generally has a configuration of a protective glass (front surface side transparent protective member), a sealing sheet, a solar cell element, a sealing sheet, and a back sheet (back surface side protective member).
- a protective glass front surface side transparent protective member
- a sealing sheet a sealing sheet
- a solar cell element a solar cell element
- a sealing sheet a sealing sheet
- a back sheet back surface side protective member
- Patent Document 1 Japanese Patent Laid-Open No. 2010-532978 discloses a sealing film that is made of an EVA composition containing a cross-linking agent and trimellitic acid ester and has both excellent adhesion and film-forming properties. Yes.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2008-53379 describes that the transparency of the solar cell encapsulating sheet is improved by including a (meth) acrylate compound in the encapsulating sheet.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2008-53379 describes that the transparency of the solar cell encapsulating sheet is improved by including a (meth) acrylate compound in the encapsulating sheet.
- this document does not describe that the occurrence of the PID phenomenon of the module can be suppressed.
- the present invention has been made in view of the above circumstances, and provides a sealing sheet that can suppress the occurrence of the PID phenomenon of a solar cell module.
- the present inventors diligently studied to provide a sealing sheet that can suppress the occurrence of the PID phenomenon of the solar cell module. As a result, the inventors have found that the use of a specific tri (meth) acrylate compound as a constituent component of the encapsulating sheet can prevent the occurrence of the PID phenomenon of the solar cell module, leading to the present invention.
- the following sealing sheet and solar cell module are provided.
- a sealing sheet used for sealing a solar cell element An ethylene / polar monomer copolymer; A crosslinking agent; One or more crosslinking aids selected from the group consisting of divinyl aromatic compounds, cyanurate compounds, diallyl compounds, triallyl compounds, oxime compounds and maleimide compounds; A glycerol tri (meth) acrylate compound represented by the following formula (I): The sealing sheet containing.
- R 1 , R 2 and R 3 are each independently a hydrogen atom or a methyl group, and R 4 , R 5 and R 6 are each independently —CH (CH 3 ) CH 2 -, -CH 2 CH (CH 3 )-or -CH 2 CH 2- , and x + y + z is an integer of 2 or more and 20 or less)
- R 4 , R 5 and R 6 are each independently —CH (CH 3 ) CH 2 -, -CH 2 CH (CH 3 )-or -CH 2 CH 2- , and x + y + z is an integer of 2 or more and 20 or less
- the content of the glycerin tri (meth) acrylate compound represented by the formula (I) is 0.1 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the ethylene / polar monomer copolymer. Stop sheet.
- a sealing layer to A solar cell module comprising:
- the solar cell module using the encapsulating sheet of the present invention has little decrease in output and parallel resistance Rsh even after a high voltage is applied, and can maintain power generation characteristics over a long period of time.
- the sealing sheet of this embodiment is used in order to seal a solar cell element, and ethylene / polar monomer copolymer, a crosslinking agent, a divinyl aromatic compound, a cyanurate compound, and a diallyl compound.
- 1 type, or 2 or more types of crosslinking adjuvants selected from the group which consists of a triallyl compound, an oxime compound, and a maleimide compound, and the glycerol tri (meth) acrylate compound shown by following formula (I).
- R 1 , R 2 and R 3 are each independently a hydrogen atom or a methyl group
- R 4 , R 5 and R 6 are each independently —CH (CH 3 ) CH 2 -, -CH 2 CH (CH 3 )-or -CH 2 CH 2-
- x + y + z is an integer of 2 or more and 20 or less
- a solar cell module using a sealing sheet containing a glycerin tri (meth) acrylate compound represented by the above formula (I) in addition to an ethylene / polar monomer copolymer, a crosslinking agent, and a crosslinking auxiliary agent is PID. It was found that the occurrence of the phenomenon can be suppressed. That is, the sealing sheet of this embodiment can suppress generation
- each component which comprises the sealing sheet of this embodiment is demonstrated.
- the encapsulating sheet of the present embodiment contains an ethylene / polar monomer copolymer.
- the ethylene / polar monomer copolymer include ethylene / (meth) ethyl acrylate copolymers, ethylene / (meth) methyl acrylate copolymers, ethylene / (meth) propyl propyl copolymers, ethylene ⁇ (Meth) butyl acrylate copolymer, ethylene ⁇ (meth) acrylic acid hexyl copolymer, ethylene ⁇ (meth) acrylic acid-2-hydroxyethyl copolymer, ethylene ⁇ (meth) acrylic acid-2-hydroxy Propylene copolymer, ethylene / (meth) acrylate glycidyl copolymer, ethylene / dimethyl maleate copolymer, ethylene / diethyl maleate copolymer, ethylene / dimethyl fuma
- the ethylene / polar monomer copolymer is one or two selected from an ethylene / vinyl ester copolymer and an ethylene / unsaturated carboxylic acid ester copolymer from the balance between availability and performance. It is preferable to contain a seed or more, and it is particularly preferable to include an ethylene / vinyl acetate copolymer.
- the ethylene / vinyl acetate copolymer is a copolymer of ethylene and vinyl acetate, and is usually a random copolymer.
- the content ratio of the structural unit derived from vinyl acetate in the ethylene / vinyl acetate copolymer is preferably 10% by mass to 47% by mass, and more preferably 13% by mass to 35% by mass.
- the vinyl acetate content can be measured according to JIS K6730.
- the ethylene / vinyl acetate copolymer is preferably a binary copolymer consisting only of ethylene and vinyl acetate.
- ethylene and vinyl acetate for example, vinyl formate, vinyl glycolate, vinyl propionate, vinyl benzoate.
- a vinyl ester monomer such as acrylic acid, methacrylic acid, ethacrylic acid, or an acrylic monomer such as a salt or alkyl ester thereof; .
- the amount of the copolymer component other than ethylene and vinyl acetate in the ethylene / vinyl acetate copolymer may be 0.5 mass% or more and 5 mass% or less. preferable.
- the melt flow rate (MFR) of the ethylene / vinyl acetate copolymer at 190 ° C. and 2160 g load according to ASTM D 1238 is preferably 5 g / 10 min to 45 g / 10 min, more preferably 5 g / 10 min to 40 g / It is 10 minutes or less, more preferably 10 g / 10 minutes or more and 30 g / 10 minutes or less.
- MFR melt flow rate
- the MFR of the ethylene / vinyl acetate copolymer can be adjusted by adjusting the polymerization temperature during the polymerization reaction, the polymerization pressure, and the molar ratio between the monomer concentration and the hydrogen concentration of the polar monomer in the polymerization system. .
- the sealing sheet of this embodiment may use, for example, two or more ethylene / vinyl acetate copolymers having different vinyl acetate contents, melt flow rates, etc. When using coalescence, it is preferable that the total amount of these be in the above range.
- the content of the ethylene / polar monomer copolymer is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 100% by mass when the entire resin component contained in the sealing sheet is 100% by mass. It is 95% by mass or more, and particularly preferably 100% by mass.
- the content of the resin component is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass when the entire sealing sheet is 100% by mass. % Or more.
- the method for producing the ethylene / polar monomer copolymer is not particularly limited, and can be produced by a known method.
- a radical generator copolymerization of ethylene, polar monomers, and other copolymerization components as necessary in the presence or absence of a solvent or chain transfer agent at 500 to 4000 atm and 100 to 300 ° C Can be manufactured.
- the crosslinking agent for example, an organic peroxide can be used.
- the ethylene / polar monomer copolymer can be cross-linked by containing a cross-linking agent, or the silane coupling agent can be grafted onto the ethylene / polar monomer copolymer. I can do it.
- the content of the crosslinking agent in the sealing sheet is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 0.2 parts by mass or more and 2 parts by mass with respect to 100 parts by mass of the ethylene / polar monomer copolymer. It is not more than part by mass, and more preferably not less than 0.2 part by mass and not more than 1 part by mass.
- the content of the cross-linking agent is not less than the above lower limit value, the deterioration of the cross-linking characteristics of the sealing sheet is suppressed, and the graft reaction to the main chain of the ethylene / polar monomer copolymer of the silane coupling agent is improved. A decrease in heat resistance and adhesiveness can be suppressed. Further, when the content of the cross-linking agent is not more than the above upper limit value, the generation amount of the decomposition product of the cross-linking agent is further reduced, and generation of bubbles in the sealing sheet can be more reliably suppressed. .
- the organic peroxide has a half-life of 10 hours or less and a decomposition temperature of 105 ° C. or less. From the viewpoint of safety, it is preferable that the maximum storage temperature is 10 ° C. or higher.
- organic peroxides examples include dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dibenzoyl peroxide, cyclohexanone peroxide, di-t -Butyl perphthalate, cumene hydroperoxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexane, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, 1,1-di (t-amylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-a
- 2,5-dimethyl-2,5-di (t-butylperoxy) hexene 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperoxy- It is preferable to use one or more selected from 2-ethylhexyl carbonate and t-butyl peroxybenzoate.
- the sealing sheet of the present embodiment has excellent crosslinking characteristics by containing a crosslinking agent, it is not necessary to go through a two-step bonding process of a vacuum laminator and a crosslinking furnace, and at a high temperature in a short time. Can be completed.
- Crosslinking aid one or more selected from the group consisting of divinyl aromatic compounds, cyanurate compounds, diallyl compounds, triallyl compounds, oxime compounds and maleimide compounds can be used.
- the content of the crosslinking aid in the encapsulating sheet is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, with respect to 100 parts by mass of the ethylene / polar monomer copolymer.
- the amount is particularly preferably 2.0 parts by mass or less.
- Examples of the divinyl aromatic compound include divinylbenzene and di-i-propenylbenzene.
- Examples of the cyanurate compound include triallyl cyanurate and triallyl isocyanurate.
- Examples of diallyl compounds include diallyl phthalate.
- Examples of the triallyl compound include pentaerythritol triallyl ether.
- Examples of the oxime compound include p-quinone dioxime, pp′-dibenzoylquinone dioxime, and the like.
- Examples of the maleimide compound include m-phenylene dimaleimide.
- the sealing sheet of this embodiment contains a glycerin tri (meth) acrylate compound represented by the following formula (I).
- R 1 , R 2 and R 3 are each independently a hydrogen atom or a methyl group
- R 4 , R 5 and R 6 are each independently —CH (CH 3 ) CH 2 — , —CH 2 CH (CH 3 ) — or —CH 2 CH 2 —
- x + y + z is an integer of 2 or more and 20 or less.
- x + y + z is preferably an integer of 3 or more and 6 or less, more preferably 3 or 6.
- Each of x, y and z is preferably independently 1 or 2.
- R 1 , R 2 and R 3 in the above formula (I) are preferably all hydrogen atoms.
- R 1 , R 2, and R 3 are hydrogen atoms, the PID resistance is excellent as compared with a compound that is a methyl group.
- the glycerin tri (meth) acrylate compound represented by the above formula (I) glycerin propoxytri (meth) acrylate and glycerin ethoxytri (meth) acrylate are preferable, and glycerin propoxytriacrylate and glycerin ethoxytriacrylate are more preferable. .
- x + y + z in the above formula (I) is preferably an integer of 3 or more, and particularly preferably 3 or 6.
- a mixture of a compound having x + y + z of 3 and a compound having x + y + z of 6 may be used, or a compound other than x + y + z of 3 or 6 may be mixed by 30% by mass or less.
- the content of the glycerin tri (meth) acrylate compound represented by the above formula (I) is 0.1 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the ethylene / polar monomer copolymer. It is particularly preferably 0.1 parts by mass or more and 1.0 part by mass or less.
- the content of the glycerin tri (meth) acrylate compound is not less than the above lower limit value, the PID resistance of the obtained solar cell module can be further improved.
- content of a glycerol tri (meth) acrylate compound is below the said upper limit, generation
- the total content of the crosslinking aid and the glycerin tri (meth) acrylate compound represented by the above formula (I) is preferably 0.2 parts by mass or more with respect to 100 parts by mass of the ethylene / polar monomer copolymer. 5.0 parts by mass or less, more preferably 0.5 parts by mass or more and 3.0 parts by mass or less, and further preferably 0.5 parts by mass or more and 2.0 parts by mass or less.
- the encapsulating sheet of the present embodiment may appropriately contain various components other than the components detailed above in a range not impairing the object of the present invention.
- one or two or more additives selected from silane coupling agents, ultraviolet absorbers, light stabilizers, antioxidants and the like can be appropriately contained.
- the content of the silane coupling agent in the sealing sheet of the present embodiment is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 100 parts by mass of the ethylene / polar monomer copolymer. It is 0.1 mass part or more and 3 mass parts or less, More preferably, it is 0.1 mass part or more and 1.5 mass parts or less.
- the adhesive strength between the sealing sheet and the other member can be further improved.
- silane coupling agent when the silane coupling agent is not more than the above upper limit value, methanol and ethanol generated by hydrolysis derived from the methoxy group and ethoxy group of the silane coupling agent are reduced, and bubbles are generated in the sealing sheet. It can suppress more reliably.
- silane coupling agent examples include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris ( ⁇ -methoxyethoxysilane), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropylmethyl.
- the encapsulating sheet of this embodiment may contain one or two or more additives selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant.
- the total content of these additives is preferably 0.005 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the ethylene / polar monomer copolymer. By making it within this range, the effect of improving the resistance to high temperature and high humidity, heat cycle resistance, weather resistance stability, and heat stability is sufficiently secured, and the transparency and adhesiveness of the sealing sheet are lowered. Can be prevented.
- Examples of the ultraviolet absorber include 2-hydroxy-4-normal-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2- Benzophenone ultraviolet absorbers such as carboxybenzophenone and 2-hydroxy-4-N-octoxybenzophenone; 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy- Benzotriazole ultraviolet absorbers such as 5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-t-octylphenyl) benzotriazole; salicylic acid esters such as phenyl salicylate and p-octylphenyl salicylate Select from UV absorbers, etc. It is the one or may be used two or more.
- Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino-1,3. , 5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ ]
- the like selected from hindered amine compounds, hindered piperidine compounds and the like can be used.
- antioxidants examples include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid Tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphos Phosphite-based antioxidants such as phites; Lactone-based antioxidants such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene; 3,3 ′ , 3 ", 5,5 ', 5" -hexa-tert-butyl-a, a', a "-(methylene-2,4,6-triyl) tri-p-cresol
- the thickness of the sealing sheet in this embodiment is not specifically limited, 0.01 mm or more and 2 mm or less are preferable, and 0.2 mm or more and 1.2 mm or less are more preferable. When the thickness is within this range, damage to the light-receiving surface side protective member, solar cell element, thin film electrode, etc. in the laminating step can be suppressed, and a high amount of photovoltaic power can be obtained by ensuring sufficient light transmittance. be able to. Furthermore, it is preferable because the solar cell module can be laminated at a low temperature.
- the sealing sheet of this embodiment may be laminated with other layers as long as the object of the present invention is not impaired.
- layers such as a hard-coat layer for surface or back surface protection, an adhesion layer, an antireflection layer, a gas barrier layer, and an antifouling layer.
- layer made of UV curable resin layer made of thermosetting resin
- layer made of polyolefin resin layer made of carboxylic acid modified polyolefin resin
- layer made of fluorine-containing resin cyclic olefin (co)
- examples thereof include a layer made of a polymer and a layer made of an inorganic compound.
- the thermal shrinkage rate measured according to JIS C2318-1997 is preferably 25% or less, and more preferably 15% or less.
- Method for producing sealing sheet Although the manufacturing method of the sealing sheet of this embodiment is not particularly limited, various known molding methods (cast molding, extrusion sheet molding, inflation molding, injection molding, compression molding, calendar molding, etc.) can be employed. is there. In particular, extrusion molding and calendar molding are preferable.
- the manufacturing method of the sealing sheet of this embodiment is not specifically limited, For example, the following method is mentioned. First, an ethylene / polar monomer copolymer, a crosslinking agent, a crosslinking assistant, a glycerin tri (meth) acrylate compound represented by the above formula (I), and other additives as needed are dry blended. . Next, the obtained mixture is supplied from the hopper to the extruder and melt-kneaded at a temperature lower than the one-hour half-life temperature of the crosslinking agent as necessary. Thereafter, a sealing sheet is produced by extrusion from the tip of the extruder into a sheet.
- the molding can be performed by a known method using a T-die extruder, a calendar molding machine, an inflation molding machine or the like.
- seat which does not contain a crosslinking agent may be produced by the said method, and a crosslinking agent may be added to the produced sheet
- melt kneading may be performed at a temperature lower than the one-hour half-life temperature of the lowest crosslinking agent.
- the sealing sheet of this embodiment is used in order to seal a solar cell element in a solar cell module.
- seat) in this order is mentioned, it is not specifically limited.
- the sealing sheet of this embodiment is used for either one or both of the light receiving surface side sealing sheet and the back surface side sealing sheet.
- the solar cell module 10 includes a plurality of solar cell elements 13, a pair of light-receiving surface side sealing sheet 11 and back surface side sealing sheet 12 that are sealed with the solar cell element 13 interposed therebetween, and a front surface side transparent protective member 14 and a back surface.
- solar cell element 13 examples include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and III-V and II-VI compound semiconductors such as gallium-arsenic, copper-indium-selenium, and cadmium-tellurium.
- Various solar cell elements such as a system can be used.
- the plurality of solar cell elements 13 are electrically connected in series via an interconnector 16 having a conducting wire and a solder joint.
- Examples of the surface-side transparent protective member 14 include a glass plate; a resin plate formed of acrylic resin, polycarbonate, polyester, fluorine-containing resin, and the like.
- back surface side protection member (back sheet) 15 examples include single or multilayer sheets such as metals and various thermoplastic resin films. Examples thereof include metals such as tin, aluminum, and stainless steel; inorganic materials such as glass; various thermoplastic resin films formed of polyester, inorganic material-deposited polyester, fluorine-containing resin, polyolefin, and the like.
- the back surface side protection member 15 may be a single layer or a multilayer.
- the sealing sheet of the present embodiment exhibits good adhesion to the front surface side transparent protective member 14 and the back surface side protective member 15.
- the manufacturing method of the solar cell module 10 of this embodiment is not specifically limited, For example, the following method is mentioned.
- a plurality of solar cell elements 13 that are electrically connected using the interconnector 16 are sandwiched between a pair of light-receiving surface side sealing sheet 11 and back surface side sealing sheet 12, and further, these light receiving surface side sealing sheet 11 and back surface A laminated body is produced by sandwiching the side sealing sheet 12 between the front surface side transparent protective member 14 and the back surface side protective member 15.
- the laminate is heated to receive the light-receiving surface side sealing sheet 11 and the back surface side sealing sheet 12, the light receiving surface side sealing sheet 11 and the front surface side transparent protective member 14, and the back surface side sealing sheet 12 and the back surface side protective member. 15 is bonded. More specifically, the sealing sheet is heated to such a temperature that the crosslinking agent contained in the sealing sheet is not substantially decomposed and the ethylene / polar monomer copolymer is melted, and the light receiving surface side sealing is performed. The sheet 11 and the rear surface side sealing sheet 12, the light receiving surface side sealing sheet 11 and the front surface side transparent protective member 14, and the rear surface side sealing sheet 12 and the rear surface side protective member 15 are temporarily bonded.
- the bonding and crosslinking temperature may be a temperature at which a satisfactory crosslinking rate can be obtained and swelling does not occur, and can be in a temperature range of about 100 to 180 ° C., for example.
- sealing sheets were produced as follows. First, an ethylene / vinyl acetate copolymer (EVA), a crosslinking agent, a crosslinking aid, an acrylate compound, a silane coupling agent, a light stabilizer, and an antioxidant are blended in the formulation shown in Table 1 to obtain a resin composition. Obtained. The obtained resin composition was extrusion molded into a sealing sheet having a thickness of about 450 ⁇ m with an extruder with a T-die.
- EVA ethylene / vinyl acetate copolymer
- each component in Table 1 is part by mass.
- the detail of each component in Table 1 is as follows.
- EVA ethylene-vinyl acetate copolymer (vinyl acetate content 28% by mass, MFR: 15 g / 10 min)
- Crosslinking agent t-butylperoxy-2-ethylhexyl carbonate
- Crosslinking aid triallyl isocyanurate
- Acrylate compound 1 Glycerol propoxytriacrylate (in formula (I), x + y + z is 3, R 1 , R 2 , R 3 Wherein R 4 , R 5 and R 6 are —CH (CH 3 ) CH 2 — or —CH 2 CH (CH 3 ) —)
- Acrylate compound 2 Nonaethylene glycol dimethacrylate
- Acrylate compound 3 Glycerol ethoxytriacrylate (in formula (I), x + y + z is 3, R 1 , R 2 , R 3 are hydrogen atoms, R 4 , R 5 and R Compound in which 6 is —CH 2 CH 2 — Silane coupling agent:
- a PET backsheet containing silica-deposited PET as the backsheet cut a portion of the backsheet with a cutter-knife about 2 cm, take out the positive and negative terminals of the cell, and use a vacuum laminator (NPC: LM -110 ⁇ 160-S) was laminated at a heating plate temperature of 150 ° C., a vacuum time of 3 minutes, and a pressurization time of 15 minutes. Thereafter, the sealing sheet and the back sheet that protruded from the glass were cut, an end face sealing material was applied to the glass edge, and an aluminum frame was attached. Thereafter, the cut portion of the terminal portion taken out from the back sheet was cured by applying RTV silicone to obtain a mini module.
- NPC vacuum laminator
- This module was set in a constant temperature and humidity chamber at 60 ° C. and 85% Rh, and after waiting for the temperature to rise, it was held for 96 hours while applying ⁇ 1000 V.
- HARb-3R10-LF manufactured by Matsusada Precision Co., Ltd. was used as the high voltage power source, and FS-214C2 manufactured by ETAC Co., Ltd. was used as the constant temperature and humidity chamber.
- the IV characteristics of the module are the maximum output power at a light irradiation power density of 1000 W / m 2 using a xenon light source with AM (air mass) 1.5 class A light intensity distribution and PVS-116i-S manufactured by Nisshinbo Mechatronics. P max was evaluated. Furthermore, since the parallel resistance in the dark (dark Rsh) in PID evaluation is the most sensitive parameter for indicating cell deterioration, dark Rsh was also added to the evaluation item. Specifically, the module is installed in a dark room, IV characteristics in the dark are measured using 6242 made by ADC, and dark Rsh is calculated from the slope ( ⁇ V / ⁇ I) of the voltage when the current is near zero. evaluated.
- the evaluation results were classified as follows. The results are shown in Table 1.
- the maximum output power P max of the IV characteristic after the test is less than 5% compared to the initial value: A: Output power drop exceeds 5%: B
- the parallel resistance (dark Rsh) in the dark of IV characteristics after the test is less than 50% of the decrease in dark Rsh: A Dark Rsh reduction exceeds 50%: B
- P max and dark Rsh were A, it was judged that there was no PID degradation.
- P max or dark Rsh was B, it was judged that PID was degraded.
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Abstract
This sealing sheet is used for the purpose of sealing a solar cell element, and contains an ethylene-polar monomer copolymer, a crosslinking agent, one or more crosslinking assistants selected from the group consisting of divinyl aromatic compounds, cyanurate compounds, diallyl compounds, triallyl compounds, oxime compounds and maleimide compounds, and a glycerol tri(meth)acrylate compound represented by formula (I).
In formula (I), each of R1, R2 and R3 independently represents a hydrogen atom or a methyl group; each of R4, R5 and R6 independently represents -CH(CH3)CH2-, -CH2CH(CH3)- or -CH2CH2-; and x + y + z represents an integer of from 2 to 20 (inclusive).
Description
本発明は、封止シートおよび太陽電池モジュールに関する。
The present invention relates to a sealing sheet and a solar cell module.
近年、クリーンなエネルギーとして太陽光発電が脚光を浴び、太陽光発電用の太陽電池モジュールの開発が進められている。太陽電池モジュールは、一般に、保護ガラス（表面側透明保護部材）、封止シート、太陽電池素子、封止シート、バックシート（裏面側保護部材）という構成になっている。太陽電池モジュールの製造の際、上記各層を積層した状態で封止シートを加熱することによって、封止シート中の樹脂が溶融して太陽電池素子を封止し、さらには保護ガラスやバックシートと接着する。
In recent years, photovoltaic power generation has attracted attention as clean energy, and the development of solar cell modules for photovoltaic power generation has been promoted. The solar cell module generally has a configuration of a protective glass (front surface side transparent protective member), a sealing sheet, a solar cell element, a sealing sheet, and a back sheet (back surface side protective member). During the production of the solar cell module, by heating the sealing sheet in a state where the respective layers are laminated, the resin in the sealing sheet is melted to seal the solar cell element, and further, with a protective glass and a back sheet. Adhere.
太陽電池素子用の封止シートとしては、従来からエチレン・酢酸ビニル共重合体（ＥＶＡ）シートが、透明性、柔軟性、加工性、および耐久性等に優れていることから広く用いられてきた。例えば、特許文献１（特開２０１０－５３２９８号公報）には、架橋剤およびトリメリット酸エステルを含むＥＶＡ組成物からなる、接着性と製膜性の双方に優れた封止膜が開示されている。
As a sealing sheet for a solar cell element, an ethylene / vinyl acetate copolymer (EVA) sheet has been widely used since it has excellent transparency, flexibility, workability, durability, and the like. . For example, Patent Document 1 (Japanese Patent Laid-Open No. 2010-53298) discloses a sealing film that is made of an EVA composition containing a cross-linking agent and trimellitic acid ester and has both excellent adhesion and film-forming properties. Yes.
メガソーラの普及に伴い、伝送損失を下げる等の目的で、システム電圧の高電圧化が進んでいる。高電圧が維持された状態で用いられる太陽電池モジュールの中には、出力が大きく低下して特性が劣化してしまうＰＩＤ（Ｐｏｔｅｎｔｉａｌ Ｉｎｄｕｃｅｄ Ｄｅｇｒａｄａｔｉｏｎの略）現象が発生する場合がある。ＰＩＤ現象を防止し、長期にわたって発電特性を維持できる太陽電池モジュールが求められている。
例えば、特許文献２（特開２００８－５３３７９号公報）に（メタ）アクリレート化合物を封止シートに含有させることにより太陽電池封止シートの透明性が向上することが記載されている。しかしながら同文献にはモジュールのＰＩＤ現象の発生を抑制できることは記載されていない。 With the widespread use of mega solar, the system voltage is increasing for the purpose of reducing transmission loss. Among solar cell modules used in a state where a high voltage is maintained, a PID (abbreviation of Potential Induced Degradation) phenomenon in which the output is greatly reduced and the characteristics deteriorate may occur. There is a demand for a solar cell module that can prevent the PID phenomenon and maintain power generation characteristics over a long period of time.
For example, Patent Document 2 (Japanese Patent Application Laid-Open No. 2008-53379) describes that the transparency of the solar cell encapsulating sheet is improved by including a (meth) acrylate compound in the encapsulating sheet. However, this document does not describe that the occurrence of the PID phenomenon of the module can be suppressed.
例えば、特許文献２（特開２００８－５３３７９号公報）に（メタ）アクリレート化合物を封止シートに含有させることにより太陽電池封止シートの透明性が向上することが記載されている。しかしながら同文献にはモジュールのＰＩＤ現象の発生を抑制できることは記載されていない。 With the widespread use of mega solar, the system voltage is increasing for the purpose of reducing transmission loss. Among solar cell modules used in a state where a high voltage is maintained, a PID (abbreviation of Potential Induced Degradation) phenomenon in which the output is greatly reduced and the characteristics deteriorate may occur. There is a demand for a solar cell module that can prevent the PID phenomenon and maintain power generation characteristics over a long period of time.
For example, Patent Document 2 (Japanese Patent Application Laid-Open No. 2008-53379) describes that the transparency of the solar cell encapsulating sheet is improved by including a (meth) acrylate compound in the encapsulating sheet. However, this document does not describe that the occurrence of the PID phenomenon of the module can be suppressed.
本発明は上記事情に鑑みてなされたものであり、太陽電池モジュールのＰＩＤ現象の発生を抑制できる封止シートを提供するものである。
The present invention has been made in view of the above circumstances, and provides a sealing sheet that can suppress the occurrence of the PID phenomenon of a solar cell module.
本発明者らは、太陽電池モジュールのＰＩＤ現象の発生を抑制できる封止シートを提供するために鋭意検討した。その結果、封止シートの構成成分として、特定のトリ（メタ）アクリレート化合物を用いることで、太陽電池モジュールのＰＩＤ現象の発生を防止できることを見出し、本発明に至った。
The present inventors diligently studied to provide a sealing sheet that can suppress the occurrence of the PID phenomenon of the solar cell module. As a result, the inventors have found that the use of a specific tri (meth) acrylate compound as a constituent component of the encapsulating sheet can prevent the occurrence of the PID phenomenon of the solar cell module, leading to the present invention.
すなわち、本発明によれば、以下に示す封止シートおよび太陽電池モジュールが提供される。
That is, according to the present invention, the following sealing sheet and solar cell module are provided.
［１］
太陽電池素子を封止するために用いられる封止シートであって、
エチレン・極性モノマー共重合体と、
架橋剤と、
ジビニル芳香族化合物、シアヌレート化合物、ジアリル化合物、トリアリル化合物、オキシム化合物およびマレイミド化合物からなる群より選択される一種または二種以上の架橋助剤と、
下記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物と、
を含む封止シート。
（上記式（Ｉ）中、Ｒ１、Ｒ２およびＲ３はそれぞれ独立して水素原子またはメチル基であり、Ｒ４、Ｒ５およびＲ６はそれぞれ独立して－ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）－または－ＣＨ２ＣＨ２－であり、ｘ＋ｙ＋ｚは２以上２０以下の整数である）
［２］
上記［１］に記載の封止シートにおいて、
上記エチレン・極性モノマー共重合体がエチレン・酢酸ビニル共重合体を含む封止シート。
［３］
上記［２］に記載の封止シートにおいて、
上記エチレン・酢酸ビニル共重合体中の酢酸ビニルに由来する構成単位の含有割合が１０質量％以上４７質量％以下である封止シート。
［４］
上記［１］乃至［３］いずれか一つに記載の封止シートにおいて、
上記式（Ｉ）におけるＲ１、Ｒ２およびＲ３が水素原子である封止シート。
［５］
上記［１］乃至［４］いずれか一つに記載の封止シートにおいて、
上記式（Ｉ）におけるｘ＋ｙ＋ｚが３または６である封止シート。
［６］
上記［１］乃至［５］いずれか一つに記載の封止シートにおいて、
上記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物の含有量が、上記エチレン・極性モノマー共重合体１００質量部に対して、０．１質量部以上２．０質量部以下である封止シート。
［７］
表面側透明保護部材と、
裏面側保護部材と、
太陽電池素子と、
上記［１］乃至［６］いずれか一つに記載の封止シートの架橋物により構成され、かつ、上記太陽電池素子を上記表面側透明保護部材と上記裏面側保護部材との間に封止する封止層と、
を備える太陽電池モジュール。 [1]
A sealing sheet used for sealing a solar cell element,
An ethylene / polar monomer copolymer;
A crosslinking agent;
One or more crosslinking aids selected from the group consisting of divinyl aromatic compounds, cyanurate compounds, diallyl compounds, triallyl compounds, oxime compounds and maleimide compounds;
A glycerol tri (meth) acrylate compound represented by the following formula (I):
The sealing sheet containing.
(In the above formula (I), R 1 , R 2 and R 3 are each independently a hydrogen atom or a methyl group, and R 4 , R 5 and R 6 are each independently —CH (CH 3 ) CH 2 -, -CH 2 CH (CH 3 )-or -CH 2 CH 2- , and x + y + z is an integer of 2 or more and 20 or less)
[2]
In the sealing sheet according to the above [1],
A sealing sheet in which the ethylene / polar monomer copolymer comprises an ethylene / vinyl acetate copolymer.
[3]
In the sealing sheet according to the above [2],
The sealing sheet whose content rate of the structural unit derived from the vinyl acetate in the said ethylene-vinyl acetate copolymer is 10 mass% or more and 47 mass% or less.
[4]
In the sealing sheet according to any one of the above [1] to [3],
The sealing sheet whose R < 1 >, R < 2 > and R < 3 > in said formula (I) are a hydrogen atom.
[5]
In the sealing sheet according to any one of the above [1] to [4],
The sealing sheet whose x + y + z in the said formula (I) is 3 or 6.
[6]
In the sealing sheet according to any one of [1] to [5] above,
The content of the glycerin tri (meth) acrylate compound represented by the formula (I) is 0.1 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the ethylene / polar monomer copolymer. Stop sheet.
[7]
A surface-side transparent protective member;
A back side protection member;
A solar cell element;
It is comprised by the bridge | crosslinking material of the sealing sheet as described in any one of said [1] thru | or [6], and seals the said solar cell element between the said surface side transparent protective member and the said back surface side protective member. A sealing layer to
A solar cell module comprising:
太陽電池素子を封止するために用いられる封止シートであって、
エチレン・極性モノマー共重合体と、
架橋剤と、
ジビニル芳香族化合物、シアヌレート化合物、ジアリル化合物、トリアリル化合物、オキシム化合物およびマレイミド化合物からなる群より選択される一種または二種以上の架橋助剤と、
下記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物と、
を含む封止シート。
［２］
上記［１］に記載の封止シートにおいて、
上記エチレン・極性モノマー共重合体がエチレン・酢酸ビニル共重合体を含む封止シート。
［３］
上記［２］に記載の封止シートにおいて、
上記エチレン・酢酸ビニル共重合体中の酢酸ビニルに由来する構成単位の含有割合が１０質量％以上４７質量％以下である封止シート。
［４］
上記［１］乃至［３］いずれか一つに記載の封止シートにおいて、
上記式（Ｉ）におけるＲ１、Ｒ２およびＲ３が水素原子である封止シート。
［５］
上記［１］乃至［４］いずれか一つに記載の封止シートにおいて、
上記式（Ｉ）におけるｘ＋ｙ＋ｚが３または６である封止シート。
［６］
上記［１］乃至［５］いずれか一つに記載の封止シートにおいて、
上記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物の含有量が、上記エチレン・極性モノマー共重合体１００質量部に対して、０．１質量部以上２．０質量部以下である封止シート。
［７］
表面側透明保護部材と、
裏面側保護部材と、
太陽電池素子と、
上記［１］乃至［６］いずれか一つに記載の封止シートの架橋物により構成され、かつ、上記太陽電池素子を上記表面側透明保護部材と上記裏面側保護部材との間に封止する封止層と、
を備える太陽電池モジュール。 [1]
A sealing sheet used for sealing a solar cell element,
An ethylene / polar monomer copolymer;
A crosslinking agent;
One or more crosslinking aids selected from the group consisting of divinyl aromatic compounds, cyanurate compounds, diallyl compounds, triallyl compounds, oxime compounds and maleimide compounds;
A glycerol tri (meth) acrylate compound represented by the following formula (I):
The sealing sheet containing.
[2]
In the sealing sheet according to the above [1],
A sealing sheet in which the ethylene / polar monomer copolymer comprises an ethylene / vinyl acetate copolymer.
[3]
In the sealing sheet according to the above [2],
The sealing sheet whose content rate of the structural unit derived from the vinyl acetate in the said ethylene-vinyl acetate copolymer is 10 mass% or more and 47 mass% or less.
[4]
In the sealing sheet according to any one of the above [1] to [3],
The sealing sheet whose R < 1 >, R < 2 > and R < 3 > in said formula (I) are a hydrogen atom.
[5]
In the sealing sheet according to any one of the above [1] to [4],
The sealing sheet whose x + y + z in the said formula (I) is 3 or 6.
[6]
In the sealing sheet according to any one of [1] to [5] above,
The content of the glycerin tri (meth) acrylate compound represented by the formula (I) is 0.1 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the ethylene / polar monomer copolymer. Stop sheet.
[7]
A surface-side transparent protective member;
A back side protection member;
A solar cell element;
It is comprised by the bridge | crosslinking material of the sealing sheet as described in any one of said [1] thru | or [6], and seals the said solar cell element between the said surface side transparent protective member and the said back surface side protective member. A sealing layer to
A solar cell module comprising:
本発明によれば、太陽電池モジュールのＰＩＤ現象の発生を抑制できる封止シートを実現できる。すなわち、本発明の封止シートを用いた太陽電池モジュールは高電圧が印加された後にも出力ならびに並列抵抗Ｒｓｈの低下が小さく、長期にわたり発電特性を維持することができる。
According to the present invention, it is possible to realize a sealing sheet that can suppress the occurrence of the PID phenomenon of the solar cell module. That is, the solar cell module using the encapsulating sheet of the present invention has little decrease in output and parallel resistance Rsh even after a high voltage is applied, and can maintain power generation characteristics over a long period of time.
上述した目的、およびその他の目的、特徴および利点は、以下に述べる好適な実施の形態、およびそれに付随する以下の図面によってさらに明らかになる。
The above-described object and other objects, features, and advantages will be further clarified by a preferred embodiment described below and the following drawings attached thereto.
以下、本発明の実施の形態について、図面を用いて説明する。なお、数値範囲の「Ａ～Ｂ」は特に断りがなければ、Ａ以上Ｂ以下を表す。また、本明細書において「（メタ）アクリレート」とは、「アクリレート」または「メタクリレート」を意味する。また、本明細書において「（メタ）アクリル酸」は「アクリル酸」または「メタクリル酸」を意味する。
Hereinafter, embodiments of the present invention will be described with reference to the drawings. The numerical range “A to B” represents A or more and B or less unless otherwise specified. In the present specification, “(meth) acrylate” means “acrylate” or “methacrylate”. In the present specification, “(meth) acrylic acid” means “acrylic acid” or “methacrylic acid”.
１．封止シートについて
本実施形態の封止シートは太陽電池素子を封止するために用いられるものであり、エチレン・極性モノマー共重合体と、架橋剤と、ジビニル芳香族化合物、シアヌレート化合物、ジアリル化合物、トリアリル化合物、オキシム化合物およびマレイミド化合物からなる群より選択される一種または二種以上の架橋助剤と、下記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物と、を含む。 1. About sealing sheet The sealing sheet of this embodiment is used in order to seal a solar cell element, and ethylene / polar monomer copolymer, a crosslinking agent, a divinyl aromatic compound, a cyanurate compound, and a diallyl compound. 1 type, or 2 or more types of crosslinking adjuvants selected from the group which consists of a triallyl compound, an oxime compound, and a maleimide compound, and the glycerol tri (meth) acrylate compound shown by following formula (I).
本実施形態の封止シートは太陽電池素子を封止するために用いられるものであり、エチレン・極性モノマー共重合体と、架橋剤と、ジビニル芳香族化合物、シアヌレート化合物、ジアリル化合物、トリアリル化合物、オキシム化合物およびマレイミド化合物からなる群より選択される一種または二種以上の架橋助剤と、下記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物と、を含む。 1. About sealing sheet The sealing sheet of this embodiment is used in order to seal a solar cell element, and ethylene / polar monomer copolymer, a crosslinking agent, a divinyl aromatic compound, a cyanurate compound, and a diallyl compound. 1 type, or 2 or more types of crosslinking adjuvants selected from the group which consists of a triallyl compound, an oxime compound, and a maleimide compound, and the glycerol tri (meth) acrylate compound shown by following formula (I).
本発明者らは、ＰＩＤ現象の発生を抑制できる封止シートを提供するために鋭意検討した。その結果、エチレン・極性モノマー共重合体、架橋剤、および架橋助剤に加えて、上記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物を含む封止シートを用いた太陽電池モジュールはＰＩＤ現象の発生を抑制できることを見出した。
すなわち、本実施形態の封止シートは、得られる太陽電池モジュールのＰＩＤ現象の発生を抑制することができる。
以下、本実施形態の封止シートを構成する各成分について説明する。 The present inventors diligently studied to provide a sealing sheet that can suppress the occurrence of the PID phenomenon. As a result, a solar cell module using a sealing sheet containing a glycerin tri (meth) acrylate compound represented by the above formula (I) in addition to an ethylene / polar monomer copolymer, a crosslinking agent, and a crosslinking auxiliary agent is PID. It was found that the occurrence of the phenomenon can be suppressed.
That is, the sealing sheet of this embodiment can suppress generation | occurrence | production of the PID phenomenon of the solar cell module obtained.
Hereinafter, each component which comprises the sealing sheet of this embodiment is demonstrated.
すなわち、本実施形態の封止シートは、得られる太陽電池モジュールのＰＩＤ現象の発生を抑制することができる。
以下、本実施形態の封止シートを構成する各成分について説明する。 The present inventors diligently studied to provide a sealing sheet that can suppress the occurrence of the PID phenomenon. As a result, a solar cell module using a sealing sheet containing a glycerin tri (meth) acrylate compound represented by the above formula (I) in addition to an ethylene / polar monomer copolymer, a crosslinking agent, and a crosslinking auxiliary agent is PID. It was found that the occurrence of the phenomenon can be suppressed.
That is, the sealing sheet of this embodiment can suppress generation | occurrence | production of the PID phenomenon of the solar cell module obtained.
Hereinafter, each component which comprises the sealing sheet of this embodiment is demonstrated.
＜エチレン・極性モノマー共重合体＞
本実施形態の封止シートは、エチレン・極性モノマー共重合体を含有している。
上記エチレン・極性モノマー共重合体としては、例えば、エチレン・（メタ）アクリル酸エチル共重合体、エチレン・（メタ）アクリル酸メチル共重合体、エチレン・（メタ）アクリル酸プロピル共重合体、エチレン・（メタ）アクリル酸ブチル共重合体、エチレン・（メタ）アクリル酸ヘキシル共重合体、エチレン・（メタ）アクリル酸－２－ヒドロキシエチル共重合体、エチレン・（メタ）アクリル酸－２－ヒドロキシプロピル共重合体、エチレン・（メタ）アクリル酸グリシジル共重合体、エチレン・マレイン酸ジメチル共重合体、エチレン・マレイン酸ジエチル共重合体、エチレン・フマル酸ジメチル共重合体、エチレン・フマル酸ジエチル共重合体等のエチレン・不飽和カルボン酸エステル共重合体；エチレン・（メタ）アクリル酸共重合体、エチレン・マレイン酸共重合体、エチレン・フマル酸共重合体、エチレン・クロトン酸共重合体等のエチレン・不飽和カルボン酸共重合体およびそれらの塩；エチレン・酢酸ビニル共重合体、エチレン・プロピオン酸ビニル共重合体、エチレン・酪酸ビニル共重合体、エチレン・ステアリン酸ビニル共重合体等のエチレン・ビニルエステル共重合体：エチレン・スチレン共重合体等から選択される一種または二種以上を挙げることができる。
これらの中でも、上記エチレン・極性モノマー共重合体としては、その入手容易性と性能とのバランスからエチレン・ビニルエステル共重合体、エチレン・不飽和カルボン酸エステル共重合体から選択される一種または二種以上を含むことが好ましく、特に、エチレン・酢酸ビニル共重合体を含むことが好ましい。 <Ethylene / polar monomer copolymer>
The encapsulating sheet of the present embodiment contains an ethylene / polar monomer copolymer.
Examples of the ethylene / polar monomer copolymer include ethylene / (meth) ethyl acrylate copolymers, ethylene / (meth) methyl acrylate copolymers, ethylene / (meth) propyl propyl copolymers, ethylene・ (Meth) butyl acrylate copolymer, ethylene ・ (meth) acrylic acid hexyl copolymer, ethylene ・ (meth) acrylic acid-2-hydroxyethyl copolymer, ethylene ・ (meth) acrylic acid-2-hydroxy Propylene copolymer, ethylene / (meth) acrylate glycidyl copolymer, ethylene / dimethyl maleate copolymer, ethylene / diethyl maleate copolymer, ethylene / dimethyl fumarate copolymer, ethylene / diethyl fumarate copolymer Ethylene / unsaturated carboxylic acid ester copolymer such as polymer; ethylene / (meth) acrylic Copolymers, ethylene / maleic acid copolymers, ethylene / fumaric acid copolymers, ethylene / unsaturated carboxylic acid copolymers such as ethylene / crotonic acid copolymers and their salts; ethylene / vinyl acetate copolymers Ethylene / vinyl ester copolymer such as ethylene / vinyl propionate copolymer, ethylene / vinyl butyrate copolymer, ethylene / vinyl stearate copolymer: one or two selected from ethylene / styrene copolymer, etc. More than species can be mentioned.
Among these, the ethylene / polar monomer copolymer is one or two selected from an ethylene / vinyl ester copolymer and an ethylene / unsaturated carboxylic acid ester copolymer from the balance between availability and performance. It is preferable to contain a seed or more, and it is particularly preferable to include an ethylene / vinyl acetate copolymer.
本実施形態の封止シートは、エチレン・極性モノマー共重合体を含有している。
上記エチレン・極性モノマー共重合体としては、例えば、エチレン・（メタ）アクリル酸エチル共重合体、エチレン・（メタ）アクリル酸メチル共重合体、エチレン・（メタ）アクリル酸プロピル共重合体、エチレン・（メタ）アクリル酸ブチル共重合体、エチレン・（メタ）アクリル酸ヘキシル共重合体、エチレン・（メタ）アクリル酸－２－ヒドロキシエチル共重合体、エチレン・（メタ）アクリル酸－２－ヒドロキシプロピル共重合体、エチレン・（メタ）アクリル酸グリシジル共重合体、エチレン・マレイン酸ジメチル共重合体、エチレン・マレイン酸ジエチル共重合体、エチレン・フマル酸ジメチル共重合体、エチレン・フマル酸ジエチル共重合体等のエチレン・不飽和カルボン酸エステル共重合体；エチレン・（メタ）アクリル酸共重合体、エチレン・マレイン酸共重合体、エチレン・フマル酸共重合体、エチレン・クロトン酸共重合体等のエチレン・不飽和カルボン酸共重合体およびそれらの塩；エチレン・酢酸ビニル共重合体、エチレン・プロピオン酸ビニル共重合体、エチレン・酪酸ビニル共重合体、エチレン・ステアリン酸ビニル共重合体等のエチレン・ビニルエステル共重合体：エチレン・スチレン共重合体等から選択される一種または二種以上を挙げることができる。
これらの中でも、上記エチレン・極性モノマー共重合体としては、その入手容易性と性能とのバランスからエチレン・ビニルエステル共重合体、エチレン・不飽和カルボン酸エステル共重合体から選択される一種または二種以上を含むことが好ましく、特に、エチレン・酢酸ビニル共重合体を含むことが好ましい。 <Ethylene / polar monomer copolymer>
The encapsulating sheet of the present embodiment contains an ethylene / polar monomer copolymer.
Examples of the ethylene / polar monomer copolymer include ethylene / (meth) ethyl acrylate copolymers, ethylene / (meth) methyl acrylate copolymers, ethylene / (meth) propyl propyl copolymers, ethylene・ (Meth) butyl acrylate copolymer, ethylene ・ (meth) acrylic acid hexyl copolymer, ethylene ・ (meth) acrylic acid-2-hydroxyethyl copolymer, ethylene ・ (meth) acrylic acid-2-hydroxy Propylene copolymer, ethylene / (meth) acrylate glycidyl copolymer, ethylene / dimethyl maleate copolymer, ethylene / diethyl maleate copolymer, ethylene / dimethyl fumarate copolymer, ethylene / diethyl fumarate copolymer Ethylene / unsaturated carboxylic acid ester copolymer such as polymer; ethylene / (meth) acrylic Copolymers, ethylene / maleic acid copolymers, ethylene / fumaric acid copolymers, ethylene / unsaturated carboxylic acid copolymers such as ethylene / crotonic acid copolymers and their salts; ethylene / vinyl acetate copolymers Ethylene / vinyl ester copolymer such as ethylene / vinyl propionate copolymer, ethylene / vinyl butyrate copolymer, ethylene / vinyl stearate copolymer: one or two selected from ethylene / styrene copolymer, etc. More than species can be mentioned.
Among these, the ethylene / polar monomer copolymer is one or two selected from an ethylene / vinyl ester copolymer and an ethylene / unsaturated carboxylic acid ester copolymer from the balance between availability and performance. It is preferable to contain a seed or more, and it is particularly preferable to include an ethylene / vinyl acetate copolymer.
上記エチレン・酢酸ビニル共重合体は、エチレンと酢酸ビニルとの共重合体であり、通常はランダム共重合体である。
上記エチレン・酢酸ビニル共重合体中の酢酸ビニルに由来する構成単位の含有割合は、好ましくは１０質量％以上４７質量％以下、より好ましくは１３質量％以上３５質量％以下である。酢酸ビニルの含有量がこの範囲にあると、封止シートの接着性、耐候性、透明性、機械的性質のバランスにより一層優れる。また、封止シートを成膜する際にも、成膜性が良好となる。
酢酸ビニル含有量は、ＪＩＳ Ｋ６７３０に準拠して測定可能である。 The ethylene / vinyl acetate copolymer is a copolymer of ethylene and vinyl acetate, and is usually a random copolymer.
The content ratio of the structural unit derived from vinyl acetate in the ethylene / vinyl acetate copolymer is preferably 10% by mass to 47% by mass, and more preferably 13% by mass to 35% by mass. When the content of vinyl acetate is in this range, the balance of adhesion, weather resistance, transparency, and mechanical properties of the sealing sheet is further improved. In addition, when the sealing sheet is formed, the film forming property is improved.
The vinyl acetate content can be measured according to JIS K6730.
上記エチレン・酢酸ビニル共重合体中の酢酸ビニルに由来する構成単位の含有割合は、好ましくは１０質量％以上４７質量％以下、より好ましくは１３質量％以上３５質量％以下である。酢酸ビニルの含有量がこの範囲にあると、封止シートの接着性、耐候性、透明性、機械的性質のバランスにより一層優れる。また、封止シートを成膜する際にも、成膜性が良好となる。
酢酸ビニル含有量は、ＪＩＳ Ｋ６７３０に準拠して測定可能である。 The ethylene / vinyl acetate copolymer is a copolymer of ethylene and vinyl acetate, and is usually a random copolymer.
The content ratio of the structural unit derived from vinyl acetate in the ethylene / vinyl acetate copolymer is preferably 10% by mass to 47% by mass, and more preferably 13% by mass to 35% by mass. When the content of vinyl acetate is in this range, the balance of adhesion, weather resistance, transparency, and mechanical properties of the sealing sheet is further improved. In addition, when the sealing sheet is formed, the film forming property is improved.
The vinyl acetate content can be measured according to JIS K6730.
なお、エチレン・酢酸ビニル共重合体は、エチレンおよび酢酸ビニルのみからなる二元共重合体が好ましいが、エチレンおよび酢酸ビニルの他に、例えばギ酸ビニル、グリコール酸ビニル、プロピオン酸ビニル、安息香酸ビニル等のビニルエステル系単量体；アクリル酸、メタクリル酸、エタクリル酸、或いはこれらの塩もしくはアルキルエステル等のアクリル系単重体；等から選択される一種または二種以上の共重合成分として含んでもよい。上記エチレンおよび酢酸ビニル以外の共重合成分を含む場合、エチレン・酢酸ビニル共重合体中の上記エチレンおよび酢酸ビニル以外の共重合成分の量を０．５質量％以上５質量％以下とすることが好ましい。
The ethylene / vinyl acetate copolymer is preferably a binary copolymer consisting only of ethylene and vinyl acetate. In addition to ethylene and vinyl acetate, for example, vinyl formate, vinyl glycolate, vinyl propionate, vinyl benzoate. A vinyl ester monomer such as acrylic acid, methacrylic acid, ethacrylic acid, or an acrylic monomer such as a salt or alkyl ester thereof; . When a copolymer component other than ethylene and vinyl acetate is included, the amount of the copolymer component other than ethylene and vinyl acetate in the ethylene / vinyl acetate copolymer may be 0.5 mass% or more and 5 mass% or less. preferable.
ＡＳＴＭ Ｄ １２３８による１９０℃、２１６０ｇ荷重でのエチレン・酢酸ビニル共重合体のメルトフローレート（ＭＦＲ）は、好ましくは５ｇ／１０分以上４５ｇ／１０分以下、より好ましくは５ｇ／１０分以上４０ｇ／１０分以下、更に好ましくは１０ｇ／１０分以上３０ｇ／１０分以下である。
エチレン・酢酸ビニル共重合体のＭＦＲが上記範囲であると、押出成形性が優れる。エチレン・酢酸ビニル共重合体のＭＦＲは、重合反応の際の重合温度、重合圧力、並びに重合系内の極性モノマーのモノマー濃度と水素濃度のモル比率等を調整することにより、調整することができる。 The melt flow rate (MFR) of the ethylene / vinyl acetate copolymer at 190 ° C. and 2160 g load according to ASTM D 1238 is preferably 5 g / 10 min to 45 g / 10 min, more preferably 5 g / 10 min to 40 g / It is 10 minutes or less, more preferably 10 g / 10 minutes or more and 30 g / 10 minutes or less.
When the MFR of the ethylene / vinyl acetate copolymer is within the above range, the extrusion moldability is excellent. The MFR of the ethylene / vinyl acetate copolymer can be adjusted by adjusting the polymerization temperature during the polymerization reaction, the polymerization pressure, and the molar ratio between the monomer concentration and the hydrogen concentration of the polar monomer in the polymerization system. .
エチレン・酢酸ビニル共重合体のＭＦＲが上記範囲であると、押出成形性が優れる。エチレン・酢酸ビニル共重合体のＭＦＲは、重合反応の際の重合温度、重合圧力、並びに重合系内の極性モノマーのモノマー濃度と水素濃度のモル比率等を調整することにより、調整することができる。 The melt flow rate (MFR) of the ethylene / vinyl acetate copolymer at 190 ° C. and 2160 g load according to ASTM D 1238 is preferably 5 g / 10 min to 45 g / 10 min, more preferably 5 g / 10 min to 40 g / It is 10 minutes or less, more preferably 10 g / 10 minutes or more and 30 g / 10 minutes or less.
When the MFR of the ethylene / vinyl acetate copolymer is within the above range, the extrusion moldability is excellent. The MFR of the ethylene / vinyl acetate copolymer can be adjusted by adjusting the polymerization temperature during the polymerization reaction, the polymerization pressure, and the molar ratio between the monomer concentration and the hydrogen concentration of the polar monomer in the polymerization system. .
本実施形態の封止シートは、例えば、酢酸ビニル含有量や、メルトフローレート等が異なる２種以上のエチレン・酢酸ビニル共重合体を用いてもよい、２種以上のエチレン・酢酸ビニル共重合体を用いる場合には、これらの総量を上記範囲とすることが好ましい。
The sealing sheet of this embodiment may use, for example, two or more ethylene / vinyl acetate copolymers having different vinyl acetate contents, melt flow rates, etc. When using coalescence, it is preferable that the total amount of these be in the above range.
上記エチレン・極性モノマー共重合体の含有量は、当該封止シートに含まれる樹脂成分の全体を１００質量％としたとき、好ましくは８０質量％以上、より好ましくは９０質量％以上、さらに好ましくは９５質量％以上、そして、特に好ましくは１００質量％である。これにより、透明性、接着性、耐熱性、柔軟性、外観、架橋特性、電気特性および押出成形性等の諸特性のバランスにより優れた封止シートを得ることができる。
The content of the ethylene / polar monomer copolymer is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 100% by mass when the entire resin component contained in the sealing sheet is 100% by mass. It is 95% by mass or more, and particularly preferably 100% by mass. Thereby, the sealing sheet excellent in the balance of various characteristics, such as transparency, adhesiveness, heat resistance, a softness | flexibility, an external appearance, a crosslinking characteristic, an electrical property, and extrusion moldability, can be obtained.
上記樹脂成分の含有量は、当該封止シートの全体を１００質量％としたとき、好ましくは５０質量％以上、より好ましくは７０質量％以上、さらに好ましくは８０質量％以上、特に好ましくは９０質量％以上である。これにより、透明性、接着性、耐熱性、柔軟性、外観、架橋特性、電気特性および押出成形性等の諸特性のバランスにより優れた封止シートを得ることができる。
The content of the resin component is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass when the entire sealing sheet is 100% by mass. % Or more. Thereby, the sealing sheet excellent in the balance of various characteristics, such as transparency, adhesiveness, heat resistance, a softness | flexibility, an external appearance, a crosslinking characteristic, an electrical property, and extrusion moldability, can be obtained.
上記エチレン・極性モノマー共重合体の製造方法は特に限定されず、公知の方法により製造することができる。例えば、ラジカル発生剤の存在下、５００～４０００気圧、１００～３００℃で溶媒や連鎖移動剤の存在下または不存在下で、エチレン、極性モノマー、必要に応じて他の共重合成分を共重合させることにより製造することができる。
The method for producing the ethylene / polar monomer copolymer is not particularly limited, and can be produced by a known method. For example, in the presence of a radical generator, copolymerization of ethylene, polar monomers, and other copolymerization components as necessary in the presence or absence of a solvent or chain transfer agent at 500 to 4000 atm and 100 to 300 ° C Can be manufactured.
＜架橋剤＞
架橋剤としては、例えば、有機過酸化物を用いることができる。
本実施形態の封止シートにおいて、架橋剤を含有することにより、上記エチレン・極性モノマー共重合体を架橋することができたり、シランカップリング剤を上記エチレン・極性モノマー共重合体へグラフトすることができたりする。上記エチレン・極性モノマー共重合体を架橋することにより、得られる封止シートの耐熱性や耐候性が良好となる。 <Crosslinking agent>
As the crosslinking agent, for example, an organic peroxide can be used.
In the encapsulating sheet of this embodiment, the ethylene / polar monomer copolymer can be cross-linked by containing a cross-linking agent, or the silane coupling agent can be grafted onto the ethylene / polar monomer copolymer. I can do it. By crosslinking the ethylene / polar monomer copolymer, the heat resistance and weather resistance of the obtained sealing sheet are improved.
架橋剤としては、例えば、有機過酸化物を用いることができる。
本実施形態の封止シートにおいて、架橋剤を含有することにより、上記エチレン・極性モノマー共重合体を架橋することができたり、シランカップリング剤を上記エチレン・極性モノマー共重合体へグラフトすることができたりする。上記エチレン・極性モノマー共重合体を架橋することにより、得られる封止シートの耐熱性や耐候性が良好となる。 <Crosslinking agent>
As the crosslinking agent, for example, an organic peroxide can be used.
In the encapsulating sheet of this embodiment, the ethylene / polar monomer copolymer can be cross-linked by containing a cross-linking agent, or the silane coupling agent can be grafted onto the ethylene / polar monomer copolymer. I can do it. By crosslinking the ethylene / polar monomer copolymer, the heat resistance and weather resistance of the obtained sealing sheet are improved.
封止シート中の架橋剤の含有量は、エチレン・極性モノマー共重合体１００質量部に対し、好ましくは０．１質量部以上５質量部以下であり、より好ましくは０．２質量部以上２質量部以下であり、さらに好ましくは０．２質量部以上１質量部以下である。架橋剤の含有量が上記下限値以上であると、封止シートの架橋特性の低下を抑制し、シランカップリング剤のエチレン・極性モノマー共重合体の主鎖へのグラフト反応を良好にして、耐熱性、接着性の低下を抑制することができる。また、架橋剤の含有量が上記上限値以下であると、架橋剤の分解生成物等の発生量が一層低下し、封止シート中に気泡が発生するのをより確実に抑制することができる。
The content of the crosslinking agent in the sealing sheet is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 0.2 parts by mass or more and 2 parts by mass with respect to 100 parts by mass of the ethylene / polar monomer copolymer. It is not more than part by mass, and more preferably not less than 0.2 part by mass and not more than 1 part by mass. When the content of the cross-linking agent is not less than the above lower limit value, the deterioration of the cross-linking characteristics of the sealing sheet is suppressed, and the graft reaction to the main chain of the ethylene / polar monomer copolymer of the silane coupling agent is improved. A decrease in heat resistance and adhesiveness can be suppressed. Further, when the content of the cross-linking agent is not more than the above upper limit value, the generation amount of the decomposition product of the cross-linking agent is further reduced, and generation of bubbles in the sealing sheet can be more reliably suppressed. .
太陽電池モジュールの生産性を考慮すると、有機過酸化物としては、半減期が１０時間以下であり、かつ分解温度が１０５℃以下であるものが好ましい。また安全性の面から、最高保存温度が１０℃以上であるものが好ましい。このような有機過酸化物の例としては、ジラウロイルパーオキサイド、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート、ジベンゾイルパーオキサイド、シクロヘキサノンパーオキサイド、ジ－ｔ－ブチルパーフタレート、クメンヒドロパーオキシド、ｔ－ブチルヒドロパーオキシド、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキセン、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、ｔ－アミルパーオキシ－２－エチルヘキサノエート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔ－ブチルパーオキシイソブチレート、ｔ－ブチルパーオキシマレイン酸、１，１－ジ（ｔ－アミルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ジ（ｔ－アミルパーオキシ）シクロヘキサン、ｔ－アミルパーオキシイソノナノエート、ｔ－アミルパーオキシノルマルオクトエート、１，１－ジ（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－ジ（ｔ－ブチルパーオキシ）シクロヘキサン、ｔ－ブチルパーオキシイソプロピルカーボネート、ｔ－ブチルパーオキシ－２－エチルヘキシルカーボネート、２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン、ｔ－アミルパーオキシベンゾエート、ｔ－ブチルパーオキシアセテート、ｔ－ブチルパーオキシイソノナノエート、ｔ－ブチルパーオキシベンゾエート、２，２－ジ（ブチルパーオキシ）ブタン、ｎ－ブチル－４，４－ジ（ｔ－ブチルパーオキシ）プチレート、メチルエチルケトンパ－オキサイド、エチル－３，３－ジ（ｔ－ブチルパーオキシ）ブチレート、ジクミルパーオキサイド、ｔ－ブチルクミルパーオキサイド、ｔ－ブチルパーオキシベンゾエート、ジ－ｔ－ブチルパーオキサイド、１，１，３，３－テトララメチルブチルハイドロパーオキサイド、アセチルアセトンパーオキサイド等から選択される一種または二種以上を用いることができる。
Considering the productivity of the solar cell module, it is preferable that the organic peroxide has a half-life of 10 hours or less and a decomposition temperature of 105 ° C. or less. From the viewpoint of safety, it is preferable that the maximum storage temperature is 10 ° C. or higher. Examples of such organic peroxides include dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dibenzoyl peroxide, cyclohexanone peroxide, di-t -Butyl perphthalate, cumene hydroperoxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexane, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, 1,1-di (t-amylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-amyl) -Oxy) cyclohexane, t-amylperoxyisononanoate, t-amylperoxynormal octoate, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di ( t-butylperoxy) cyclohexane, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-amylperoxy Benzoate, t-butyl peroxyacetate, t-butyl peroxyisononanoate, t-butyl peroxybenzoate, 2,2-di (butylperoxy) butane, n-butyl-4,4-di (t-butyl Peroxy) petitate, methyl ethyl ketone peroxide, ethyl −3,3-di (t-butylperoxy) butyrate, dicumyl peroxide, t-butylcumyl peroxide, t-butylperoxybenzoate, di-t-butylperoxide, 1,1,3,3- One or more selected from tetralamethylbutyl hydroperoxide, acetylacetone peroxide, and the like can be used.
これらの中でも、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキセン、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、ｔ－ブチルパーオキシ－２－エチルヘキシルカーボネート、ｔ－ブチルパーオキシベンゾエートから選択される一種または二種以上を用いることが好ましい。
Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperoxy- It is preferable to use one or more selected from 2-ethylhexyl carbonate and t-butyl peroxybenzoate.
本実施形態の封止シートは、架橋剤を含有することで優れた架橋特性を有しているため、真空ラミネーターと架橋炉の二段階の接着工程を経る必要はなく、高温度で短時間に完結することができる。
Since the sealing sheet of the present embodiment has excellent crosslinking characteristics by containing a crosslinking agent, it is not necessary to go through a two-step bonding process of a vacuum laminator and a crosslinking furnace, and at a high temperature in a short time. Can be completed.
＜架橋助剤＞
架橋助剤としては、ジビニル芳香族化合物、シアヌレート化合物、ジアリル化合物、トリアリル化合物、オキシム化合物およびマレイミド化合物からなる群より選択される一種または二種以上を用いることができる。
封止シート中の架橋助剤の含有量は、エチレン・極性モノマー共重合体１００質量部に対して、１０質量部以下であることが好ましく、５．０質量部以下であることがより好ましく、２．０質量部以下であることが特に好ましい。
また、封止シート中の架橋助剤の含有量は、エチレン・極性モノマー共重合体１００質量部に対して、０．１質量部以上であることが好ましく、０．５質量部以上であることがより好ましい。これにより、適度な架橋構造とすることができ、封止シートの耐熱性、機械物性、および接着性を向上できる。 <Crosslinking aid>
As the crosslinking aid, one or more selected from the group consisting of divinyl aromatic compounds, cyanurate compounds, diallyl compounds, triallyl compounds, oxime compounds and maleimide compounds can be used.
The content of the crosslinking aid in the encapsulating sheet is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, with respect to 100 parts by mass of the ethylene / polar monomer copolymer. The amount is particularly preferably 2.0 parts by mass or less.
Moreover, it is preferable that it is 0.1 mass part or more with respect to 100 mass parts of ethylene / polar monomer copolymers, and content of the crosslinking adjuvant in a sealing sheet is 0.5 mass part or more. Is more preferable. Thereby, it can be set as a moderate crosslinked structure and can improve the heat resistance of a sealing sheet, a mechanical physical property, and adhesiveness.
架橋助剤としては、ジビニル芳香族化合物、シアヌレート化合物、ジアリル化合物、トリアリル化合物、オキシム化合物およびマレイミド化合物からなる群より選択される一種または二種以上を用いることができる。
封止シート中の架橋助剤の含有量は、エチレン・極性モノマー共重合体１００質量部に対して、１０質量部以下であることが好ましく、５．０質量部以下であることがより好ましく、２．０質量部以下であることが特に好ましい。
また、封止シート中の架橋助剤の含有量は、エチレン・極性モノマー共重合体１００質量部に対して、０．１質量部以上であることが好ましく、０．５質量部以上であることがより好ましい。これにより、適度な架橋構造とすることができ、封止シートの耐熱性、機械物性、および接着性を向上できる。 <Crosslinking aid>
As the crosslinking aid, one or more selected from the group consisting of divinyl aromatic compounds, cyanurate compounds, diallyl compounds, triallyl compounds, oxime compounds and maleimide compounds can be used.
The content of the crosslinking aid in the encapsulating sheet is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, with respect to 100 parts by mass of the ethylene / polar monomer copolymer. The amount is particularly preferably 2.0 parts by mass or less.
Moreover, it is preferable that it is 0.1 mass part or more with respect to 100 mass parts of ethylene / polar monomer copolymers, and content of the crosslinking adjuvant in a sealing sheet is 0.5 mass part or more. Is more preferable. Thereby, it can be set as a moderate crosslinked structure and can improve the heat resistance of a sealing sheet, a mechanical physical property, and adhesiveness.
ジビニル芳香族化合物としては、例えば、ジビニルベンゼン、ジ－ｉ－プロペニルベンゼン等が挙げられる。
シアヌレート化合物としては、例えば、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が挙げられる。
ジアリル化合物としては、例えば、ジアリルフタレート等が挙げられる。
トリアリル化合物としては、例えば、ペンタエリスリトールトリアリルエーテル等が挙げられる。
オキシム化合物としては、例えば、ｐ－キノンジオキシム、ｐ－ｐ'－ジベンゾイルキノンジオキシム等が挙げられる。
マレイミド化合物としては、例えば、ｍ－フェニレンジマレイミド等が挙げられる。 Examples of the divinyl aromatic compound include divinylbenzene and di-i-propenylbenzene.
Examples of the cyanurate compound include triallyl cyanurate and triallyl isocyanurate.
Examples of diallyl compounds include diallyl phthalate.
Examples of the triallyl compound include pentaerythritol triallyl ether.
Examples of the oxime compound include p-quinone dioxime, pp′-dibenzoylquinone dioxime, and the like.
Examples of the maleimide compound include m-phenylene dimaleimide.
シアヌレート化合物としては、例えば、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が挙げられる。
ジアリル化合物としては、例えば、ジアリルフタレート等が挙げられる。
トリアリル化合物としては、例えば、ペンタエリスリトールトリアリルエーテル等が挙げられる。
オキシム化合物としては、例えば、ｐ－キノンジオキシム、ｐ－ｐ'－ジベンゾイルキノンジオキシム等が挙げられる。
マレイミド化合物としては、例えば、ｍ－フェニレンジマレイミド等が挙げられる。 Examples of the divinyl aromatic compound include divinylbenzene and di-i-propenylbenzene.
Examples of the cyanurate compound include triallyl cyanurate and triallyl isocyanurate.
Examples of diallyl compounds include diallyl phthalate.
Examples of the triallyl compound include pentaerythritol triallyl ether.
Examples of the oxime compound include p-quinone dioxime, pp′-dibenzoylquinone dioxime, and the like.
Examples of the maleimide compound include m-phenylene dimaleimide.
＜トリ（メタ）アクリレート化合物＞
本実施形態の封止シートは下記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物を含有している。 <Tri (meth) acrylate compound>
The sealing sheet of this embodiment contains a glycerin tri (meth) acrylate compound represented by the following formula (I).
本実施形態の封止シートは下記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物を含有している。 <Tri (meth) acrylate compound>
The sealing sheet of this embodiment contains a glycerin tri (meth) acrylate compound represented by the following formula (I).
上記式（Ｉ）におけるＲ１、Ｒ２およびＲ３がすべて水素原子であることが好ましい。
Ｒ１、Ｒ２およびＲ３が水素原子であると、メチル基である化合物に比べ、耐ＰＩＤ性能に優れる。
また、上記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物としては、グリセリンプロポキシトリ（メタ）アクリレートおよびグリセリンエトキシトリ（メタ）アクリレートが好ましく、グリセリンプロポキシトリアクリレートおよびグリセリンエトキシトリアクリレートがより好ましい。 R 1 , R 2 and R 3 in the above formula (I) are preferably all hydrogen atoms.
When R 1 , R 2, and R 3 are hydrogen atoms, the PID resistance is excellent as compared with a compound that is a methyl group.
Further, as the glycerin tri (meth) acrylate compound represented by the above formula (I), glycerin propoxytri (meth) acrylate and glycerin ethoxytri (meth) acrylate are preferable, and glycerin propoxytriacrylate and glycerin ethoxytriacrylate are more preferable. .
Ｒ１、Ｒ２およびＲ３が水素原子であると、メチル基である化合物に比べ、耐ＰＩＤ性能に優れる。
また、上記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物としては、グリセリンプロポキシトリ（メタ）アクリレートおよびグリセリンエトキシトリ（メタ）アクリレートが好ましく、グリセリンプロポキシトリアクリレートおよびグリセリンエトキシトリアクリレートがより好ましい。 R 1 , R 2 and R 3 in the above formula (I) are preferably all hydrogen atoms.
When R 1 , R 2, and R 3 are hydrogen atoms, the PID resistance is excellent as compared with a compound that is a methyl group.
Further, as the glycerin tri (meth) acrylate compound represented by the above formula (I), glycerin propoxytri (meth) acrylate and glycerin ethoxytri (meth) acrylate are preferable, and glycerin propoxytriacrylate and glycerin ethoxytriacrylate are more preferable. .
また、封止シートの成形時の分散性に優れる観点から、上記式（Ｉ）におけるｘ＋ｙ＋ｚが３以上６以下の整数であることが好ましく、３または６であることが特に好ましい。この場合、ｘ＋ｙ＋ｚが３の化合物とｘ＋ｙ＋ｚが６の化合物との混合物であってもよいし、ｘ＋ｙ＋ｚが３または６以外の化合物が３０質量％以下混合していてもよい。
Further, from the viewpoint of excellent dispersibility during molding of the sealing sheet, x + y + z in the above formula (I) is preferably an integer of 3 or more, and particularly preferably 3 or 6. In this case, a mixture of a compound having x + y + z of 3 and a compound having x + y + z of 6 may be used, or a compound other than x + y + z of 3 or 6 may be mixed by 30% by mass or less.
上記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物の含有量は、エチレン・極性モノマー共重合体１００質量部に対して、０．１質量部以上２．０質量部以下であることが好ましく、０．１質量部以上１．０質量部以下であることが特に好ましい。グリセリントリ（メタ）アクリレート化合物の含有量が上記下限値以上であると、得られる太陽電池モジュールのＰＩＤ耐性をより良好なものとすることができる。また、グリセリントリ（メタ）アクリレート化合物の含有量が上記上限値以下であると、封止シートを保管した際に、ブリードアウトの発生を抑制することができる。
また、架橋助剤と上記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物の含有量の合計が、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０．２質量部以上５．０質量部以下であり、より好ましくは０．５質量部以上３．０質量部以下であり、さらに好ましくは０．５質量部以上２．０質量部以下である。 The content of the glycerin tri (meth) acrylate compound represented by the above formula (I) is 0.1 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the ethylene / polar monomer copolymer. It is particularly preferably 0.1 parts by mass or more and 1.0 part by mass or less. When the content of the glycerin tri (meth) acrylate compound is not less than the above lower limit value, the PID resistance of the obtained solar cell module can be further improved. Moreover, when content of a glycerol tri (meth) acrylate compound is below the said upper limit, generation | occurrence | production of bleed-out can be suppressed when a sealing sheet is stored.
Further, the total content of the crosslinking aid and the glycerin tri (meth) acrylate compound represented by the above formula (I) is preferably 0.2 parts by mass or more with respect to 100 parts by mass of the ethylene / polar monomer copolymer. 5.0 parts by mass or less, more preferably 0.5 parts by mass or more and 3.0 parts by mass or less, and further preferably 0.5 parts by mass or more and 2.0 parts by mass or less.
また、架橋助剤と上記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物の含有量の合計が、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０．２質量部以上５．０質量部以下であり、より好ましくは０．５質量部以上３．０質量部以下であり、さらに好ましくは０．５質量部以上２．０質量部以下である。 The content of the glycerin tri (meth) acrylate compound represented by the above formula (I) is 0.1 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the ethylene / polar monomer copolymer. It is particularly preferably 0.1 parts by mass or more and 1.0 part by mass or less. When the content of the glycerin tri (meth) acrylate compound is not less than the above lower limit value, the PID resistance of the obtained solar cell module can be further improved. Moreover, when content of a glycerol tri (meth) acrylate compound is below the said upper limit, generation | occurrence | production of bleed-out can be suppressed when a sealing sheet is stored.
Further, the total content of the crosslinking aid and the glycerin tri (meth) acrylate compound represented by the above formula (I) is preferably 0.2 parts by mass or more with respect to 100 parts by mass of the ethylene / polar monomer copolymer. 5.0 parts by mass or less, more preferably 0.5 parts by mass or more and 3.0 parts by mass or less, and further preferably 0.5 parts by mass or more and 2.0 parts by mass or less.
＜その他の添加剤＞
本実施形態の封止シートは、以上詳述した諸成分以外の各種成分を、本発明の目的を損なわない範囲において、適宜含有してもよい。例えば、シランカップリング剤、紫外線吸収剤、光安定剤、酸化防止剤等から選ばれる一種または二種以上の添加剤を適宜含有することができる。 <Other additives>
The encapsulating sheet of the present embodiment may appropriately contain various components other than the components detailed above in a range not impairing the object of the present invention. For example, one or two or more additives selected from silane coupling agents, ultraviolet absorbers, light stabilizers, antioxidants and the like can be appropriately contained.
本実施形態の封止シートは、以上詳述した諸成分以外の各種成分を、本発明の目的を損なわない範囲において、適宜含有してもよい。例えば、シランカップリング剤、紫外線吸収剤、光安定剤、酸化防止剤等から選ばれる一種または二種以上の添加剤を適宜含有することができる。 <Other additives>
The encapsulating sheet of the present embodiment may appropriately contain various components other than the components detailed above in a range not impairing the object of the present invention. For example, one or two or more additives selected from silane coupling agents, ultraviolet absorbers, light stabilizers, antioxidants and the like can be appropriately contained.
（シランカップリング剤）
本実施形態の封止シート中のシランカップリング剤の含有量は、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質量部以上５質量部以下であり、より好ましくは０．１質量部以上３質量部以下であり、さらに好ましくは０．１質量部以上１．５質量部以下である。
シランカップリング剤の含有量が上記下限値以上であると、封止シートと他の部材との接着強度をより良好なものとすることができる。一方、シランカップリング剤が上記上限値以下であると、シランカップリング剤のメトキシ基、エトキシ基由来の加水分解により発生するメタノール、エタノールが少なくなり、封止シート中に気泡が発生するのをより確実に抑制することができる。 (Silane coupling agent)
The content of the silane coupling agent in the sealing sheet of the present embodiment is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 100 parts by mass of the ethylene / polar monomer copolymer. It is 0.1 mass part or more and 3 mass parts or less, More preferably, it is 0.1 mass part or more and 1.5 mass parts or less.
When the content of the silane coupling agent is not less than the above lower limit value, the adhesive strength between the sealing sheet and the other member can be further improved. On the other hand, when the silane coupling agent is not more than the above upper limit value, methanol and ethanol generated by hydrolysis derived from the methoxy group and ethoxy group of the silane coupling agent are reduced, and bubbles are generated in the sealing sheet. It can suppress more reliably.
本実施形態の封止シート中のシランカップリング剤の含有量は、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質量部以上５質量部以下であり、より好ましくは０．１質量部以上３質量部以下であり、さらに好ましくは０．１質量部以上１．５質量部以下である。
シランカップリング剤の含有量が上記下限値以上であると、封止シートと他の部材との接着強度をより良好なものとすることができる。一方、シランカップリング剤が上記上限値以下であると、シランカップリング剤のメトキシ基、エトキシ基由来の加水分解により発生するメタノール、エタノールが少なくなり、封止シート中に気泡が発生するのをより確実に抑制することができる。 (Silane coupling agent)
The content of the silane coupling agent in the sealing sheet of the present embodiment is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 100 parts by mass of the ethylene / polar monomer copolymer. It is 0.1 mass part or more and 3 mass parts or less, More preferably, it is 0.1 mass part or more and 1.5 mass parts or less.
When the content of the silane coupling agent is not less than the above lower limit value, the adhesive strength between the sealing sheet and the other member can be further improved. On the other hand, when the silane coupling agent is not more than the above upper limit value, methanol and ethanol generated by hydrolysis derived from the methoxy group and ethoxy group of the silane coupling agent are reduced, and bubbles are generated in the sealing sheet. It can suppress more reliably.
シランカップリング剤としては、例えば、ビニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリス（β－メトキシエトキシシラン）、２－（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、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジトリエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、ｐ－スチリルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、３－イソシアネートプロピルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－アクリロキシプロピルトリメトキシシラン等から選択される一種または二種以上を用いることができる。
これらの中でも、接着性向上の観点から、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－アミノプロピルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、ビニルトリエトキシシランから選択される一種または二種以上を用いることが好ましい。 Examples of the silane coupling agent include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxysilane), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropylmethyl. Dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethylditriethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- ( 1,3-di Til-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl One or more selected from dimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, etc. Can be used.
Among these, from the viewpoint of improving adhesion, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- It is preferable to use one or more selected from methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and vinyltriethoxysilane.
これらの中でも、接着性向上の観点から、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－アミノプロピルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、ビニルトリエトキシシランから選択される一種または二種以上を用いることが好ましい。 Examples of the silane coupling agent include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxysilane), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropylmethyl. Dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethylditriethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- ( 1,3-di Til-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl One or more selected from dimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, etc. Can be used.
Among these, from the viewpoint of improving adhesion, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- It is preferable to use one or more selected from methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and vinyltriethoxysilane.
（紫外線吸収剤、光安定剤、酸化防止剤）
本実施形態の封止シートは、紫外線吸収剤、光安定剤および酸化防止剤からなる群より選択される一種または二種以上の添加剤が含有されてもよい。これらの添加剤の合計含有量は、エチレン・極性モノマー共重合体１００質量部に対して、０．００５質量部以上５質量部以下であることが好ましい。この範囲とすることで、高温高湿への耐性、ヒートサイクルの耐性、耐候安定性、及び耐熱安定性を向上する効果を十分に確保し、かつ、封止シートの透明性や接着性の低下を防ぐことができる。さらに、上記三種から選ばれる少なくとも二種の添加剤を含有することが好ましく、とくに、上記三種の全てが含有されていることが好ましい。 (UV absorber, light stabilizer, antioxidant)
The encapsulating sheet of this embodiment may contain one or two or more additives selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant. The total content of these additives is preferably 0.005 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the ethylene / polar monomer copolymer. By making it within this range, the effect of improving the resistance to high temperature and high humidity, heat cycle resistance, weather resistance stability, and heat stability is sufficiently secured, and the transparency and adhesiveness of the sealing sheet are lowered. Can be prevented. Furthermore, it is preferable to contain at least two kinds of additives selected from the above three kinds, and it is particularly preferred that all of the above three kinds are contained.
本実施形態の封止シートは、紫外線吸収剤、光安定剤および酸化防止剤からなる群より選択される一種または二種以上の添加剤が含有されてもよい。これらの添加剤の合計含有量は、エチレン・極性モノマー共重合体１００質量部に対して、０．００５質量部以上５質量部以下であることが好ましい。この範囲とすることで、高温高湿への耐性、ヒートサイクルの耐性、耐候安定性、及び耐熱安定性を向上する効果を十分に確保し、かつ、封止シートの透明性や接着性の低下を防ぐことができる。さらに、上記三種から選ばれる少なくとも二種の添加剤を含有することが好ましく、とくに、上記三種の全てが含有されていることが好ましい。 (UV absorber, light stabilizer, antioxidant)
The encapsulating sheet of this embodiment may contain one or two or more additives selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant. The total content of these additives is preferably 0.005 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the ethylene / polar monomer copolymer. By making it within this range, the effect of improving the resistance to high temperature and high humidity, heat cycle resistance, weather resistance stability, and heat stability is sufficiently secured, and the transparency and adhesiveness of the sealing sheet are lowered. Can be prevented. Furthermore, it is preferable to contain at least two kinds of additives selected from the above three kinds, and it is particularly preferred that all of the above three kinds are contained.
紫外線吸収剤としては、例えば、２－ヒドロキシ－４－ノルマル－オクチルオキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２，２－ジヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－メトキシ－２－カルボキシベンゾフェノン、２－ヒドロキシ－４－Ｎ－オクトキシベンゾフェノン等のベンゾフェノン系紫外線吸収剤；２－（２－ヒドロキシ－３，５－ジ－ｔ－ブチルフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－５－ｔ－オクチルフェニル）ベンゾトリアゾール等のベンゾトリアゾール系紫外線吸収剤；フェニルサリチレート、ｐ－オクチルフェニルサリチレート等のサリチル酸エステル系紫外線吸収剤等から選択される一種または二種以上を用いることができる。
Examples of the ultraviolet absorber include 2-hydroxy-4-normal-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2- Benzophenone ultraviolet absorbers such as carboxybenzophenone and 2-hydroxy-4-N-octoxybenzophenone; 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy- Benzotriazole ultraviolet absorbers such as 5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-t-octylphenyl) benzotriazole; salicylic acid esters such as phenyl salicylate and p-octylphenyl salicylate Select from UV absorbers, etc. It is the one or may be used two or more.
光安定剤としては、例えば、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、ポリ［｛６－（１，１，３，３－テトラメチルブチル）アミノ－１，３，５－トリアジン－２，４－ジイル｝｛（２，２，６，６－テトラメチル－４－ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６－テトラメチル－４－ピペリジル）イミノ｝］等のヒンダードアミン系化合物、ヒンダードピペリジン系化合物等から選択される一種または二種以上を用いることができる。
Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3. , 5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino }] Or the like selected from hindered amine compounds, hindered piperidine compounds and the like can be used.
酸化防止剤としては、例えば、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、ビス［２，４－ビス（１，１－ジメチルエチル）－６－メチルフェニル］エチルエステル亜リン酸、テトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）［１，１－ビフェニル］－４，４'－ジイルビスホスフォナイト、ビス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールジホスファイト等のホスファイト系酸化防止剤；３－ヒドロキシ－５，７－ジ－ｔｅｒｔ－ブチル－フラン－２－オンとｏ－キシレンとの反応生成物等のラクトン系酸化防止剤；３，３'，３"，５，５'，５"－ヘキサ－ｔｅｒｔ－ブチル－ａ，ａ'，ａ"－（メチレン－２，４，６－トリイル）トリ－ｐ－クレゾール、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）ベンジルベンゼン、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、チオジエチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］等のヒンダードフェノール系酸化防止剤；硫黄系酸化防止剤；アミン系酸化防止剤等から選択される一種または二種以上を用いることができる。これらの中でも、ホスファイト系酸化防止剤、およびヒンダードフェノール系酸化防止剤が好ましい。
Examples of the antioxidant include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid Tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphos Phosphite-based antioxidants such as phites; Lactone-based antioxidants such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene; 3,3 ′ , 3 ", 5,5 ', 5" -hexa-tert-butyl-a, a', a "-(methylene-2,4,6-triyl) tri-p-cresol, 1,3,5-trimethyl -2, 4, 6-tris (3,5-di-tert-butyl-4-hydroxyphenyl) benzylbenzene, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3 Hindered phenolic oxidation of-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], etc. One or two or more selected from an antioxidant, a sulfur-based antioxidant, an amine-based antioxidant, etc. Among these, a phosphite-based antioxidant and a hindered phenol-based antioxidant can be used. preferable.
＜封止シート＞
本実施形態における封止シートの厚みは特に限定されないが、０．０１ｍｍ以上２ｍｍ以下が好ましく、０．２ｍｍ以上１．２ｍｍ以下がより好ましい。厚みがこの範囲内であると、ラミネート工程における、受光面側保護部材、太陽電池素子、薄膜電極等の破損が抑制でき、かつ、十分な光線透過率を確保することにより高い光発電量を得ることができる。さらには、低温での太陽電池モジュールのラミネート成形ができるので好ましい。 <Sealing sheet>
Although the thickness of the sealing sheet in this embodiment is not specifically limited, 0.01 mm or more and 2 mm or less are preferable, and 0.2 mm or more and 1.2 mm or less are more preferable. When the thickness is within this range, damage to the light-receiving surface side protective member, solar cell element, thin film electrode, etc. in the laminating step can be suppressed, and a high amount of photovoltaic power can be obtained by ensuring sufficient light transmittance. be able to. Furthermore, it is preferable because the solar cell module can be laminated at a low temperature.
本実施形態における封止シートの厚みは特に限定されないが、０．０１ｍｍ以上２ｍｍ以下が好ましく、０．２ｍｍ以上１．２ｍｍ以下がより好ましい。厚みがこの範囲内であると、ラミネート工程における、受光面側保護部材、太陽電池素子、薄膜電極等の破損が抑制でき、かつ、十分な光線透過率を確保することにより高い光発電量を得ることができる。さらには、低温での太陽電池モジュールのラミネート成形ができるので好ましい。 <Sealing sheet>
Although the thickness of the sealing sheet in this embodiment is not specifically limited, 0.01 mm or more and 2 mm or less are preferable, and 0.2 mm or more and 1.2 mm or less are more preferable. When the thickness is within this range, damage to the light-receiving surface side protective member, solar cell element, thin film electrode, etc. in the laminating step can be suppressed, and a high amount of photovoltaic power can be obtained by ensuring sufficient light transmittance. be able to. Furthermore, it is preferable because the solar cell module can be laminated at a low temperature.
本実施形態の封止シートは本発明の目的を損なわない範囲で、他の層を積層してもよい。例えば、表面または裏面保護のためのハードコート層、接着層、反射防止層、ガスバリア層、防汚層等の層を有していてもよい。材質で分類するならば、紫外線硬化性樹脂からなる層、熱硬化性樹脂からなる層、ポリオレフィン樹脂からなる層、カルボン酸変性ポリオレフィン樹脂からなる層、フッ素含有樹脂からなる層、環状オレフィン（共）重合体からなる層、無機化合物からなる層等を挙げることができる。
The sealing sheet of this embodiment may be laminated with other layers as long as the object of the present invention is not impaired. For example, you may have layers, such as a hard-coat layer for surface or back surface protection, an adhesion layer, an antireflection layer, a gas barrier layer, and an antifouling layer. If classified by material, layer made of UV curable resin, layer made of thermosetting resin, layer made of polyolefin resin, layer made of carboxylic acid modified polyolefin resin, layer made of fluorine-containing resin, cyclic olefin (co) Examples thereof include a layer made of a polymer and a layer made of an inorganic compound.
本実施形態の封止シートの加熱時の収縮性について、ＪＩＳ Ｃ２３１８－１９９７に準じて測定した熱収縮率が２５％以下であることが好ましく、１５％以下であることがより好ましい。熱収縮率が上記上限値以下とすることにより、太陽電池モジュールを作製する際、太陽電池モジュール内で太陽電池素子が位置ずれすることや、太陽電池素子が破損することをより効果的に抑制することができる。
Regarding the shrinkability of the encapsulating sheet of the present embodiment when heated, the thermal shrinkage rate measured according to JIS C2318-1997 is preferably 25% or less, and more preferably 15% or less. By making the thermal shrinkage rate equal to or less than the above upper limit value, when the solar cell module is manufactured, the solar cell element is more effectively suppressed from being displaced or damaged in the solar cell module. be able to.
（封止シートの製造方法）
本実施形態の封止シートの製造方法は特に限定されないが、公知の各種の成形方法（キャスト成形、押出シート成形、インフレーション成形、射出成形、圧縮成形、カレンダ成形等）を採用することが可能である。とくに、押出成形とカレンダ成形が好ましい。 (Method for producing sealing sheet)
Although the manufacturing method of the sealing sheet of this embodiment is not particularly limited, various known molding methods (cast molding, extrusion sheet molding, inflation molding, injection molding, compression molding, calendar molding, etc.) can be employed. is there. In particular, extrusion molding and calendar molding are preferable.
本実施形態の封止シートの製造方法は特に限定されないが、公知の各種の成形方法（キャスト成形、押出シート成形、インフレーション成形、射出成形、圧縮成形、カレンダ成形等）を採用することが可能である。とくに、押出成形とカレンダ成形が好ましい。 (Method for producing sealing sheet)
Although the manufacturing method of the sealing sheet of this embodiment is not particularly limited, various known molding methods (cast molding, extrusion sheet molding, inflation molding, injection molding, compression molding, calendar molding, etc.) can be employed. is there. In particular, extrusion molding and calendar molding are preferable.
本実施形態の封止シートの製造方法は特に限定されないが、例えば、以下の方法が挙げられる。まず、エチレン・極性モノマー共重合体と、架橋剤と、架橋助剤と、上記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物と、必要に応じてその他の添加剤とをドライブレンドする。次いで、得られた混合物をホッパーから押出機に供給して必要に応じて架橋剤の一時間半減期温度よりも低い温度で溶融混練する。その後、押出機の先端からシート状に押出成形して封止シートを製造する。成形は、Ｔ－ダイ押出機、カレンダ成形機、インフレーション成形機等を使用する公知の方法によって行なうことができる。
また、架橋剤を含まないシートを上記方法により作製し、作製したシートに架橋剤を含浸法により添加してもよい。なお、架橋剤が二種以上含有されている場合には、最も低い架橋剤の一時間半減期温度よりも低い温度にて溶融混練すればよい。 Although the manufacturing method of the sealing sheet of this embodiment is not specifically limited, For example, the following method is mentioned. First, an ethylene / polar monomer copolymer, a crosslinking agent, a crosslinking assistant, a glycerin tri (meth) acrylate compound represented by the above formula (I), and other additives as needed are dry blended. . Next, the obtained mixture is supplied from the hopper to the extruder and melt-kneaded at a temperature lower than the one-hour half-life temperature of the crosslinking agent as necessary. Thereafter, a sealing sheet is produced by extrusion from the tip of the extruder into a sheet. The molding can be performed by a known method using a T-die extruder, a calendar molding machine, an inflation molding machine or the like.
Moreover, the sheet | seat which does not contain a crosslinking agent may be produced by the said method, and a crosslinking agent may be added to the produced sheet | seat by the impregnation method. In the case where two or more kinds of crosslinking agents are contained, melt kneading may be performed at a temperature lower than the one-hour half-life temperature of the lowest crosslinking agent.
また、架橋剤を含まないシートを上記方法により作製し、作製したシートに架橋剤を含浸法により添加してもよい。なお、架橋剤が二種以上含有されている場合には、最も低い架橋剤の一時間半減期温度よりも低い温度にて溶融混練すればよい。 Although the manufacturing method of the sealing sheet of this embodiment is not specifically limited, For example, the following method is mentioned. First, an ethylene / polar monomer copolymer, a crosslinking agent, a crosslinking assistant, a glycerin tri (meth) acrylate compound represented by the above formula (I), and other additives as needed are dry blended. . Next, the obtained mixture is supplied from the hopper to the extruder and melt-kneaded at a temperature lower than the one-hour half-life temperature of the crosslinking agent as necessary. Thereafter, a sealing sheet is produced by extrusion from the tip of the extruder into a sheet. The molding can be performed by a known method using a T-die extruder, a calendar molding machine, an inflation molding machine or the like.
Moreover, the sheet | seat which does not contain a crosslinking agent may be produced by the said method, and a crosslinking agent may be added to the produced sheet | seat by the impregnation method. In the case where two or more kinds of crosslinking agents are contained, melt kneading may be performed at a temperature lower than the one-hour half-life temperature of the lowest crosslinking agent.
２．太陽電池モジュールについて
本実施形態の封止シートは、太陽電池モジュールにおいて、太陽電池素子を封止するために用いられる。
太陽電池モジュールの構成としては、例えば表面側透明保護部材／受光面側封止シート（受光面側封止層）／太陽電池素子／裏面側封止シート（裏面側封止層）／裏面側保護部材（バックシート）をこの順に積層した構成が挙げられるが、特に限定されない。
本実施形態の封止シートは、上記受光面側封止シートおよび上記裏面側封止シートのいずれか一方、あるいは両方に用いられる。 2. About solar cell module The sealing sheet of this embodiment is used in order to seal a solar cell element in a solar cell module.
As the configuration of the solar cell module, for example, a front surface side transparent protective member / light receiving surface side sealing sheet (light receiving surface side sealing layer) / solar cell element / back surface side sealing sheet (back surface side sealing layer) / back surface side protection Although the structure which laminated | stacked the member (back sheet | seat) in this order is mentioned, it is not specifically limited.
The sealing sheet of this embodiment is used for either one or both of the light receiving surface side sealing sheet and the back surface side sealing sheet.
本実施形態の封止シートは、太陽電池モジュールにおいて、太陽電池素子を封止するために用いられる。
太陽電池モジュールの構成としては、例えば表面側透明保護部材／受光面側封止シート（受光面側封止層）／太陽電池素子／裏面側封止シート（裏面側封止層）／裏面側保護部材（バックシート）をこの順に積層した構成が挙げられるが、特に限定されない。
本実施形態の封止シートは、上記受光面側封止シートおよび上記裏面側封止シートのいずれか一方、あるいは両方に用いられる。 2. About solar cell module The sealing sheet of this embodiment is used in order to seal a solar cell element in a solar cell module.
As the configuration of the solar cell module, for example, a front surface side transparent protective member / light receiving surface side sealing sheet (light receiving surface side sealing layer) / solar cell element / back surface side sealing sheet (back surface side sealing layer) / back surface side protection Although the structure which laminated | stacked the member (back sheet | seat) in this order is mentioned, it is not specifically limited.
The sealing sheet of this embodiment is used for either one or both of the light receiving surface side sealing sheet and the back surface side sealing sheet.
図１に、本実施形態の太陽電池モジュール１０の断面図の一例を示す。
太陽電池モジュール１０は、複数の太陽電池素子１３と、太陽電池素子１３を挟んで封止する一対の受光面側封止シート１１と裏面側封止シート１２、および表面側透明保護部材１４および裏面側保護部材（バックシート）１５とを備える。 In FIG. 1, an example of sectional drawing of thesolar cell module 10 of this embodiment is shown.
Thesolar cell module 10 includes a plurality of solar cell elements 13, a pair of light-receiving surface side sealing sheet 11 and back surface side sealing sheet 12 that are sealed with the solar cell element 13 interposed therebetween, and a front surface side transparent protective member 14 and a back surface. A side protection member (back sheet) 15.
太陽電池モジュール１０は、複数の太陽電池素子１３と、太陽電池素子１３を挟んで封止する一対の受光面側封止シート１１と裏面側封止シート１２、および表面側透明保護部材１４および裏面側保護部材（バックシート）１５とを備える。 In FIG. 1, an example of sectional drawing of the
The
（太陽電池素子）
太陽電池素子１３としては、例えば、単結晶シリコン、多結晶シリコン、アモルファスシリコン等のシリコン系、ガリウム－砒素、銅－インジウム－セレン、カドミウム－テルル等のＩＩＩ－Ｖ族やＩＩ－ＶＩ族化合物半導体系等の各種太陽電池素子を用いることができる。
太陽電池モジュール１０においては、複数の太陽電池素子１３は、導線および半田接合部を備えたインターコネクタ１６を介して電気的に直列に接続されている。 (Solar cell element)
Examples of thesolar cell element 13 include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and III-V and II-VI compound semiconductors such as gallium-arsenic, copper-indium-selenium, and cadmium-tellurium. Various solar cell elements such as a system can be used.
In thesolar cell module 10, the plurality of solar cell elements 13 are electrically connected in series via an interconnector 16 having a conducting wire and a solder joint.
太陽電池素子１３としては、例えば、単結晶シリコン、多結晶シリコン、アモルファスシリコン等のシリコン系、ガリウム－砒素、銅－インジウム－セレン、カドミウム－テルル等のＩＩＩ－Ｖ族やＩＩ－ＶＩ族化合物半導体系等の各種太陽電池素子を用いることができる。
太陽電池モジュール１０においては、複数の太陽電池素子１３は、導線および半田接合部を備えたインターコネクタ１６を介して電気的に直列に接続されている。 (Solar cell element)
Examples of the
In the
（表面側透明保護部材）
表面側透明保護部材１４としては、例えば、ガラス板；アクリル樹脂、ポリカーボネート、ポリエステル、フッ素含有樹脂等により形成された樹脂板等が挙げられる。 (Front side transparent protective member)
Examples of the surface-side transparentprotective member 14 include a glass plate; a resin plate formed of acrylic resin, polycarbonate, polyester, fluorine-containing resin, and the like.
表面側透明保護部材１４としては、例えば、ガラス板；アクリル樹脂、ポリカーボネート、ポリエステル、フッ素含有樹脂等により形成された樹脂板等が挙げられる。 (Front side transparent protective member)
Examples of the surface-side transparent
（裏面側保護部材）
裏面側保護部材（バックシート）１５としては、例えば、金属や各種熱可塑性樹脂フィルム等の単体もしくは多層のシートが挙げられる。例えば、錫、アルミ、ステンレススチール等の金属；ガラス等の無機材料；ポリエステル、無機物蒸着ポリエステル、フッ素含有樹脂、ポリオレフィン等により形成された各種熱可塑性樹脂フィルム等が挙げられる。
裏面側保護部材１５は、単層であってもよく、多層であってもよい。 (Back side protection member)
Examples of the back surface side protection member (back sheet) 15 include single or multilayer sheets such as metals and various thermoplastic resin films. Examples thereof include metals such as tin, aluminum, and stainless steel; inorganic materials such as glass; various thermoplastic resin films formed of polyester, inorganic material-deposited polyester, fluorine-containing resin, polyolefin, and the like.
The back surfaceside protection member 15 may be a single layer or a multilayer.
裏面側保護部材（バックシート）１５としては、例えば、金属や各種熱可塑性樹脂フィルム等の単体もしくは多層のシートが挙げられる。例えば、錫、アルミ、ステンレススチール等の金属；ガラス等の無機材料；ポリエステル、無機物蒸着ポリエステル、フッ素含有樹脂、ポリオレフィン等により形成された各種熱可塑性樹脂フィルム等が挙げられる。
裏面側保護部材１５は、単層であってもよく、多層であってもよい。 (Back side protection member)
Examples of the back surface side protection member (back sheet) 15 include single or multilayer sheets such as metals and various thermoplastic resin films. Examples thereof include metals such as tin, aluminum, and stainless steel; inorganic materials such as glass; various thermoplastic resin films formed of polyester, inorganic material-deposited polyester, fluorine-containing resin, polyolefin, and the like.
The back surface
本実施形態の封止シートは、これらの表面側透明保護部材１４および裏面側保護部材１５に対して良好な接着性を示す。
The sealing sheet of the present embodiment exhibits good adhesion to the front surface side transparent protective member 14 and the back surface side protective member 15.
（太陽電池モジュールの製造方法）
本実施形態の太陽電池モジュール１０の製造方法は特に限定されないが、例えば、以下の方法が挙げられる。
まず、インターコネクタ１６を用いて電気的に接続した複数の太陽電池素子１３を一対の受光面側封止シート１１と裏面側封止シート１２で挟み、さらにこれら受光面側封止シート１１と裏面側封止シート１２を表面側透明保護部材１４と裏面側保護部材１５とで挟んで積層体を作製する。次いで、積層体を加熱して、受光面側封止シート１１と裏面側封止シート１２、受光面側封止シート１１と表面側透明保護部材１４、裏面側封止シート１２と裏面側保護部材１５とを接着する。
より具体的には、封止シートに含まれる架橋剤が実質的に分解せず、かつ、エチレン・極性モノマー共重合体が溶融するような温度に封止シートを加熱し、受光面側封止シート１１と裏面側封止シート１２、受光面側封止シート１１と表面側透明保護部材１４、裏面側封止シート１２と裏面側保護部材１５とをそれぞれ仮接着する。次いで昇温して、充分な接着を行い、さらに封止シート内のエチレン・極性モノマー共重合体の架橋を行う。接着及び架橋の温度は、満足すべき架橋速度が得られ、かつ膨れが発生しないような温度であればよく、例えば１００～１８０℃程度の温度範囲とすることができる。 (Method for manufacturing solar cell module)
Although the manufacturing method of thesolar cell module 10 of this embodiment is not specifically limited, For example, the following method is mentioned.
First, a plurality ofsolar cell elements 13 that are electrically connected using the interconnector 16 are sandwiched between a pair of light-receiving surface side sealing sheet 11 and back surface side sealing sheet 12, and further, these light receiving surface side sealing sheet 11 and back surface A laminated body is produced by sandwiching the side sealing sheet 12 between the front surface side transparent protective member 14 and the back surface side protective member 15. Next, the laminate is heated to receive the light-receiving surface side sealing sheet 11 and the back surface side sealing sheet 12, the light receiving surface side sealing sheet 11 and the front surface side transparent protective member 14, and the back surface side sealing sheet 12 and the back surface side protective member. 15 is bonded.
More specifically, the sealing sheet is heated to such a temperature that the crosslinking agent contained in the sealing sheet is not substantially decomposed and the ethylene / polar monomer copolymer is melted, and the light receiving surface side sealing is performed. Thesheet 11 and the rear surface side sealing sheet 12, the light receiving surface side sealing sheet 11 and the front surface side transparent protective member 14, and the rear surface side sealing sheet 12 and the rear surface side protective member 15 are temporarily bonded. Next, the temperature is raised, sufficient adhesion is performed, and the ethylene / polar monomer copolymer in the sealing sheet is further crosslinked. The bonding and crosslinking temperature may be a temperature at which a satisfactory crosslinking rate can be obtained and swelling does not occur, and can be in a temperature range of about 100 to 180 ° C., for example.
本実施形態の太陽電池モジュール１０の製造方法は特に限定されないが、例えば、以下の方法が挙げられる。
まず、インターコネクタ１６を用いて電気的に接続した複数の太陽電池素子１３を一対の受光面側封止シート１１と裏面側封止シート１２で挟み、さらにこれら受光面側封止シート１１と裏面側封止シート１２を表面側透明保護部材１４と裏面側保護部材１５とで挟んで積層体を作製する。次いで、積層体を加熱して、受光面側封止シート１１と裏面側封止シート１２、受光面側封止シート１１と表面側透明保護部材１４、裏面側封止シート１２と裏面側保護部材１５とを接着する。
より具体的には、封止シートに含まれる架橋剤が実質的に分解せず、かつ、エチレン・極性モノマー共重合体が溶融するような温度に封止シートを加熱し、受光面側封止シート１１と裏面側封止シート１２、受光面側封止シート１１と表面側透明保護部材１４、裏面側封止シート１２と裏面側保護部材１５とをそれぞれ仮接着する。次いで昇温して、充分な接着を行い、さらに封止シート内のエチレン・極性モノマー共重合体の架橋を行う。接着及び架橋の温度は、満足すべき架橋速度が得られ、かつ膨れが発生しないような温度であればよく、例えば１００～１８０℃程度の温度範囲とすることができる。 (Method for manufacturing solar cell module)
Although the manufacturing method of the
First, a plurality of
More specifically, the sealing sheet is heated to such a temperature that the crosslinking agent contained in the sealing sheet is not substantially decomposed and the ethylene / polar monomer copolymer is melted, and the light receiving surface side sealing is performed. The
以上、図面を参照して本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することもできる。
As described above, the embodiments of the present invention have been described with reference to the drawings. However, these are exemplifications of the present invention, and various configurations other than the above can be adopted.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
＜封止シートの作製＞
実施例１～６および比較例１、２について、次のように封止シートを作製した。まず、エチレン・酢酸ビニル共重合体（ＥＶＡ）、架橋剤、架橋助剤、アクリレート化合物、シランカップリング剤、光安定剤、および酸化防止剤を表１に示す処方で配合して樹脂組成物を得た。
得られた樹脂組成物を、Ｔダイ付押出機にて、厚さ約４５０μｍの封止シートに押出成形した。 <Preparation of sealing sheet>
For Examples 1 to 6 and Comparative Examples 1 and 2, sealing sheets were produced as follows. First, an ethylene / vinyl acetate copolymer (EVA), a crosslinking agent, a crosslinking aid, an acrylate compound, a silane coupling agent, a light stabilizer, and an antioxidant are blended in the formulation shown in Table 1 to obtain a resin composition. Obtained.
The obtained resin composition was extrusion molded into a sealing sheet having a thickness of about 450 μm with an extruder with a T-die.
実施例１～６および比較例１、２について、次のように封止シートを作製した。まず、エチレン・酢酸ビニル共重合体（ＥＶＡ）、架橋剤、架橋助剤、アクリレート化合物、シランカップリング剤、光安定剤、および酸化防止剤を表１に示す処方で配合して樹脂組成物を得た。
得られた樹脂組成物を、Ｔダイ付押出機にて、厚さ約４５０μｍの封止シートに押出成形した。 <Preparation of sealing sheet>
For Examples 1 to 6 and Comparative Examples 1 and 2, sealing sheets were produced as follows. First, an ethylene / vinyl acetate copolymer (EVA), a crosslinking agent, a crosslinking aid, an acrylate compound, a silane coupling agent, a light stabilizer, and an antioxidant are blended in the formulation shown in Table 1 to obtain a resin composition. Obtained.
The obtained resin composition was extrusion molded into a sealing sheet having a thickness of about 450 μm with an extruder with a T-die.
なお、表１中における各成分の配合割合の単位は質量部である。また、表１中における各成分の詳細は下記のとおりである。
In addition, the unit of the mixing ratio of each component in Table 1 is part by mass. Moreover, the detail of each component in Table 1 is as follows.
・ＥＶＡ：エチレン・酢酸ビニル共重合体（酢酸ビニル含有率２８質量％、ＭＦＲ：１５ｇ／１０分）
・架橋剤：ｔ－ブチルパーオキシ－２－エチルヘキシルカーボネート
・架橋助剤：トリアリルイソシアヌレート
・アクリレート化合物１：グリセリンプロポキシトリアクリレート（式（Ｉ）においてｘ＋ｙ＋ｚが３、Ｒ１、Ｒ２、Ｒ３が水素原子であり、Ｒ４、Ｒ５およびＲ６が－ＣＨ（ＣＨ３）ＣＨ２－または－ＣＨ２ＣＨ（ＣＨ３）－である化合物）
・アクリレート化合物２：ノナエチレングリコールジメタクリレート
・アクリレート化合物３：グリセリンエトキシトリアクリレート（式（Ｉ）においてｘ＋ｙ＋ｚが３、Ｒ１、Ｒ２、Ｒ３が水素原子であり、Ｒ４、Ｒ５およびＲ６が－ＣＨ２ＣＨ２－である化合物）
・シランカップリング剤：３－メタクリロキシプロピルトリメトキシシラン
・光安定剤：ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート
・酸化防止剤：オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート EVA: ethylene-vinyl acetate copolymer (vinyl acetate content 28% by mass, MFR: 15 g / 10 min)
Crosslinking agent: t-butylperoxy-2-ethylhexyl carbonate Crosslinking aid: triallyl isocyanurate Acrylate compound 1: Glycerol propoxytriacrylate (in formula (I), x + y + z is 3, R 1 , R 2 , R 3 Wherein R 4 , R 5 and R 6 are —CH (CH 3 ) CH 2 — or —CH 2 CH (CH 3 ) —)
Acrylate compound 2: Nonaethylene glycol dimethacrylate Acrylate compound 3: Glycerol ethoxytriacrylate (in formula (I), x + y + z is 3, R 1 , R 2 , R 3 are hydrogen atoms, R 4 , R 5 and R Compound in which 6 is —CH 2 CH 2 —
Silane coupling agent: 3-methacryloxypropyltrimethoxysilane Light stabilizer: Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate Antioxidant: Octadecyl-3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate
・架橋剤：ｔ－ブチルパーオキシ－２－エチルヘキシルカーボネート
・架橋助剤：トリアリルイソシアヌレート
・アクリレート化合物１：グリセリンプロポキシトリアクリレート（式（Ｉ）においてｘ＋ｙ＋ｚが３、Ｒ１、Ｒ２、Ｒ３が水素原子であり、Ｒ４、Ｒ５およびＲ６が－ＣＨ（ＣＨ３）ＣＨ２－または－ＣＨ２ＣＨ（ＣＨ３）－である化合物）
・アクリレート化合物２：ノナエチレングリコールジメタクリレート
・アクリレート化合物３：グリセリンエトキシトリアクリレート（式（Ｉ）においてｘ＋ｙ＋ｚが３、Ｒ１、Ｒ２、Ｒ３が水素原子であり、Ｒ４、Ｒ５およびＲ６が－ＣＨ２ＣＨ２－である化合物）
・シランカップリング剤：３－メタクリロキシプロピルトリメトキシシラン
・光安定剤：ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート
・酸化防止剤：オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート EVA: ethylene-vinyl acetate copolymer (vinyl acetate content 28% by mass, MFR: 15 g / 10 min)
Crosslinking agent: t-butylperoxy-2-ethylhexyl carbonate Crosslinking aid: triallyl isocyanurate Acrylate compound 1: Glycerol propoxytriacrylate (in formula (I), x + y + z is 3, R 1 , R 2 , R 3 Wherein R 4 , R 5 and R 6 are —CH (CH 3 ) CH 2 — or —CH 2 CH (CH 3 ) —)
Acrylate compound 2: Nonaethylene glycol dimethacrylate Acrylate compound 3: Glycerol ethoxytriacrylate (in formula (I), x + y + z is 3, R 1 , R 2 , R 3 are hydrogen atoms, R 4 , R 5 and R Compound in which 6 is —CH 2 CH 2 —
Silane coupling agent: 3-methacryloxypropyltrimethoxysilane Light stabilizer: Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate Antioxidant: Octadecyl-3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate
＜ＰＩＤ性能評価＞
実施例および比較例で得られた封止シートを用いて、１セル小モジュールを作製し、評価した。ガラスには、２４×２１ｃｍにカットした旭硝子ファブリテック社製の白板フロートガラス（３．２ｍｍ厚みのエンボス付き熱処理ガラス）を用いた。太陽電池素子は、１５６ｍｍ×１５６ｍｍのセル（Ｇｉｎｔｅｃｈ社製）を用いた。バックシートとして、シリカ蒸着ＰＥＴを含むＰＥＴ系バックシートを用い、バックシートの一部にカッタ－ナイフで約２ｃｍ切り込みを入れ、セルのプラス端子とマイナス端子を取り出し、真空ラミネーター（ＮＰＣ社製：ＬＭ－１１０ｘ１６０－Ｓ）を用いて熱盤温度１５０℃、真空時間３分、加圧時間１５分にてラミネートした。その後、ガラスからはみ出した封止シートおよびバックシートをカットし、ガラスエッジには端面封止材を付与して、アルミフレームを取り付けた。その後、バックシートから取り出した端子部分の切れ込み部位はＲＴＶシリコーンを付与して硬化させ、ミニモジュールを得た。 <PID performance evaluation>
Using the sealing sheets obtained in Examples and Comparative Examples, 1-cell small modules were produced and evaluated. As the glass, white plate float glass (3.2 mm thick heat-treated glass with embossing) manufactured by Asahi Glass Fabrictech Co., Ltd. cut to 24 × 21 cm was used. As the solar cell element, a 156 mm × 156 mm cell (manufactured by Gintech) was used. Using a PET backsheet containing silica-deposited PET as the backsheet, cut a portion of the backsheet with a cutter-knife about 2 cm, take out the positive and negative terminals of the cell, and use a vacuum laminator (NPC: LM -110 × 160-S) was laminated at a heating plate temperature of 150 ° C., a vacuum time of 3 minutes, and a pressurization time of 15 minutes. Thereafter, the sealing sheet and the back sheet that protruded from the glass were cut, an end face sealing material was applied to the glass edge, and an aluminum frame was attached. Thereafter, the cut portion of the terminal portion taken out from the back sheet was cured by applying RTV silicone to obtain a mini module.
実施例および比較例で得られた封止シートを用いて、１セル小モジュールを作製し、評価した。ガラスには、２４×２１ｃｍにカットした旭硝子ファブリテック社製の白板フロートガラス（３．２ｍｍ厚みのエンボス付き熱処理ガラス）を用いた。太陽電池素子は、１５６ｍｍ×１５６ｍｍのセル（Ｇｉｎｔｅｃｈ社製）を用いた。バックシートとして、シリカ蒸着ＰＥＴを含むＰＥＴ系バックシートを用い、バックシートの一部にカッタ－ナイフで約２ｃｍ切り込みを入れ、セルのプラス端子とマイナス端子を取り出し、真空ラミネーター（ＮＰＣ社製：ＬＭ－１１０ｘ１６０－Ｓ）を用いて熱盤温度１５０℃、真空時間３分、加圧時間１５分にてラミネートした。その後、ガラスからはみ出した封止シートおよびバックシートをカットし、ガラスエッジには端面封止材を付与して、アルミフレームを取り付けた。その後、バックシートから取り出した端子部分の切れ込み部位はＲＴＶシリコーンを付与して硬化させ、ミニモジュールを得た。 <PID performance evaluation>
Using the sealing sheets obtained in Examples and Comparative Examples, 1-cell small modules were produced and evaluated. As the glass, white plate float glass (3.2 mm thick heat-treated glass with embossing) manufactured by Asahi Glass Fabrictech Co., Ltd. cut to 24 × 21 cm was used. As the solar cell element, a 156 mm × 156 mm cell (manufactured by Gintech) was used. Using a PET backsheet containing silica-deposited PET as the backsheet, cut a portion of the backsheet with a cutter-knife about 2 cm, take out the positive and negative terminals of the cell, and use a vacuum laminator (NPC: LM -110 × 160-S) was laminated at a heating plate temperature of 150 ° C., a vacuum time of 3 minutes, and a pressurization time of 15 minutes. Thereafter, the sealing sheet and the back sheet that protruded from the glass were cut, an end face sealing material was applied to the glass edge, and an aluminum frame was attached. Thereafter, the cut portion of the terminal portion taken out from the back sheet was cured by applying RTV silicone to obtain a mini module.
このミニモジュールのプラス端子とマイナス端子を短絡し、電源の高圧側ケーブルを接続した。また電源の低圧側のケーブルはアルミフレームに接続し、アルミレームは接地した。このモジュールを６０℃、８５％Ｒｈの恒温恒湿槽内にセットし、温度上昇を待った後、－１０００Ｖを印加したまま９６時間保持した。
∙ Short-circuited the plus and minus terminals of this mini module and connected the high-voltage cable of the power supply. The cable on the low voltage side of the power supply was connected to an aluminum frame, and the aluminum frame was grounded. This module was set in a constant temperature and humidity chamber at 60 ° C. and 85% Rh, and after waiting for the temperature to rise, it was held for 96 hours while applying −1000 V.
高圧電源には、松定プレシジョン社製ＨＡＲｂ－３Ｒ１０－ＬＦを用い、恒温恒湿槽にはエタック社製ＦＳ－２１４Ｃ２を用いた。
HARb-3R10-LF manufactured by Matsusada Precision Co., Ltd. was used as the high voltage power source, and FS-214C2 manufactured by ETAC Co., Ltd. was used as the constant temperature and humidity chamber.
モジュールのＩＶ特性はＡＭ（エアマス）１．５クラスＡの光強度分布を有するキセノン光源および日清紡メカトロニクス社製のＰＶＳ－１１６ｉ－Ｓを用い、光照射パワー密度１０００Ｗ／ｍ２の時の最大出力電力Ｐｍａｘを評価した。
また更に、ＰＩＤ評価において暗時での並列抵抗（ダークＲｓｈ）がセルの劣化を示す上で最も感度の高いパラメータであるので、ダークＲｓｈも評価項目に加えた。具体的には、モジュールを暗室に設置し、ＡＤＣ社製の６２４２を用いて暗時でのＩＶ特性を測定し、電流がゼロ近傍での電圧の電流に対する傾き（ΔＶ／ΔＩ）からダークＲｓｈを評価した。 The IV characteristics of the module are the maximum output power at a light irradiation power density of 1000 W / m 2 using a xenon light source with AM (air mass) 1.5 class A light intensity distribution and PVS-116i-S manufactured by Nisshinbo Mechatronics. P max was evaluated.
Furthermore, since the parallel resistance in the dark (dark Rsh) in PID evaluation is the most sensitive parameter for indicating cell deterioration, dark Rsh was also added to the evaluation item. Specifically, the module is installed in a dark room, IV characteristics in the dark are measured using 6242 made by ADC, and dark Rsh is calculated from the slope (ΔV / ΔI) of the voltage when the current is near zero. evaluated.
また更に、ＰＩＤ評価において暗時での並列抵抗（ダークＲｓｈ）がセルの劣化を示す上で最も感度の高いパラメータであるので、ダークＲｓｈも評価項目に加えた。具体的には、モジュールを暗室に設置し、ＡＤＣ社製の６２４２を用いて暗時でのＩＶ特性を測定し、電流がゼロ近傍での電圧の電流に対する傾き（ΔＶ／ΔＩ）からダークＲｓｈを評価した。 The IV characteristics of the module are the maximum output power at a light irradiation power density of 1000 W / m 2 using a xenon light source with AM (air mass) 1.5 class A light intensity distribution and PVS-116i-S manufactured by Nisshinbo Mechatronics. P max was evaluated.
Furthermore, since the parallel resistance in the dark (dark Rsh) in PID evaluation is the most sensitive parameter for indicating cell deterioration, dark Rsh was also added to the evaluation item. Specifically, the module is installed in a dark room, IV characteristics in the dark are measured using 6242 made by ADC, and dark Rsh is calculated from the slope (ΔV / ΔI) of the voltage when the current is near zero. evaluated.
評価結果は以下の通りに分類した。結果を表１に示す。
試験後のＩＶ特性の最大出力電力Ｐｍａｘが初期値と比べて
出力電力の低下が５％以下：Ａ
出力電力の低下が５％を超える：Ｂ
試験後のＩＶ特性の暗時での並列抵抗（ダークＲｓｈ）が初期値と比べて
ダークＲｓｈの低下が５０％以下：Ａ
ダークＲｓｈの低下が５０％を超える：Ｂ
Ｐｍａｘ及びダークＲｓｈのいずれもＡとなるものをＰＩＤ劣化がない、逆にＰｍａｘ及びダークＲｓｈのいずれかがＢとなった場合にはＰＩＤ劣化していると判断した。 The evaluation results were classified as follows. The results are shown in Table 1.
The maximum output power P max of the IV characteristic after the test is less than 5% compared to the initial value: A:
Output power drop exceeds 5%: B
Compared to the initial value, the parallel resistance (dark Rsh) in the dark of IV characteristics after the test is less than 50% of the decrease in dark Rsh: A
Dark Rsh reduction exceeds 50%: B
When both P max and dark Rsh were A, it was judged that there was no PID degradation. Conversely, when either P max or dark Rsh was B, it was judged that PID was degraded.
試験後のＩＶ特性の最大出力電力Ｐｍａｘが初期値と比べて
出力電力の低下が５％以下：Ａ
出力電力の低下が５％を超える：Ｂ
試験後のＩＶ特性の暗時での並列抵抗（ダークＲｓｈ）が初期値と比べて
ダークＲｓｈの低下が５０％以下：Ａ
ダークＲｓｈの低下が５０％を超える：Ｂ
Ｐｍａｘ及びダークＲｓｈのいずれもＡとなるものをＰＩＤ劣化がない、逆にＰｍａｘ及びダークＲｓｈのいずれかがＢとなった場合にはＰＩＤ劣化していると判断した。 The evaluation results were classified as follows. The results are shown in Table 1.
The maximum output power P max of the IV characteristic after the test is less than 5% compared to the initial value: A:
Output power drop exceeds 5%: B
Compared to the initial value, the parallel resistance (dark Rsh) in the dark of IV characteristics after the test is less than 50% of the decrease in dark Rsh: A
Dark Rsh reduction exceeds 50%: B
When both P max and dark Rsh were A, it was judged that there was no PID degradation. Conversely, when either P max or dark Rsh was B, it was judged that PID was degraded.
実施例１～６は、ＰＩＤ試験後も最大出力Ｐｍａｘが保持されており、ダークＲｓｈの低下も小さいことがわかる。
これに対しアクリレート化合物を配合しない比較例１はＰＩＤ試験後にＰｍａｘが初期値と比べて低下する。
本発明とは異なるアクリレート化合物を用いた比較例２は、ＰＩＤ試験後のＰｍａｘこそ保持されているが、ダークＲｓｈの低下が大きく、セルの劣化が観察された。
以上より、本発明においては、特定の（メタ）アクリレート化合物を使用することでＰＩＤ試験後の最大出力電力だけでなく、ダークＲｓｈの低下も抑制できており、ＰＩＤに対してより効果を発揮しているものといえる。 In Examples 1 to 6, it can be seen that the maximum output P max is maintained even after the PID test, and the decrease in the dark Rsh is small.
On the other hand, in Comparative Example 1 in which no acrylate compound is blended, P max is lower than the initial value after the PID test.
In Comparative Example 2 using an acrylate compound different from the present invention, the P max after the PID test was maintained, but the dark Rsh was greatly reduced, and cell deterioration was observed.
From the above, in the present invention, by using a specific (meth) acrylate compound, not only the maximum output power after the PID test but also the decrease in dark Rsh can be suppressed, and the effect is more effective for PID. It can be said that.
これに対しアクリレート化合物を配合しない比較例１はＰＩＤ試験後にＰｍａｘが初期値と比べて低下する。
本発明とは異なるアクリレート化合物を用いた比較例２は、ＰＩＤ試験後のＰｍａｘこそ保持されているが、ダークＲｓｈの低下が大きく、セルの劣化が観察された。
以上より、本発明においては、特定の（メタ）アクリレート化合物を使用することでＰＩＤ試験後の最大出力電力だけでなく、ダークＲｓｈの低下も抑制できており、ＰＩＤに対してより効果を発揮しているものといえる。 In Examples 1 to 6, it can be seen that the maximum output P max is maintained even after the PID test, and the decrease in the dark Rsh is small.
On the other hand, in Comparative Example 1 in which no acrylate compound is blended, P max is lower than the initial value after the PID test.
In Comparative Example 2 using an acrylate compound different from the present invention, the P max after the PID test was maintained, but the dark Rsh was greatly reduced, and cell deterioration was observed.
From the above, in the present invention, by using a specific (meth) acrylate compound, not only the maximum output power after the PID test but also the decrease in dark Rsh can be suppressed, and the effect is more effective for PID. It can be said that.
この出願は、２０１５年４月２４日に出願された日本出願特願２０１５－０８９２３５号を基礎とする優先権を主張し、その開示の全てをここに取り込む。
This application claims priority based on Japanese Patent Application No. 2015-089235 filed on April 24, 2015, the entire disclosure of which is incorporated herein.
Claims (7)
- 太陽電池素子を封止するために用いられる封止シートであって、
エチレン・極性モノマー共重合体と、
架橋剤と、
ジビニル芳香族化合物、シアヌレート化合物、ジアリル化合物、トリアリル化合物、オキシム化合物およびマレイミド化合物からなる群より選択される一種または二種以上の架橋助剤と、
下記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物と、
を含む封止シート。
An ethylene / polar monomer copolymer;
A crosslinking agent;
One or more crosslinking aids selected from the group consisting of divinyl aromatic compounds, cyanurate compounds, diallyl compounds, triallyl compounds, oxime compounds and maleimide compounds;
A glycerol tri (meth) acrylate compound represented by the following formula (I):
The sealing sheet containing.
- 請求項１に記載の封止シートにおいて、
前記エチレン・極性モノマー共重合体がエチレン・酢酸ビニル共重合体を含む封止シート。 In the sealing sheet according to claim 1,
A sealing sheet in which the ethylene / polar monomer copolymer comprises an ethylene / vinyl acetate copolymer. - 請求項２に記載の封止シートにおいて、
前記エチレン・酢酸ビニル共重合体中の酢酸ビニルに由来する構成単位の含有割合が１０質量％以上４７質量％以下である封止シート。 In the sealing sheet according to claim 2,
The sealing sheet whose content rate of the structural unit derived from the vinyl acetate in the said ethylene-vinyl acetate copolymer is 10 mass% or more and 47 mass% or less. - 請求項１乃至３いずれか一項に記載の封止シートにおいて、
前記式（Ｉ）におけるＲ１、Ｒ２およびＲ３が水素原子である封止シート。 In the sealing sheet according to any one of claims 1 to 3,
The sealing sheet whose R < 1 >, R < 2 > and R < 3 > in the said formula (I) are a hydrogen atom. - 請求項１乃至４いずれか一項に記載の封止シートにおいて、
前記式（Ｉ）におけるｘ＋ｙ＋ｚが３または６である封止シート。 In the sealing sheet according to any one of claims 1 to 4,
The sealing sheet whose x + y + z in the said formula (I) is 3 or 6. - 請求項１乃至５いずれか一項に記載の封止シートにおいて、
前記式（Ｉ）により示されるグリセリントリ（メタ）アクリレート化合物の含有量が、前記エチレン・極性モノマー共重合体１００質量部に対して、０．１質量部以上２．０質量部以下である封止シート。 In the sealing sheet according to any one of claims 1 to 5,
The content of the glycerin tri (meth) acrylate compound represented by the formula (I) is 0.1 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the ethylene / polar monomer copolymer. Stop sheet. - 表面側透明保護部材と、
裏面側保護部材と、
太陽電池素子と、
請求項１乃至６いずれか一項に記載の封止シートの架橋物により構成され、かつ、前記太陽電池素子を前記表面側透明保護部材と前記裏面側保護部材との間に封止する封止層と、
を備える太陽電池モジュール。 A surface-side transparent protective member;
A back side protection member;
A solar cell element;
Sealing comprising the cross-linked product of the sealing sheet according to any one of claims 1 to 6 and sealing the solar cell element between the front surface side transparent protective member and the back surface side protective member. Layers,
A solar cell module comprising:
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016547629A JP6035001B1 (en) | 2015-04-24 | 2016-04-15 | Sealing sheet and solar cell module |
| KR1020177022014A KR20170102964A (en) | 2015-04-24 | 2016-04-15 | Sealing sheet and solar cell module |
| CN201680008428.8A CN107396640A (en) | 2015-04-24 | 2016-04-15 | Diaphragm seal and solar module |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-089235 | 2015-04-24 | ||
| JP2015089235 | 2015-04-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2016171080A1 true WO2016171080A1 (en) | 2016-10-27 |
Family
ID=57143006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2016/062119 WO2016171080A1 (en) | 2015-04-24 | 2016-04-15 | Sealing sheet and solar cell module |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6035001B1 (en) |
| KR (1) | KR20170102964A (en) |
| CN (1) | CN107396640A (en) |
| WO (1) | WO2016171080A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021200035A1 (en) * | 2020-03-30 | 2021-10-07 | 日東電工株式会社 | Optical semiconductor device sealing sheet |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964447A (en) * | 2018-09-30 | 2020-04-07 | 上海海优威新材料股份有限公司 | Packaging adhesive film for photovoltaic module |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013118504A1 (en) * | 2012-02-10 | 2013-08-15 | 三井化学株式会社 | Solar cell sealing material and solar cell module |
-
2016
- 2016-04-15 CN CN201680008428.8A patent/CN107396640A/en not_active Withdrawn
- 2016-04-15 KR KR1020177022014A patent/KR20170102964A/en not_active Application Discontinuation
- 2016-04-15 WO PCT/JP2016/062119 patent/WO2016171080A1/en active Application Filing
- 2016-04-15 JP JP2016547629A patent/JP6035001B1/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013118504A1 (en) * | 2012-02-10 | 2013-08-15 | 三井化学株式会社 | Solar cell sealing material and solar cell module |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021200035A1 (en) * | 2020-03-30 | 2021-10-07 | 日東電工株式会社 | Optical semiconductor device sealing sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107396640A (en) | 2017-11-24 |
| KR20170102964A (en) | 2017-09-12 |
| JPWO2016171080A1 (en) | 2017-05-18 |
| JP6035001B1 (en) | 2016-11-30 |
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