JP6256758B2 - Sealant for photoelectric conversion element - Google Patents
Sealant for photoelectric conversion element Download PDFInfo
- Publication number
- JP6256758B2 JP6256758B2 JP2014053905A JP2014053905A JP6256758B2 JP 6256758 B2 JP6256758 B2 JP 6256758B2 JP 2014053905 A JP2014053905 A JP 2014053905A JP 2014053905 A JP2014053905 A JP 2014053905A JP 6256758 B2 JP6256758 B2 JP 6256758B2
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- Japan
- Prior art keywords
- component
- meth
- photoelectric conversion
- acrylate
- mass
- Prior art date
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- 238000006243 chemical reaction Methods 0.000 title claims description 38
- 239000000565 sealant Substances 0.000 title description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 48
- 238000007789 sealing Methods 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- -1 acrylic compound Chemical class 0.000 claims description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 17
- 239000004593 Epoxy Substances 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- 239000003566 sealing material Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 description 23
- 239000011521 glass Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000000758 substrate Substances 0.000 description 19
- 239000003822 epoxy resin Substances 0.000 description 17
- 229920000647 polyepoxide Polymers 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 12
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 239000007870 radical polymerization initiator Substances 0.000 description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 description 7
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- VZTQQYMRXDUHDO-UHFFFAOYSA-N [2-hydroxy-3-[4-[2-[4-(2-hydroxy-3-prop-2-enoyloxypropoxy)phenyl]propan-2-yl]phenoxy]propyl] prop-2-enoate Chemical compound C=1C=C(OCC(O)COC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCC(O)COC(=O)C=C)C=C1 VZTQQYMRXDUHDO-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- MYEFGHBUFAPKJO-UHFFFAOYSA-N 3-[methyl(dipropoxy)silyl]propyl prop-2-enoate Chemical compound CCCO[Si](C)(OCCC)CCCOC(=O)C=C MYEFGHBUFAPKJO-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
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- 230000002040 relaxant effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- JEAPEYGGHJNSII-UHFFFAOYSA-N 1-(4-morpholin-4-ylphenyl)butan-2-one Chemical compound C1=CC(CC(=O)CC)=CC=C1N1CCOCC1 JEAPEYGGHJNSII-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-UHFFFAOYSA-N 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- XXHDHAPOSIFMIG-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-phenoxyethanol Chemical compound OCCOCCOCCOCC(O)OC1=CC=CC=C1 XXHDHAPOSIFMIG-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- UDWIZRDPCQAYRF-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C=C UDWIZRDPCQAYRF-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- JUINTNKGYWNEDR-UHFFFAOYSA-N 3-[dimethyl(propoxy)silyl]propyl prop-2-enoate Chemical compound CCCO[Si](C)(C)CCCOC(=O)C=C JUINTNKGYWNEDR-UHFFFAOYSA-N 0.000 description 1
- JSOZORWBKQSQCJ-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(C)CCCOC(=O)C(C)=C JSOZORWBKQSQCJ-UHFFFAOYSA-N 0.000 description 1
- DGBFOBNYTYHFPN-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(C)CCCOC(=O)C=C DGBFOBNYTYHFPN-UHFFFAOYSA-N 0.000 description 1
- JBDMKOVTOUIKFI-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C(C)=C JBDMKOVTOUIKFI-UHFFFAOYSA-N 0.000 description 1
- ZCRUJAKCJLCJCP-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C=C ZCRUJAKCJLCJCP-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- 125000004864 4-thiomethylphenyl group Chemical group 0.000 description 1
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- 239000005909 Kieselgur Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- 229920002367 Polyisobutene Polymers 0.000 description 1
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- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- QWEDYNXINZOSSV-AATRIKPKSA-N [2-methyl-4-oxo-3-[(e)-prop-1-enyl]cyclopent-2-en-1-yl] n,n-dimethylcarbamate Chemical compound C\C=C\C1=C(C)C(OC(=O)N(C)C)CC1=O QWEDYNXINZOSSV-AATRIKPKSA-N 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- JFBKTKZPBKFWMU-UHFFFAOYSA-N dimethyl-[3-(oxiran-2-ylmethoxy)propyl]-propoxysilane Chemical compound CCCO[Si](C)(C)CCCOCC1CO1 JFBKTKZPBKFWMU-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- HHBOIIOOTUCYQD-UHFFFAOYSA-N ethoxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(C)CCCOCC1CO1 HHBOIIOOTUCYQD-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- VOARQMXRPHXHID-UHFFFAOYSA-N methyl-[3-(oxiran-2-ylmethoxy)propyl]-dipropoxysilane Chemical compound CCCO[Si](C)(OCCC)CCCOCC1CO1 VOARQMXRPHXHID-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 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
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 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
Classifications
-
- 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
- Y02E10/542—Dye sensitized solar cells
Description
本発明は紫外線等の光などの活性エネルギー線の照射により重合反応が速やかに進み、ガラス等の基板への接着力に優れ、且つ、水蒸気バリア性の高い硬化物が得られる光電変換素子用シール剤に関するものである。 The present invention is a photoelectric conversion element seal that allows a polymerization reaction to proceed rapidly by irradiation with active energy rays such as light such as ultraviolet rays, and that provides a cured product having excellent adhesion to a substrate such as glass and having a high water vapor barrier property. It relates to the agent.
従来より、シリコン系太陽電池、色素増感太陽電池、有機薄膜系太陽電池などの光電変換素子は、グリーンエネルギーや省エネルギーデバイスとして注目されている。これら光電変換素子は、特に湿度に対して敏感であり、高温高湿などの環境下で長期にわたって使用されると、外部から侵入した湿度によって変質や劣化が起こり、素子の性能が低下してしまうため、封止性（水蒸気バリア性）の高い光硬化性シール剤が多用されている。 Conventionally, photoelectric conversion elements such as silicon-based solar cells, dye-sensitized solar cells, and organic thin-film solar cells have attracted attention as green energy and energy-saving devices. These photoelectric conversion elements are particularly sensitive to humidity, and when used for a long period of time in an environment such as high temperature and high humidity, deterioration or deterioration occurs due to humidity entering from the outside, and the performance of the element is lowered. For this reason, a photocurable sealing agent having a high sealing property (water vapor barrier property) is frequently used.
光電変換素子用シール剤としては、例えば、特許文献１には、エポキシ樹脂、熱硬化剤、エポキシ（メタ）アクリレート及び光重合開始剤を含有することを特徴とする光電変換素子用シール剤が開示されている。また、特許文献２には、炭素数１０〜２２の単官能（メタ）アクリレート、液状飽和エラストマー及び光重合開始剤を含有する色素増感型太陽電池用シーリング材が開示されている。 As a sealing agent for photoelectric conversion elements, for example, Patent Document 1 discloses a sealing agent for photoelectric conversion elements containing an epoxy resin, a thermosetting agent, an epoxy (meth) acrylate, and a photopolymerization initiator. Has been. Patent Document 2 discloses a dye-sensitized solar cell sealing material containing a monofunctional (meth) acrylate having 10 to 22 carbon atoms, a liquid saturated elastomer, and a photopolymerization initiator.
しかしながら、特許文献１、２に開示された光電変換素子用シール剤は、ガラス等の基板への接着力及び水蒸気バリア性などの特性を満足するものではなかった。 However, the sealants for photoelectric conversion elements disclosed in Patent Documents 1 and 2 do not satisfy characteristics such as adhesion to a substrate such as glass and water vapor barrier properties.
本発明の光電変換素子用シール剤は、紫外線等の光などの活性エネルギー線の照射により重合反応が速やかに進み水蒸気バリア性の高い硬化物が得られ、且つガラス等の基板への接着力に優れる光電変換素子用シール剤を提供することを目的とする。 The sealing agent for a photoelectric conversion element of the present invention has a polymerization reaction that proceeds rapidly by irradiation with an active energy ray such as light such as ultraviolet rays, and a cured product having a high water vapor barrier property is obtained. It aims at providing the sealing agent for photoelectric conversion elements which is excellent.
本発明の要旨を次に説明する。本発明の実施態様は、本発明は上述した従来の問題点を克服するものである。
ビスフェノール構造及びアルキレンオキサイド単位の繰返し平均数１〜８を有する（メタ）アクリル化合物（（Ａ）成分）と、エポキシ（メタ）アクリレート（（Ｂ）成分）と、光開始剤（（Ｃ）成分）を含有し、
（Ａ）成分と（Ｂ）成分の合計量１００質量部中、（Ａ）成分が２５〜９５質量部含有することを特徴とする光電変換素子用シール剤。
The gist of the present invention will be described next. The embodiments of the present invention overcome the above-mentioned conventional problems.
(Meth) acrylic compound ((A) component) having a bisphenol structure and an alkylene oxide unit repeating average number of 1 to 8, epoxy (meth) acrylate ((B) component), and photoinitiator ((C) component) Containing
The sealing agent for photoelectric conversion elements, wherein the component (A) is contained in an amount of 25 to 95 parts by mass in 100 parts by mass of the total amount of the component (A) and the component (B).
本発明の光電変換素子用シール剤は、紫外線等の光などの活性エネルギー線の照射により重合反応が速やかに進み水蒸気バリア性の高い硬化物が得られ、且つガラス等の基板への接着力に優れるものである。 The sealing agent for a photoelectric conversion element of the present invention has a polymerization reaction that proceeds rapidly by irradiation with an active energy ray such as light such as ultraviolet rays, and a cured product having a high water vapor barrier property is obtained. It is excellent.
以下本発明を詳細に説明する。
＜（Ａ）成分＞
本発明の（Ａ）成分は、ビスフェノール構造及びアルキレンオキサイド単位の繰返し平均数１〜８を有する（メタ）アクリル化合物である。好ましくは、ビスフェノール構造及びアルキレンオキサイド単位の繰返し平均数を１．５〜６有する（メタ）アクリル化合物であり、特に好ましくは、ビスフェノール構造及びアルキレンオキサイド単位の繰返し平均数を２〜５有する（メタ）アクリル化合物である。
The present invention will be described in detail below.
<(A) component>
The component (A) of the present invention is a (meth) acrylic compound having a bisphenol structure and a repeating average number of 1 to 8 alkylene oxide units. Preferably, it is a (meth) acryl compound having a repeating average number of bisphenol structures and alkylene oxide units of 1.5 to 6, particularly preferably having a repeating average number of 2 to 5 (meth) of bisphenol structures and alkylene oxide units. It is an acrylic compound.
前記（Ａ）成分の合成方法は特に限定されないが、例えばビスフェノールＡ、ビスフェノールＦ又はビスフェノールＥにエチレンオキサイド（以下ＥＯと略す）又はプロピレンオキサイド（以下ＰＯと略す）等のアルキレンオキサイドを付加させた２価アルコールと（メタ）アクリル酸とのエステル反応物などにより得ることができる。又は、ビスフェノールＡ、ビスフェノールＦ又はビスフェノールＥにエチレンオキサイド又はプロピレンオキサイド等のアルキレンオキサイドを付加させた２価アルコールとエピハロヒドリンとを反応させアルキレンオキサイド付加ビスフェノールジグリシジルを得て、その後（メタ）アクリル酸とを反応させ得ることができる。 The method for synthesizing the component (A) is not particularly limited. For example, 2 is obtained by adding alkylene oxide such as ethylene oxide (hereinafter abbreviated as EO) or propylene oxide (hereinafter abbreviated as PO) to bisphenol A, bisphenol F or bisphenol E. It can be obtained by an ester reaction product of a monohydric alcohol and (meth) acrylic acid. Alternatively, a dihydric alcohol obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to bisphenol A, bisphenol F or bisphenol E is reacted with an epihalohydrin to obtain an alkylene oxide-added bisphenol diglycidyl, and then (meth) acrylic acid and Can be reacted.
（Ａ）成分の市販品としては、例えば、ライトエステルＢＰ−２ＥＭ、ＢＰ−４ＥＭ、ＢＰ−６ＥＭ、ＢＰ−４ＥＡ、ＢＰ−６ＰＡ（共栄社化学株式会社製）、Ａ−ＢＰＥ−４、Ａ−ＢＰＰ−３（新中村化学工業株式会社製）、ＦＡ−３２４Ａ（日立化成株式会社製）などがあげられる。これらは単独で用いられてもよく、２種以上が併用されてもよい。 As a commercial item of (A) component, for example, light ester BP-2EM, BP-4EM, BP-6EM, BP-4EA, BP-6PA (manufactured by Kyoeisha Chemical Co., Ltd.), A-BPE-4, A-BPP -3 (manufactured by Shin-Nakamura Chemical Co., Ltd.), FA-324A (manufactured by Hitachi Chemical Co., Ltd.) and the like. These may be used independently and 2 or more types may be used together.
＜（Ｂ）成分＞
本発明の（Ｂ）成分は、エポキシ（メタ）アクリレートである。（Ｂ）成分の合成方法は、特に限定されないが、例えば１分子中に少なくとも２個以上のエポキシ基を有するエポキシ樹脂を（メタ）アクリル酸で付加させ得られる反応物などがあげられる。なお、エチレンオキサイド又はプロピレンオキサイド等のアルキレンオキサイドの繰り返し単位を構造中に有し、且つ２個以上のエポキシ基を有するエポキシ樹脂に対して、（メタ）アクリル酸で付加させ得られた反応物は、本発明において（Ａ）成分として扱うものとする。
<(B) component>
The component (B) of the present invention is epoxy (meth) acrylate. The method for synthesizing the component (B) is not particularly limited, and examples thereof include a reaction product obtained by adding an epoxy resin having at least two epoxy groups in one molecule with (meth) acrylic acid. The reaction product obtained by adding (meth) acrylic acid to an epoxy resin having a repeating unit of alkylene oxide such as ethylene oxide or propylene oxide in the structure and having two or more epoxy groups is In the present invention, it is treated as the component (A).
前記エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＥ型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＦ型エポキシ樹脂、水添ビスフェノールＥ型エポキシ樹脂、水添クレゾールノボラック型エポキシ樹脂、水添フェノールノボラック型エポキシ樹脂などがあげられるが、中でもビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＥ型エポキシ樹脂が好ましく用いられる。これらは単独で用いられてもよく、２種以上が併用されてもよい。 Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy. Resin, hydrogenated bisphenol E type epoxy resin, hydrogenated cresol novolak type epoxy resin, hydrogenated phenol novolak type epoxy resin, etc., among which bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin are mentioned. Preferably used. These may be used independently and 2 or more types may be used together.
（Ｂ）成分であるエポキシ（メタ）アクリレートとしては、特に限定されないが、ガラス等の基板への接着力に優れ、架橋密度が高くなることから水蒸気バリア性に優れる硬化物が得られること観点からビスフェノールＡ型エポキシ（メタ）アクリレート、ビスフェノールＦ型（メタ）アクリレート、ビスフェノールＥ型（メタ）アクリレートが好ましく用いられ、そのような化合物としては、一般式（１）で表される化合物などがあげられる。 Although it does not specifically limit as epoxy (meth) acrylate which is (B) component, From the viewpoint that the hardened | cured material which is excellent in the adhesive force to board | substrates, such as glass, and is excellent in water vapor | steam barrier property from a high crosslinking density. Bisphenol A type epoxy (meth) acrylate, bisphenol F type (meth) acrylate, and bisphenol E type (meth) acrylate are preferably used, and examples of such compounds include compounds represented by general formula (1). .
（Ｂ）成分の酸価は、好ましくは２０ＫＯＨｍｇ／ｇ以下であり、１０ＫＯＨｍｇ／ｇ以下である。上記の範囲の（Ｂ）成分を用いることで ガラス等の基板への接着力と貯蔵安定性が良好な光電変換素子用シール剤が得られる。なお、本発明における酸価とは（Ｂ）成分１ｇ中に含まれる遊離脂肪酸を中和するのに必要な水酸化カリウムｍｇ数をいう。試験方法としては中和滴定法が挙げられる。 (B) The acid value of a component becomes like this. Preferably it is 20 KOHmg / g or less, and is 10 KOHmg / g or less. By using the component (B) in the above range, a sealing agent for a photoelectric conversion element having good adhesion to a substrate such as glass and storage stability can be obtained. In addition, the acid value in this invention means the number of mg of potassium hydroxide required in order to neutralize the free fatty acid contained in 1g of (B) component. An example of the test method is a neutralization titration method.
（Ｂ）成分であるエポキシ（メタ）アクリレートの市販品としては、例えばユニディックＶ−５５００、Ｖ−５５０２（ＤＩＣ株式会社製）エポキシエステル３０００Ａ、エポキシエステル３００２Ｍ（Ｎ）、エポキシエステル３００２Ａ（Ｎ）、（共栄社化学株式会社製）、リポキシＳＰ−１５０６、ＳＰ−１５０９、ＶＲ−６０、ＶＲ−７７、ＶＲ−９０、Ｒ８０２（昭和高分子株式会社製）、エベクリル３７００（ダイセルサイテック株式会社）、ネオポールＡＣ５７４８、８１０１、８２５０、８２６０８２７０、８３１８、８４７０、８４７５、８３１９、８３５５、８３５１、８３３５、８４１４、８１９０、８１９５（日本ユピカ株式会社製）、ＢＡＥＡ−１００、ＢＡＥＭ−１００、ＢＡＥＭ−５０、ＢＥＥＭ−５０、ＢＦＥＡ−５０（ケーエスエム株式会社製）、デナコールアクリレートＤＡ−２５０（ナガセケムテックス株式会社製）、ＧＥＮＯＭＥＲ２２６３（Ｒａｈｎ ＡＧ 社製）、ビスコート５４０（大阪有機社製）などがあげられる。これらは単独で用いられてもよく、２種以上が併用されてもよい。 As a commercial item of epoxy (meth) acrylate which is (B) component, for example, Unidic V-5500, V-5502 (manufactured by DIC Corporation), epoxy ester 3000A, epoxy ester 3002M (N), epoxy ester 3002A (N) , (Manufactured by Kyoeisha Chemical Co., Ltd.), lipoxy SP-1506, SP-1509, VR-60, VR-77, VR-90, R802 (manufactured by Showa Polymer Co., Ltd.), Everacryl 3700 (Daicel Cytec Co., Ltd.), Neopole AC5748, 8101, 8250, 8260270, 8318, 8470, 8475, 8319, 8355, 8351, 8335, 8414, 8190, 8195 (manufactured by Nippon Epica Co., Ltd.), BAEA-100, BAEM-100, BAEM-50, BEEM-50 , BF A-50 (manufactured by Keesuemu Co., Ltd.), (manufactured by Nagase Chemtex Co., Ltd.) Dinah call acrylate DA-250, (manufactured by Rahn AG, Inc.) GENOMER2263, BISCOAT 540 (manufactured by Osaka Organic Co., Ltd.), and the like. These may be used independently and 2 or more types may be used together.
（Ａ）成分と（Ｂ）成分の合計量１００質量部中、好ましくは（Ａ）成分が２５〜９５質量部であり、更に好ましくは、２７〜９０質量部であり、特に好ましくは３０〜８５質量部である。上記の範囲内で（Ａ）成分を配合すると、より水蒸気バリア性の高い硬化物が得られ、且つガラス等の基板への接着力に優れた硬化性樹脂組成物を得ることができる。 In 100 parts by mass of the total amount of component (A) and component (B), component (A) is preferably 25 to 95 parts by mass, more preferably 27 to 90 parts by mass, and particularly preferably 30 to 85 parts. Part by mass. When (A) component is mix | blended within said range, the hardened | cured material with higher water vapor | steam barrier property will be obtained, and the curable resin composition excellent in the adhesive force to board | substrates, such as glass, can be obtained.
＜（Ｃ）成分＞
本発明に用いられる（Ｃ）成分である光重合開始剤は、活性エネルギー線を照射することにより、ラジカルが発生する化合物であれば限定されるものではないが、（Ｃ）成分としては、例えば、アセトフェノン系光ラジカル重合開始剤、ベンゾイン系光ラジカル重合開始剤、ベンゾフェノン系光ラジカル重合開始剤、チオキサントン系光ラジカル重合開始剤、アシルホスフィンオキサイド系光ラジカル重合開始剤、チタノセン系光ラジカル重合開始剤等が挙げられ、この中でも光硬化性に優れ、優れた封止性が得られるという観点からアセトフェノン系光ラジカル重合開始剤、アシルホスフィンオキサイド系光ラジカル重合開始剤が好ましい。またこれらは単独で用いられてもよく、２種以上が併用されてもよい。
<(C) component>
The photopolymerization initiator that is the component (C) used in the present invention is not limited as long as it is a compound that generates radicals by irradiation with active energy rays. Examples of the component (C) include , Acetophenone photo radical polymerization initiator, benzoin photo radical polymerization initiator, benzophenone photo radical polymerization initiator, thioxanthone photo radical polymerization initiator, acylphosphine oxide photo radical polymerization initiator, titanocene photo radical polymerization initiator Of these, acetophenone-based photoradical polymerization initiators and acylphosphine oxide-based photoradical polymerization initiators are preferred from the viewpoint of excellent photocurability and excellent sealing properties. Moreover, these may be used independently and 2 or more types may be used together.
前記のアセトフェノン系光ラジカル重合開始剤としては、例えばジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、ベンジルジメチルケタール、４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、２−メチル−２−モルホリノ（４−チオメチルフェニル）プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）ブタノン、２−ヒドロキシ−２−メチル−１−［４−（１−メチルビニル）フェニル］プロパノンオリゴマー等が挙げられるが、この限りではない。 Examples of the acetophenone photoradical polymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- Examples include (4-morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer, but are not limited thereto.
前記のアシルホスフィンオキサイド系光ラジカル重合開始剤としては、例えば、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、２，４，６−トリメチルベンゾイル−ジフェニルフォスフィンオキサイド等が挙げられるが、この限りではない。 Examples of the acylphosphine oxide photo radical polymerization initiator include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the like. But this is not the case.
本発明における（Ｃ）成分の配合量は、（Ａ）成分と（Ｂ）成分の合計量１００質量部に対して、０．１〜３０質量部が好ましく、より好ましくは、０．３〜２０質量部であり、特に好ましくは、０．５〜１５質量部である。０．１質量部未満では、光電変換素子用シール剤の光硬化性が低下してしまうので、硬化物の水蒸気バリア性の低下、ガラス等の基板への接着力の低下が生じるおそれがあり、３０質量部を超えると、光電変換素子用シール剤の硬化物の透明性が損なわれるおそれがある。 The blending amount of the component (C) in the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts per 100 parts by mass of the total amount of the components (A) and (B). It is a mass part, Most preferably, it is 0.5-15 mass part. If it is less than 0.1 parts by mass, the photocuring property of the sealing agent for photoelectric conversion elements is lowered, so that there is a possibility that the water vapor barrier property of the cured product is lowered, and the adhesive force to a substrate such as glass is lowered, When it exceeds 30 mass parts, there exists a possibility that transparency of the hardened | cured material of the sealing compound for photoelectric conversion elements may be impaired.
＜（Ｄ）成分＞
本発明ではさらに、（Ｄ）成分として下記の一般式（２）又は（３）で表される基を有する（メタ）アクリレートを加えてもよい。
In the present invention, (meth) acrylate having a group represented by the following general formula (2) or (3) may be added as the component (D).
（Ｄ）成分としては、例えば、２−ヒドロキシメチル（メタ）アクリレートアシッドホスフェート、２−ヒドロキシエチル（メタ）アクリレートアシッドホスフェート、２−ヒドロキシプロピル（メタ）アクリレートアシッドホスフェート、エチレンオキサイド変性リン酸ジアクリレート、エチレンオキサイド変性リン酸トリアクリレート、エチレンオキサイド変性リン酸ジメタアクリレート及びカプロラクトン変性エチレンオキサイド変性リン酸ジメタアクリレート等があげられる。これらは単独で用いられてもよく、２種以上が併用されてもよい。なお、本発明の（Ｄ）成分は、本発明の（Ａ）成分や（Ｂ）成分とは、異なる。 Examples of the component (D) include 2-hydroxymethyl (meth) acrylate acid phosphate, 2-hydroxyethyl (meth) acrylate acid phosphate, 2-hydroxypropyl (meth) acrylate acid phosphate, ethylene oxide-modified phosphate diacrylate, Examples thereof include ethylene oxide-modified phosphoric acid triacrylate, ethylene oxide-modified phosphoric acid dimethacrylate, and caprolactone-modified ethylene oxide-modified phosphoric acid dimethacrylate. These may be used independently and 2 or more types may be used together. In addition, (D) component of this invention differs from the (A) component and (B) component of this invention.
（Ｄ）成分の市販品としては、例えばライトエステルＰ−Ａ、Ｐ−１Ｍ、Ｐ−２Ｍ（共栄社化学株式会社）、カヤマーＰＭ−１（日本化薬社製）などがあげられる。 As a commercial item of (D) component, light ester PA, P-1M, P-2M (Kyoeisha Chemical Co., Ltd.), Kayamar PM-1 (made by Nippon Kayaku Co., Ltd.), etc. are mention | raise | lifted, for example.
前記（Ｄ）成分の配合量は、特に限定されないが、（Ａ）成分と（Ｂ）成分の合計量１００質量部に対して、０．１〜５０質量部であり、更に好ましくは０．５〜２５質量部であり、特に好ましくは１〜１０質量部である。０．１質量部を下回ると、ガラス基板との接着力が劣るおそれがあり、５０質量部を超えると、水蒸気バリア性が悪くなり、さらに貯蔵安定性におとるおそれがある。 Although the compounding quantity of the said (D) component is not specifically limited, It is 0.1-50 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, More preferably, it is 0.5. It is -25 mass parts, Most preferably, it is 1-10 mass parts. If the amount is less than 0.1 parts by mass, the adhesive strength to the glass substrate may be inferior, and if it exceeds 50 parts by mass, the water vapor barrier property may be deteriorated and further storage stability may be obtained.
本発明に対し、本発明の目的を損なわない範囲で、シランカップリング剤、充填材、（Ａ）成分、（Ｄ）成分以外の（メタ）アクリロイル基を有する化合物、トリス−［（３−メルカプトプロピオニルオキシ）−エチル］−イソシアヌレート、ペンタエリスリトール テトラキス（３−メルカプトプロピオネート）、トリメチロールプロパン トリス（３−メルカプトプロピオネート）、ジペンタエリスリトール ヘキサキス（３−メルカプトプロピオネート）等のポリチオール化合物、エポキシ樹脂、粘着付与剤、熱可塑性エラストマー、ゴム状ポリマー微粒子、保存安定剤、酸化防止剤、光安定剤、接着助剤、可塑剤、染料、顔料、難燃剤、増感剤、熱ラジカル開始剤、有機溶剤、重金属不活性剤、イオントラップ剤、乳化剤、水分散安定剤、消泡剤、離型剤、レベリング剤、ワックス、レオロジーコントロール剤、界面活性剤等の添加剤を適量配合しても良い。 To the present invention, a compound having a (meth) acryloyl group other than the silane coupling agent, filler, component (A), component (D), tris-[(3-mercapto, as long as the object of the present invention is not impaired. Polythiols such as propionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) Compound, Epoxy resin, Tackifier, Thermoplastic elastomer, Rubber polymer fine particle, Storage stabilizer, Antioxidant, Light stabilizer, Adhesion aid, Plasticizer, Dye, Pigment, Flame retardant, Sensitizer, Thermal radical Initiator, organic solvent, heavy metal deactivator, ion trapping agent, emulsifier, water dispersion stability , Defoamers, release agents, leveling agents, waxes, rheology control agents, additives such as a surfactant may be appropriate amount.
前記シランカップリング剤としては、例えば、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メチルジエトキシシラン、３−グリシドキシプロピルメチルジプロピルオキシシラン、３−グリシドキシプロピルジメチルモノメトキシシラン、３−グリシドキシプロピルジメチルモノエトキシシラン、３−グリシドキシプロピルジメチルモノプロピルオキシシラン、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トリエトキシシラン、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エトキシシラン等のグリシジル基含有シランカップリング剤、ビニルトリス（β−メトキシエトキシ）シラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン等のビニル基含有シランカップリング剤、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エトキシシラン、３−メタクリロキシプロピルジメチルモノメトキシシラン、３−メタクリロキシプロピルジメチルモノエトキシシラン、３−アクリロキシプロピルメチルジプロピルオキシシラン、３−アクリロキシプロピルメチルジメトキシシラン、３−ア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メチルジプロピルオキシシラン、３−アクリロキシプロピルジメチルモノプロピルオキシシラン、３−アクリロキシプロピルジメチルモノメトキシシラン、３−アクリロキシプロピルジメチルモノエトキシシラン、３−アクリロキシプロピルジメチルモノプロピルオキシシラン、γ−メタクリロキシプロピルトリメトキシシラン等の（メタ）アクリル基含有シランカップリング剤、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン等のアミノ基含有シランカップリング剤、その他γ−メルカプトプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン等が挙げられる。これらの中でもガラス基板との接着力が優れるという観点よりグリシジル基含有シランカップリング剤、ビニル基含有シランカップリング剤、（メタ）アクリル基含有シランカップリング剤が好ましい。これらは単独で用いられてもよく、２種以上が併用されてもよい。 Examples of the silane coupling agent include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldipropyloxysilane, and 3-glycidoxypropyldimethyl. Monomethoxysilane, 3-glycidoxypropyldimethylmonoethoxysilane, 3-glycidoxypropyldimethylmonopropyloxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxy Glycidyl group-containing silane coupling agents such as silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyl Vinyl group-containing silane coupling agent such as rutrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldimethylmonomethoxysilane, 3-methacryloxypropyldimethylmonoethoxy Silane, 3-acryloxypropylmethyldipropyloxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldipropyloxysilane, 3-acryloxypropyldimethylmono Propyloxysilane, 3-acryloxypropyldimethylmonomethoxysilane, 3-acryloxypropyldimethylmonoethoxysilane, 3-acryloxypropyldimethylmolybdenum (Meth) acrylic group-containing silane coupling agents such as nopropyloxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane And amino group-containing silane coupling agents such as N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like. Among these, a glycidyl group-containing silane coupling agent, a vinyl group-containing silane coupling agent, and a (meth) acryl group-containing silane coupling agent are preferable from the viewpoint of excellent adhesion to a glass substrate. These may be used independently and 2 or more types may be used together.
シランカップリング剤の配合量は、本発明の（Ａ）成分と（Ｂ）成分の合計量１００質量部に対して０．１〜２０質量部であることが好ましい。０．１質量部よりも少ないとガラス基板との接着力が劣るおそれがあり、２０質量部を上回ると、貯蔵安定性に劣るおそれがある。 It is preferable that the compounding quantity of a silane coupling agent is 0.1-20 mass parts with respect to 100 mass parts of total amounts of (A) component of this invention, and (B) component. If the amount is less than 0.1 parts by mass, the adhesion to the glass substrate may be inferior, and if it exceeds 20 parts by mass, the storage stability may be inferior.
（Ｄ）成分に対するシランカップリング剤の質量比率（シランカップリング剤／（Ｄ）成分）は、特に限定されないが、ガラス等の基板への接着力と貯蔵安定性に優れる観点から０．０１〜５００であり、更に好ましくは０．０５〜２００であり、特に好ましくは、０．１〜５０があげられる。 The mass ratio of the silane coupling agent to the component (D) (silane coupling agent / (D) component) is not particularly limited, but is 0.01 to from the viewpoint of excellent adhesion to a substrate such as glass and storage stability. 500, more preferably 0.05 to 200, and particularly preferably 0.1 to 50.
前記充填材を含有させてもよい。前記充填材としては、ガラス、シリカ、アルミナ、タルク、マイカ、シリコーンゴム粉体、炭酸カルシウム、窒化アルミ、カーボン粉、カオリンクレー、乾燥粘土鉱物、乾燥珪藻土等が挙げられるが、これらの中でも、水蒸気バリア性が優れる光電変換素子用シール剤が得られることから、ガラス、シリカ、タルクが好ましい。 The filler may be included. Examples of the filler include glass, silica, alumina, talc, mica, silicone rubber powder, calcium carbonate, aluminum nitride, carbon powder, kaolin clay, dry clay mineral, and dry diatomaceous earth. Among these, water vapor Glass, silica, and talc are preferable because a sealing agent for photoelectric conversion elements having excellent barrier properties can be obtained.
充填材の平均粒径が０．００１〜１００μｍであることが好ましく、更に好ましくは平均粒径が０．０１〜５０μｍであり、特に好ましくは、平均粒径が０．１〜２０μｍ。平均粒径が０．００１μｍを下回ると、光電変換素子用シール剤の粘度が、塗布等の作業性が劣るおそれがあり、１００μｍを上回ると、水蒸気バリア性のおとる硬化物になるおそれがある。なお、平均粒径の測定方法はレーザー回析法である。なお、充填材の配合量は、特に限定されないが、（Ａ）成分と（Ｂ）成分の合計量１００質量部中、０．１〜３００質量部が好ましく、更に好ましくは１〜２００質量部であり、特に好ましくは、５〜１００質量部である。 The average particle diameter of the filler is preferably 0.001 to 100 μm, more preferably 0.01 to 50 μm, and particularly preferably 0.1 to 20 μm. If the average particle diameter is less than 0.001 μm, the viscosity of the sealing agent for photoelectric conversion elements may be inferior in workability such as coating, and if it exceeds 100 μm, the cured product may have a water vapor barrier property. . In addition, the measuring method of an average particle diameter is a laser diffraction method. In addition, the compounding quantity of a filler is although it does not specifically limit, 0.1-300 mass parts is preferable in 100 mass parts of total amounts of (A) component and (B) component, More preferably, it is 1-200 mass parts. Yes, and particularly preferably 5 to 100 parts by mass.
シリカ系充填材は、硬化物の機械的強度を向上させる目的で配合される。好ましくは、ジメチルジクロロシラン、ヘキサメチルシラザン、シリコーンオイル、アミノシラン、炭素数１〜１２のアルキルシラン、（メタ）アクリロイル基を有するシランなどで疎水化処理したものなどが用いられる。 A silica type filler is mix | blended in order to improve the mechanical strength of hardened | cured material. Preferably, dimethyldichlorosilane, hexamethylsilazane, silicone oil, aminosilane, alkyl silane having 1 to 12 carbon atoms, silane having a (meth) acryloyl group, and the like are used.
シリカの市販品としては例えば、アエロジルＲ９７４、Ｒ９７２、Ｒ９２００、Ｒ９７６、Ｒ９７６Ｓ、ＲＸ５０、ＮＡＸ５０、ＮＸ９０、ＲＸ２００，Ｒ８２００、ＲＸ３００，Ｒ８１２、Ｒ８１２Ｓ、ＲＹ５０、ＮＹ５０、ＲＹ２００Ｓ、Ｒ２０２，ＲＹ２００、ＲＹ３００、Ｒ１０４、Ｒ１０６、ＲＡ２００Ｈ、ＲＡ２００ＨＳ、Ｒ８０５、Ｒ８１６、ＲＭ５０、Ｒ７１１、Ｒ７２００（日本アエロジル製）が挙げられる。 Examples of commercially available silicas include Aerosil R974, R972, R9200, R976, R976S, RX50, NAX50, NX90, RX200, R8200, RX300, R812, R812S, RY50, NY50, RY200S, R202, RY200, RY300, R104, R106. RA200H, RA200HS, R805, R816, RM50, R711, R7200 (manufactured by Nippon Aerosil Co., Ltd.).
本発明に対し、（Ａ）、（Ｂ）、（Ｄ）成分以外のメタ）アクリロイル基を有する化合物としては、例えば、単官能性、二官能性、三官能性及び多官能性のモノマー、オリゴマー等を使用することができる。これらは単独で若しくは二種以上の混合物として用いることができる。 For the present invention, examples of the compound having a meth) acryloyl group other than the components (A), (B) and (D) include, for example, monofunctional, bifunctional, trifunctional and polyfunctional monomers and oligomers. Etc. can be used. These can be used alone or as a mixture of two or more.
単官能性モノマーとしては、例えば、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、カプロラクトン変性テトラヒドロフルフリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシテトラエチレングリコール（メタ）アクリレート、ノニルフェノキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、グリセロール（メタ）アクリレート、変性ブチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、モルホリノ（メタ）アクリレート等が挙げられる。 Examples of the monofunctional monomer include lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl ( (Meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) ) Acrylate, butoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, glycerol (meth) acrylate, modified butyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, morpholino (meth) acrylate.
二官能性モノマーとしては、例えば、ネオペンチルグリコールジ（メタ）アクリレート、ステアリン酸変性ペンタエリスリトールジ（メタ）アクリレート、ジシクロペンテニルジアクリレート、ジ（メタ）アクリロイルイソシアヌレート等が挙げられる。 Examples of the bifunctional monomer include neopentyl glycol di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, dicyclopentenyl diacrylate, di (meth) acryloyl isocyanurate, and the like.
三官能性モノマーとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリス（アクリロイルオキシエチル）イソシアヌレート等が挙げられる。 Examples of the trifunctional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, and the like.
多官能性モノマーとしては、例えば、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールモノヒドロキシペンタ（メタ）アクリレート、アルキル変性ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。これらの重合性モノマーは単独で若しくは二種以上の混合物として用いることができる。 Examples of the polyfunctional monomer include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol pentaacrylate, dipentaerythritol hexa ( And (meth) acrylate. These polymerizable monomers can be used alone or as a mixture of two or more.
熱可塑性エラストマーは、本発明の光電変換素子用シール剤の内部応力緩和又は接着力を向上させる目的で用いられる。熱可塑性エラストマーとしては、例えば、ポリスチレンブロックとポリブタジエンブロックやポリイソプレンブロック、ポリイソブチレン等からなるブロック共重合体であるスチレン系熱可塑性エラストマー、オレフィン系熱可塑性エラストマー、ウレタン系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー、アミド系熱可塑性エラストマー等が挙げられる。これらの中でもスチレン系熱可塑性エラストマー又はウレタン系熱可塑性エラストマーが特に好ましい。これらは、単独で、又は二以上組み合わせて使用してもよい。 The thermoplastic elastomer is used for the purpose of relaxing internal stress or improving the adhesive force of the sealing agent for photoelectric conversion elements of the present invention. Examples of the thermoplastic elastomer include a styrene thermoplastic elastomer, an olefin thermoplastic elastomer, a urethane thermoplastic elastomer, and a polyester thermal copolymer that are block copolymers composed of a polystyrene block and a polybutadiene block, a polyisoprene block, a polyisobutylene, and the like. Examples thereof include a plastic elastomer and an amide thermoplastic elastomer. Among these, a styrene thermoplastic elastomer or a urethane thermoplastic elastomer is particularly preferable. These may be used alone or in combination of two or more.
ゴム状ポリマー微粒子は光電変換素子用シール剤の内部応力緩和又は接着力向上を目的として添加されてもよい。これらのゴム状ポリマー微粒子は、例えばアクリルゴム系のゴム状ポリマー、シリコ−ンゴム系のゴム状ポリマー、オレフィンゴム系ゴム状ポリマー、ポリエステルゴム系ゴム状ポリマー、ウレタンゴム系ゴム状ポリマーが挙げられ、中でもシリコ−ンゴム系のゴム状ポリマー、オレフィンゴム系ゴム状ポリマーであること好ましい。単独でも複数を併用してもよい。 The rubber-like polymer fine particles may be added for the purpose of relaxing internal stress or improving adhesive strength of the sealing agent for photoelectric conversion elements. These rubber-like polymer fine particles include, for example, acrylic rubber-based rubbery polymers, silicone rubber-based rubbery polymers, olefin rubber-based rubbery polymers, polyester rubber-based rubbery polymers, urethane rubber-based rubbery polymers, Of these, a silicone rubber-based rubber polymer and an olefin rubber-based rubber polymer are preferable. It may be used alone or in combination.
上記の任意成分のうち、酸化防止剤及び光安定剤の添加は、硬化性組成物の耐候性向上のために好ましい。酸化防止剤及び光安定剤としては市販品を使用することができる。例えば、スミライザーＢＨＴ、スミライザーＳ、スミライザーＢＰ−７６、スミライザーＭＤＰ−Ｓ、スミライザーＧＭ、スミライザーＢＢＭ−Ｓ、スミライザーＷＸ−Ｒ、スミライザーＮＷ、スミライザーＢＰ−１７９、スミライザーＢＰ−１０１、スミライザーＧＡ−８０、スミライザーＴＮＰ、スミライザーＴＰＰ−Ｒ、スミライザーＰ−１６（住友化学株式会社製）、アデカスタブＡＯ−２０、アデカスタブＡＯ−３０、アデカスタブＡＯ−４０、アデカスタブＡＯ−５０、アデカスタブＡＯ−６０、アデカスタブＡＯ−７０、アデカスタブＡＯ−８０、アデカスタブＡＯ−３３０、アデカスタブＰＥＰ−４Ｃ、アデカスタブＰＥＰ−８、アデカスタブＰＥＰ−２４Ｇ、アデカスタブＰＥＰ−３６、アデカスタブＨＰ−１０、アデカスタブ２１１２、アデカスタブ２６０、アデカスタブ５２２Ａ、アデカスタブ３２９Ｋ、アデカスタブ１５００、アデカスタブＣ、アデカスタブ１３５Ａ、アデカスタブ３０１０（旭電化工業株式会社製）、チヌビン７７０、チヌビン７６５、チヌビン１４４、チヌビン６２２、チヌビン１１１、チヌビン１２３、チヌビン２９２（チバスペシャリティケミカルズ株式会社製）等が挙げられる。これらの酸化防止剤及び光安定剤の配合量は特に限定されないが、（Ａ）成分１００質量部に対して、好ましくは０．００１〜１０質量部、より好ましくは０．０１〜５質量部である。 Among the above optional components, addition of an antioxidant and a light stabilizer is preferable for improving the weather resistance of the curable composition. Commercial products can be used as the antioxidant and the light stabilizer. For example, a Summarizer BHT, a Summarizer S, a Summarizer BP-76, a Summarizer MDP-S, a Summarizer GM, a Summarizer BBM-S, a Summarizer WX-R, a Summarizer NW, a Summarizer BP-179, a Summarizer BP-101, a Summarizer GA-80, a Sumizer TNP, Sumilyzer TPP-R, Sumilyzer P-16 (manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK Tab 2112, Adekas tab 260, Adekas tab 522A, Adekas tab 329K, Adekas tab 1500, Adekas tab C, Adekas tab 135A, Adekas tab 3010 (Asahi Denka Kogyo Co., Ltd.), Tinuvin 770, Tinuvin 765, Tinuvin 144, Tinuvin 622, Tinuvin 111, Tinuvin 123, Tinuvin 292 (Ciba Specialty Chemicals Co., Ltd.) Although the compounding quantity of these antioxidants and light stabilizers is not specifically limited, Preferably it is 0.001-10 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 0.01-5 mass parts. is there.
本発明の光電変換素子用シール剤は、紫外線等の光などの活性エネルギー線を照射することにより速やかに重合反応が進み硬化する。前記活性エネルギー線は、１５０〜７５０ｎｍの波長域の照射光が好ましく、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプ又はＬＥＤランプを使用して積算光量１〜１００ｋＪ／ｃｍ２の積算光量で硬化することができ、好ましくは５〜７０ｋＪ／ｃｍ２の積算光量である。 The sealing agent for photoelectric conversion elements of the present invention is cured by rapid polymerization reaction by irradiation with active energy rays such as light such as ultraviolet rays. The active energy ray is preferably irradiated light having a wavelength range of 150 to 750 nm, and an integrated light amount of 1 to 100 kJ / LED using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp or an LED lamp. It can be cured at the integrated light quantity of cm 2, preferably integrated quantity of light 5~70kJ / cm 2.
本発明の光電変換素子用シール剤は、紫外線等の光などの活性エネルギー線の照射により重合反応が速やかに進み水蒸気バリア性の高い硬化物が得られ、且つガラス等の基板への接着力に優れるので、各種封止用途に好適に用いられる。具体的には、特に水蒸気バリア性及びガラス等の基板への接着力が求められる封止用途であるシリコン系太陽電池、色素増感太陽電池、有機薄膜系太陽電池等の光電変換素子用途等に好ましく用いられる。 The sealing agent for a photoelectric conversion element of the present invention has a polymerization reaction that proceeds rapidly by irradiation with an active energy ray such as light such as ultraviolet rays, and a cured product having a high water vapor barrier property is obtained. Since it is excellent, it is suitably used for various sealing applications. Specifically, for use in photoelectric conversion elements such as silicon-based solar cells, dye-sensitized solar cells, and organic thin-film solar cells, which are sealing applications that require water vapor barrier properties and adhesion to substrates such as glass. Preferably used.
本発明におけるガラス等の基板への接着力とは、１．０ＭＰａ以上であるものを意味し、この特性を有する光電変換素子用シール剤は、光電変換素子などの用途に好適に用いられる。ガラス等の基板への接着力が１．０ＭＰａ未満であるシール剤を光電変換素子に用いた場合、ガラス基板基盤からはく離してしまい、電解液の漏洩が生じ、光電変換素子の性能が低下してしまうおそれがある。 The adhesive force to a substrate such as glass in the present invention means a material having a pressure of 1.0 MPa or more, and a photoelectric conversion element sealing agent having this characteristic is suitably used for applications such as a photoelectric conversion element. When a sealing agent having an adhesive strength to a substrate such as glass of less than 1.0 MPa is used for the photoelectric conversion element, it will be peeled off from the glass substrate base, resulting in leakage of the electrolyte, resulting in a decrease in the performance of the photoelectric conversion element. There is a risk that.
なお、本発明における水蒸気バリア性とは、透湿度が１５０ｇ／ｍ２・２４ｈ以下であるものを意味し、この特性を有する光電変換素子用シール剤は、光電変換素子などの用途に好適に用いられる。透湿度が１５０ｇ／ｍ２・２４ｈを上回ったシール剤を光電変換素子に用いた場合、外部から侵入した湿度によって変質や劣化が起こり、光電変換素子の性能が低下してしまうおそれがある。 In addition, the water vapor barrier property in the present invention means that the moisture permeability is 150 g / m 2 · 24 h or less, and the photoelectric conversion element sealing agent having this characteristic is suitably used for applications such as photoelectric conversion elements. It is done. When a sealing agent having a moisture permeability of more than 150 g / m 2 · 24 h is used for the photoelectric conversion element, the humidity or the like that enters from the outside may cause alteration or deterioration, and the performance of the photoelectric conversion element may be deteriorated.
以下に実施例をあげて本発明を更に詳細説明をするが、本発明はこれら実施例に限定されるものではない。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
＜組成物の調製＞
各成分を表１に示す質量部で採取し、常温にて遮光下でミキサーで６０分混合し、光電変換素子用シール剤を調整した。数値は全て質量部で表記する。
<Preparation of composition>
Each component was sampled in parts by mass shown in Table 1, and mixed for 60 minutes with a mixer under light shielding at room temperature to prepare a photoelectric conversion element sealing agent. All numerical values are expressed in parts by mass.
・（Ａ）成分
ａ１：平均２．３個のエチレンオキサイド構造部分の繰り返し単位を有するＥＯ変性ビスフェノールＡジアクリレート（製品名ＢＰＥ−８０Ｎ、新中村化学株式会社製）
ａ２：４個のエチレンオキサイド構造部分の繰り返し単位を有するＥＯ変性ビスフェノールＡジアクリレート（製品名ＦＡ３２４、日立化成株式会社製）
-(A) component a1: EO-modified bisphenol A diacrylate having an average of 2.3 ethylene oxide structural moiety repeating units (product name BPE-80N, manufactured by Shin-Nakamura Chemical Co., Ltd.)
a2: EO-modified bisphenol A diacrylate having a repeating unit of four ethylene oxide structure parts (product name FA324, manufactured by Hitachi Chemical Co., Ltd.)
（Ａ）成分の比較成分
ａ’１：１０個のエチレンオキサイド構造部分の繰り返し単位を有するＥＯ変性ビスフェノールＡジアクリレート（製品名Ａ−ＢＰＥ−１０、新中村化学工業株式会社製）
(A) Component comparison component a′1: EO-modified bisphenol A diacrylate having a repeating unit of 10 ethylene oxide structure parts (product name A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.)
（Ｂ）成分
ｂ１：一般式（１）において、ｎ＝４であり、Ｘが−Ｃ（ＣＨ３）２−である表されるエポキシ（メタ）アクリレート、酸価７．９ＫＯＨｍｇ／ｇ（製品名ＶＲ−６０、昭和電工株式会社製）
ｂ２：一般式（１）において、ｎ＝２であり、Ｘが−Ｃ（ＣＨ３）２−である表されるエポキシ（メタ）アクリレート、酸価６．６ＫＯＨｍｇ／ｇ （製品名ＶＲ−９０、昭和電工株式会社製）
(B) Component b1: An epoxy (meth) acrylate represented by the formula (1), where n = 4 and X is —C (CH 3 ) 2 —, an acid value of 7.9 KOHmg / g (product name) VR-60, manufactured by Showa Denko KK
b2: An epoxy (meth) acrylate represented by the formula (1) in which n = 2 and X is —C (CH 3 ) 2 —, an acid value of 6.6 KOHmg / g (product name VR-90, Showa Denko)
（Ｂ）成分の比較成分
Ｂ’１：ウレタン（メタ）アクリレート（製品名ＣＮ９８９３、サートマー社製）
(B) Component Comparison Component B'1: Urethane (meth) acrylate (Product name CN 9893, manufactured by Sartomer)
（Ｃ）成分
ｃ１：1-ヒドロキシ-シクロヘキシル-フェニル-ケトン（ＢＡＳＦ社製）
ｃ２：２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド（ＢＡＳＦ社製）
(C) Component c1: 1-hydroxy-cyclohexyl-phenyl-ketone (BASF)
c2: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF)
（Ｄ）成分
ｄ１：２ーヒドロキシエチルメタクリレートアシッドホスフェート
(D) Component d1: 2-hydroxyethyl methacrylate acid phosphate
＜その他成分＞
・シランカップリング剤：３−アクリロキシプロピルトリメトキシシラン（製品名ＫＢＭ５１０３、信越化学株式会社製）
・シリカ：平均粒径１．５μｍの球状シリカ
・タルク：鱗片状タルク
<Other ingredients>
Silane coupling agent: 3-acryloxypropyltrimethoxysilane (product name KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
Silica: Spherical silica with an average particle size of 1.5 μm Talc: Scale-like talc
＜特性評価＞
各種特性に関して次のようにして測定した。
<Characteristic evaluation>
Various characteristics were measured as follows.
［十字はく離接着試験］
厚み５ｍｍ×幅２５ｍｍ×長さ５０ｍｍガラス基板２枚を十字になるように各光電変換素子用シール剤ではりあわせたものに、紫外線照射機により積算光量３０ｋＪ／ｃｍ２を照射し、試験片を作成した。そして、この試験片を引っ張り試験器を用いてクロスヘッドにより押圧し、ガラス板とガラス板とが分離するまでに要する応力を測定し、結果を表１に示す。
［評価基準］
○：１．０ＭＰａ以上
×：１．０ＭＰａ未満
[Cross peel adhesion test]
Thickness 5mm x width 25mm x length 50mm Two glass substrates bonded to each other with a sealant for each photoelectric conversion element so as to form a cross are irradiated with an integrated light quantity of 30 kJ / cm 2 by an ultraviolet irradiator. Created. And this test piece was pressed with a crosshead using a tensile tester, the stress required until a glass plate and a glass plate isolate | separated was measured, and the result is shown in Table 1.
[Evaluation criteria]
○: 1.0 MPa or more
X: Less than 1.0 MPa
［水蒸気バリア性試験（透湿バリア性試験）］
２００ｍｍ×２００ｍｍ×０．２ｍｍの枠に表１の各光電変換素子用シール剤を流し込んだ。その後、紫外線照射機により積算光量３０ｋＪ／ｃｍ２を照射し、厚さ０．２ｍｍのシート状の硬化物を作成した。塩化カルシウム（無水）５ｇを直径３０ｍｍの開口部を有するアルミニウム製カップに入れて、前記硬化物をカップにセットした。「初期の全重量」（ｇ）を測定した後、雰囲気温度８５℃で相対湿度８５％に保たれた恒温恒湿槽に放置し、２４時間毎に「放置後の全重量」（ｇ）を測定して、透湿度（ｇ／ｍ２・２４ｈ）を計算した。詳細な試験方法はＪＩＳ Ｚ ０２０８に準拠する。
［評価基準］
◎：１００ｇ／ｍ２・２４ｈ未満
○：１００ｇ／ｍ２・２４ｈ以上、１５０ｇ／ｍ２・２４ｈ未満
×：１５０ｇ／ｍ２・２４ｈ以上
[Water vapor barrier property test (moisture permeability barrier property test)]
Each sealing agent for photoelectric conversion elements in Table 1 was poured into a frame of 200 mm × 200 mm × 0.2 mm. Then, the integrated light quantity 30kJ / cm < 2 > was irradiated with the ultraviolet irradiation machine, and the sheet-like hardened | cured material of thickness 0.2mm was created. 5 g of calcium chloride (anhydrous) was put in an aluminum cup having an opening with a diameter of 30 mm, and the cured product was set in the cup. After measuring the “initial total weight” (g), leave it in a constant temperature and humidity chamber maintained at an atmospheric temperature of 85 ° C. and a relative humidity of 85%, and set the “total weight after leaving” (g) every 24 hours. Measured and calculated moisture permeability (g / m 2 · 24h). The detailed test method conforms to JIS Z 0208.
[Evaluation criteria]
A: Less than 100 g / m 2 · 24 h ○: 100 g / m 2 · 24 h or more, less than 150 g / m 2 · 24 h ×: 150 g / m 2 · 24 h or more
比較例１、２は、（Ａ）成分と（Ｂ）成分の合計量１００質量部に対して、（Ａ）成分が２５質量部未満なので、本発明の実施例１〜６と比較し、ガラス等の基板への接着力が劣る結果であった。更に比較例２は、水蒸気バリア性も劣る結果であった。また、比較例３は、本発明の（Ａ）成分の代わりにＥＯの繰り返し数が１０であるＥＯ変性ビスフェノールＡジアクリレートを用いているので、本発明の実施例１〜６と比較し、水蒸気バリア性が劣る結果であった。
また、比較例４は、本発明の（Ａ）成分が非含有なので、本発明の実施例１〜６と比較し、水蒸気バリア性が劣る結果であった。また、比較例５は、本発明の（Ｂ）成分が非含有なので、本発明の実施例１〜６と比較し、ガラス等の基板への接着力が劣る結果であった。
比較例６は、本発明の（Ｂ）成分の代わりにウレタン（メタ）アクリレートを用いているので、本発明の実施例１〜６と比較し、水蒸気バリア性が劣る結果であった。
In Comparative Examples 1 and 2, since (A) component is less than 25 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B), glass is compared with Examples 1 to 6 of the present invention. As a result, the adhesive strength to the substrate was poor. Furthermore, the comparative example 2 was a result in which water vapor | steam barrier property is also inferior. Moreover, since the comparative example 3 uses EO modified bisphenol A diacrylate whose EO repetition number is 10 instead of the component (A) of the present invention, it is compared with Examples 1 to 6 of the present invention. The result was poor barrier properties.
Moreover, since the (A) component of this invention is not contained, the comparative example 4 was a result in which water vapor | steam barrier property is inferior compared with Examples 1-6 of this invention. Moreover, since the comparative example 5 does not contain (B) component of this invention, it was a result in which the adhesive force to substrates, such as glass, is inferior compared with Examples 1-6 of this invention.
In Comparative Example 6, since urethane (meth) acrylate was used instead of the component (B) of the present invention, the water vapor barrier property was inferior compared with Examples 1 to 6 of the present invention.
本発明の光電変換素子用シール剤は、紫外線等の光などの活性エネルギー線の照射により重合反応が速やかに進み水蒸気バリア性の高い硬化物が得られ、且つガラス等の基板への接着力に優れるので、各種封止用途に好適用いられる。具体的には、特に水蒸気バリア性及びガラス等の基板への接着力が求められる封止用途である液晶ディスプレイ、有機ＥＬディスプレイ、電子ペーパー等のディスプレイ用途やシリコン系太陽電池、色素増感太陽電池、有機薄膜系太陽電池等の光電変換素子用途等の封止剤として極めて有効であり、広い分野に適用可能であることから産業上有用である。 The sealing agent for a photoelectric conversion element of the present invention has a polymerization reaction that proceeds rapidly by irradiation with an active energy ray such as light such as ultraviolet rays, and a cured product having a high water vapor barrier property is obtained. Since it is excellent, it is suitably used for various sealing applications. Specifically, display applications such as liquid crystal displays, organic EL displays, electronic paper, silicon solar cells, and dye-sensitized solar cells, which are sealing applications that require water vapor barrier properties and adhesion to substrates such as glass. It is extremely effective as a sealant for use in photoelectric conversion elements such as organic thin film solar cells and is industrially useful because it can be applied to a wide range of fields.
Claims (4)
（Ａ）成分と（Ｂ）成分の合計量１００質量部中、（Ａ）成分が２５〜９５質量部含有することを特徴とする光電変換素子用シール剤。 (Meth) acrylic compound ((A) component) having a bisphenol structure and an alkylene oxide unit repeating average number of 1 to 8, epoxy (meth) acrylate ((B) component), and photoinitiator ((C) component) And 0.1-20 mass parts of silane coupling agents are contained with respect to 100 mass parts of total amounts of (A) component and (B) component ,
The sealing agent for photoelectric conversion elements, wherein the component (A) is contained in an amount of 25 to 95 parts by mass in 100 parts by mass of the total amount of the component (A) and the component (B).
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| CA2446125A1 (en) * | 2001-05-16 | 2002-11-21 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
| JP3955037B2 (en) * | 2004-04-16 | 2007-08-08 | 積水化学工業株式会社 | Curable resin composition for liquid crystal display element |
| TW200737531A (en) * | 2005-07-07 | 2007-10-01 | Nippon Kayaku Kk | Sealing agent for photoelectric conversion element and photo electric conversion element using the same |
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