JP2015071726A - Photocurable sealant composition - Google Patents
Photocurable sealant composition Download PDFInfo
- Publication number
- JP2015071726A JP2015071726A JP2013209039A JP2013209039A JP2015071726A JP 2015071726 A JP2015071726 A JP 2015071726A JP 2013209039 A JP2013209039 A JP 2013209039A JP 2013209039 A JP2013209039 A JP 2013209039A JP 2015071726 A JP2015071726 A JP 2015071726A
- Authority
- JP
- Japan
- Prior art keywords
- component
- meth
- acrylate
- group
- photocurable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000000565 sealant Substances 0.000 title claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 66
- -1 alkylene oxide-modified bisphenol Chemical class 0.000 claims abstract description 26
- 239000011521 glass Substances 0.000 claims abstract description 25
- 239000004593 Epoxy Substances 0.000 claims abstract description 17
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 6
- 239000011347 resin Substances 0.000 claims abstract description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 22
- 238000007789 sealing Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 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 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- 229920002379 silicone rubber Polymers 0.000 claims description 4
- 239000004945 silicone rubber Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 239000002734 clay mineral Substances 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 239000000758 substrate Substances 0.000 abstract description 20
- 238000003860 storage Methods 0.000 abstract description 15
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 22
- 239000003822 epoxy resin Substances 0.000 description 17
- 229920000647 polyepoxide Polymers 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 13
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 7
- 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 7
- 230000035699 permeability Effects 0.000 description 7
- 239000007870 radical polymerization initiator Substances 0.000 description 7
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000008393 encapsulating agent Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 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 4
- 239000005977 Ethylene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 239000000945 filler 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
- 238000012360 testing method Methods 0.000 description 4
- 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 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 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
- 150000001336 alkenes Chemical class 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
- 239000003505 polymerization initiator Substances 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 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
- 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 2
- 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 2
- 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 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 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
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 230000003078 antioxidant effect Effects 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
- 238000004132 cross linking Methods 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
- 239000000806 elastomer Substances 0.000 description 2
- HHBOIIOOTUCYQD-UHFFFAOYSA-N ethoxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(C)CCCOCC1CO1 HHBOIIOOTUCYQD-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- VOARQMXRPHXHID-UHFFFAOYSA-N methyl-[3-(oxiran-2-ylmethoxy)propyl]-dipropoxysilane Chemical compound CCCO[Si](C)(OCCC)CCCOCC1CO1 VOARQMXRPHXHID-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000002040 relaxant effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 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
- 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
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 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
- NREFJJBCYMZUEK-UHFFFAOYSA-N 2-[2-[4-[2-[4-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]phenyl]propan-2-yl]phenoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCOCCOC(=O)C(C)=C)C=C1 NREFJJBCYMZUEK-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
- 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
- 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
- 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
- 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
- SLDXSSRFNABVCN-UHFFFAOYSA-N 3-diethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[SiH](OCC)CCCOC(=O)C(C)=C SLDXSSRFNABVCN-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 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
- 229930185605 Bisphenol Natural products 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 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
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-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
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001343 alkyl silanes Chemical class 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
- 150000001408 amides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 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
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000001896 cresols Chemical class 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
- 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 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
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- CVDUUPMTIHXQKC-UHFFFAOYSA-N ethene 1,3,5-triazinane-2,4,6-trione Chemical group C=C.O=C1NC(=O)NC(=O)N1 CVDUUPMTIHXQKC-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 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
- 230000001771 impaired effect Effects 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
- 238000007561 laser diffraction method Methods 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
- FBNXYLDLGARYKQ-UHFFFAOYSA-N methoxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(C)CCCOCC1CO1 FBNXYLDLGARYKQ-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 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
- OURNLUUIQWKTRH-UHFFFAOYSA-N oxirane;phenol Chemical compound C1CO1.OC1=CC=CC=C1.OC1=CC=CC=C1 OURNLUUIQWKTRH-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- AJFJJTYOLHZAIE-UHFFFAOYSA-N phosphoric acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OP(O)(O)=O AJFJJTYOLHZAIE-UHFFFAOYSA-N 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
- 229920001223 polyethylene glycol 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
- 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
- 239000000376 reactant Substances 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
- 238000013112 stability test Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 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
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
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、貯蔵安定性に優れる光硬化性封止剤組成物に関するものである。 Photo-curing that polymerization reaction proceeds rapidly by irradiation of active energy rays such as ultraviolet rays and the like, a cured product having excellent adhesion to glass and other substrates and having a high water vapor barrier property, and excellent storage stability. It is related with a sealing agent composition.
従来より、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などの光電変換素子用途において、ガラス基板に対する接着力に優れ、且つ封止性(水蒸気バリア性)の高い光硬化性封止剤が多用されている。 Conventionally, it has excellent adhesion to glass substrates and is sealed in photoelectric conversion elements such as liquid crystal displays, organic EL displays, electronic paper displays, silicon solar cells, dye-sensitized solar cells, and organic thin film solar cells. A photocurable sealant having a high stopping property (water vapor barrier property) is frequently used.
例えば、特許文献1には、エポキシ樹脂を(メタ)アクリレート化して得られる硬化性樹脂、ラジカル発生型光重合開始剤、1分子中に(メタ)アクリル基とリン酸基の両方を含有する接着補助剤及び充填剤を含有することを特徴とする液晶用シール剤が開示されている。また、特許文献2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。 For example, Patent Document 1 discloses a curable resin obtained by (epoxy) epoxy resin (radical generation type photopolymerization initiator), an adhesive containing both (meth) acrylic groups and phosphoric acid groups in one molecule. A liquid crystal sealing agent characterized by containing an auxiliary agent and a filler is disclosed. Patent Document 2 discloses a sealing agent for a photoelectric conversion element containing an epoxy resin, a thermosetting agent, an epoxy (meth) acrylate, and a photopolymerization initiator.
しかしながら、特許文献1、2に開示された液晶用シール剤又は光電変換素子用シール剤は、室温或いは40℃程度の温度環境下における貯蔵安定性に問題があった。このような背景から、ガラス等の基板への接着力及び水蒸気バリア性を維持させつつ、さらに貯蔵安定性にも優れる光硬化性封止剤組成物が求められていた。 However, the liquid crystal sealing agent or photoelectric conversion element sealing agent disclosed in Patent Documents 1 and 2 has a problem in storage stability at room temperature or in a temperature environment of about 40 ° C. From such a background, there has been a demand for a photocurable sealant composition that is excellent in storage stability while maintaining adhesion to a substrate such as glass and water vapor barrier properties.
本発明の光硬化性封止剤組成物は、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、貯蔵安定性に優れる光硬化性封止剤組成物を提供することを目的とする。 The photocurable encapsulant composition of the present invention is a polymerized reaction that proceeds rapidly by irradiation with active energy rays such as ultraviolet rays, and a cured product having a high water vapor barrier property is obtained, and is adhered to a substrate such as glass. It aims at providing the photocurable sealing agent composition which is excellent in force and excellent in storage stability.
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。
(A)〜(D)成分を含有する光硬化性封止剤組成物。
(A)成分:(A−1)成分のエポキシ(メタ)アクリレート及び(A−2)成分のアルキレンオキサイド変性ビスフェノール(メタ)アクリレートからなる群から1以上選択される1分子中に(メタ)アクリル基を1以上有する硬化性樹脂
(B)成分:下記の一般式(1)又は(2)で表される基を有する(メタ)アクリレート
(C)成分:光重合開始剤
(D)成分:下記の一般式(3)で表されるケイ素化合物
The gist of the present invention will be described next. The embodiments of the present invention overcome the above-mentioned conventional problems.
A photocurable sealant composition containing the components (A) to (D).
(A) Component: (Meth) acrylic in one molecule selected from the group consisting of epoxy (meth) acrylate as component (A-1) and alkylene oxide-modified bisphenol (meth) acrylate as component (A-2) Curable resin (B) component having one or more groups: (meth) acrylate (C) component having a group represented by the following general formula (1) or (2): Photopolymerization initiator (D) component: A silicon compound represented by the general formula (3)
本発明の光硬化性封止剤組成物は、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、貯蔵安定性に優れるものである。 The photocurable encapsulant composition of the present invention is a polymerized reaction that proceeds rapidly by irradiation with active energy rays such as ultraviolet rays, and a cured product having a high water vapor barrier property is obtained, and is adhered to a substrate such as glass. It has excellent strength and storage stability.
以下本発明を詳細に説明する。
<(A)成分>
本発明の(A)成分は、(A−1)成分のエポキシ(メタ)アクリレート及び(A−2)成分のアルキレンオキサイド変性ビスフェノール(メタ)アクリレートからなる群から1以上選択される1分子中に(メタ)アクリル基を1以上有する硬化性樹脂である。好ましくは、ガラス等の基板への接着力に優れ、架橋密度が高く透湿度が低い硬化物が得られることから(A−1)成分のエポキシ(メタ)アクリレートであることがあげられる。
The present invention will be described in detail below.
<(A) component>
The component (A) of the present invention is one molecule selected from the group consisting of the epoxy (meth) acrylate of the component (A-1) and the alkylene oxide-modified bisphenol (meth) acrylate of the component (A-2). It is a curable resin having one or more (meth) acrylic groups. Preferably, it is an epoxy (meth) acrylate as the component (A-1) because a cured product having excellent adhesion to a substrate such as glass and having a high crosslinking density and low moisture permeability can be obtained.
前記の(A−1)成分のエポキシ(メタ)アクリレート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。 The method for synthesizing the epoxy (meth) acrylate as the component (A-1) is not particularly limited. For example, an epoxy resin having at least two epoxy groups in one molecule can be added with (meth) acrylic acid. And reactants.
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からビスフェノール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 others, because of its excellent adhesion to glass and other substrates and high crosslink density. A bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol E type epoxy resin are preferably used because a cured product having excellent water vapor barrier properties can be obtained. These may be used independently and 2 or more types may be used together.
(A)成分である(A−1)成分のエポキシ(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る。 Although it does not specifically limit as epoxy (meth) acrylate of (A-1) component which is (A) component, it is excellent in the adhesiveness to board | substrates, such as glass, and hardening which is excellent in water vapor | steam barrier property from a high crosslinking density. From the viewpoint of obtaining a product, bisphenol A type epoxy (meth) acrylate, bisphenol F type (meth) acrylate, and bisphenol E type (meth) acrylate are preferably used.
(A)成分である(A−1)成分のエポキシ(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)、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 the epoxy (meth) acrylate of the component (A-1) which is the component (A), 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 (Showa Polymer Co., Ltd.), Neopol AC5748, 8101, 8250, 8260270, 8318, 8470, 8475, 8319, 8355, 8351, 8335, 8414, 8190, 8195 (manufactured by Nippon Iupika Co., Ltd.), BAEA-100, BAEM-100, BAEM-50, BEEM-50, BFEA -50 (manufactured by KS Corporation) (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.
前記(A−2)成分のアルキレンオキサイド変性ビスフェノール(メタ)アクリレート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(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。或いは、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 alkylene oxide-modified bisphenol (meth) acrylate as the component (A-2) is not particularly limited. For example, a bivalent compound obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to bisphenol A, bisphenol F, or bisphenol E. It can be obtained by an ester reaction product of 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−2)成分のアルキレンオキサイド変性ビスフェノール(メタ)アクリレートの市販品としては、例えば、ライトエステルBP−2EM、BP−4EM、BP−6EM、BP−4EA、BP−6PA、BP−10EA(共栄社化学株式会社製)、ファンクリル FA−320M、FA−321M(日立化成工業株式会社製)、リポキシSP−2500(昭和高分子株式会社製)、A−B1206PE、ABE−300、A−BPE−10、A−BPE−20、A−BPE−30、A−BPE−4、A−BPP−3、BPE−80N、BPE−100、BPE−200、BPE−500、BPE−900、BPE−1300N(新中村化学工業株式会社製)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 the alkylene oxide modified bisphenol (meth) acrylate of (A-2) component, for example, light ester BP-2EM, BP-4EM, BP-6EM, BP-4EA, BP-6PA, BP-10EA (Kyoeisha) Chemical Co., Ltd.), Fancril FA-320M, FA-321M (Hitachi Chemical Industry Co., Ltd.), Lipoxy SP-2500 (Showa Polymer Co., Ltd.), A-B1206PE, ABE-300, A-BPE-10 , A-BPE-20, A-BPE-30, A-BPE-4, A-BPP-3, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BPE-1300N (new Nakamura Chemical Co., Ltd.). 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、下記の一般式(1)又は(2)で表される基を有する(メタ)アクリレートなどがあげられる。1分子中に少なくとも(メタ)アクリル基を1以上有する化合物であるものがあげられる。
Examples of the component (B) of the present invention include (meth) acrylate having a group represented by the following general formula (1) or (2). Examples thereof include compounds having at least one (meth) acryl group in one molecule.
(B)成分の具体的な化合物としては、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。 Specific examples of the component (B) include 2-hydroxymethyl (meth) acrylate acid phosphate, 2-hydroxyethyl (meth) acrylate acid phosphate, 2-hydroxypropyl (meth) acrylate acid phosphate, and ethylene oxide-modified. Examples thereof include phosphoric acid diacrylate, 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.
(B)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。 (B) As a commercial item of a 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(B)成分の配合量は、特に限定されないが、(A)成分100質量部に対して、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、さらに長蔵安定性におとるおそれがある。 Although the compounding quantity of the said (B) component is not specifically limited, It is 0.1-50 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 0.5-25 mass parts, Especially Preferably it is 1-10 mass parts. If the amount is less than 0.1 parts by mass, the adhesion to the glass substrate may be inferior. If the amount exceeds 50 parts by mass, the water vapor barrier property may be deteriorated, and the shelf life may be increased.
<(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、光硬化性封止剤組成物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、光硬化性封止剤組成物の硬化物の透明性が損なわれるおそれがある。 The compounding 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 by mass with respect to 100 parts by mass of the total amount of the component (A). Especially preferably, it is 0.5-15 mass parts. If the amount is less than 0.1 parts by mass, the photocurability of the photocurable encapsulant composition is lowered, and thus 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. If it exceeds 30 parts by mass, the transparency of the cured product of the photocurable sealant composition may be impaired.
<(D)成分>
本発明の(D)成分は、下記の一般式(3)で表されるケイ素化合物である。(D)成分は、所謂シランカップリング剤の一種ではあるが、多数存在するシランカップリング剤の中から(D)成分を選択し、本発明のその他成分と組み合わせることによって、ガラス等の基板への接着力及び貯蔵安定性を両立させることができる。
<(D) component>
The component (D) of the present invention is a silicon compound represented by the following general formula (3). The component (D) is a kind of so-called silane coupling agent, but the component (D) is selected from a large number of silane coupling agents and combined with the other components of the present invention to form a substrate such as glass. The adhesive strength and storage stability can be made compatible.
本発明の(D)成分に該当する(メタ)アクリル基を有するケイ素化合物としては、例えば、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などが挙げら、この中でも貯蔵安定性の高い光硬化性封止剤組成物が得られる観点から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 silicon compound having a (meth) acrylic group corresponding to the component (D) of the present invention include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyldimethylmono. Methoxysilane, 3-methacryloxypropyldimethylmonoethoxysilane, 3-acryloxypropylmethyldipropyloxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldi Propyloxysilane, 3-acryloxypropyldimethylmonopropyloxysilane, 3-acryloxypropyldimethylmonomethoxysilane, 3-acryloxypropyldimethylmonoethoxysilane, 3-actyl Roxypropyldimethylmonopropyloxysilane and the like. Among them, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldimethylmonoethoxy from the viewpoint of obtaining a photocurable sealant composition having high storage stability. Silane, 3-acryloxypropylmethyldipropyloxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldipropyloxysilane, 3-acryloxypropyldimethylmonopropyloxysilane, 3-acryloxypropyl Dimethylmonoethoxysilane and 3-acryloxypropyldimethylmonopropyloxysilane are preferably used. These may be used independently and 2 or more types may be used together.
また、(D)成分に該当するグリシジル基を有するケイ素化合物としては、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などが挙げられ、この中でも貯蔵安定性の高い光硬化性封止剤組成物が得られる観点から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 silicon compound having a glycidyl group corresponding to the component (D) include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropylmethyldipropyloxysilane. , 3-glycidoxypropyldimethylmonomethoxysilane, 3-glycidoxypropyldimethylmonoethoxysilane, 3-glycidoxypropyldimethylmonopropyloxysilane, and the like. Among these, photocurable sealants having high storage stability. From the viewpoint of obtaining a stopper composition, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldipropyloxysilane, 3-glycidoxypropyldimethylmonoethoxysilane, 3-glycidoxypropyldimethyl Monopropyloxysila It is preferably used. These may be used independently and 2 or more types may be used together.
(D)成分の市販品としては例えば、(メタ)アクリル基を有するケイ素化合物としては、KBM502、KBE502(信越化学株式会社製)、Z−6033(東レ・ダウコーニング株式会社製)などがあげられ、また、グリシジル基を有するケイ素化合物としては、Z−6044、Z−6042(東レ・ダウコーニング株式会社製)、KBM−402、KBE−402(信越化学株式会社製)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。 Examples of commercially available products of component (D) include KBM502, KBE502 (manufactured by Shin-Etsu Chemical Co., Ltd.), Z-6033 (manufactured by Dow Corning Toray) and the like as silicon compounds having a (meth) acrylic group. Examples of the silicon compound having a glycidyl group include Z-6044, Z-6042 (manufactured by Toray Dow Corning Co., Ltd.), KBM-402, KBE-402 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. These may be used independently and 2 or more types may be used together.
前記(D)成分の配合量は、特に限定されないが、(A)成分100質量部に対して、0.5〜100質量部であり、更に好ましくは1〜50質量部であり、特に好ましくは3〜30質量部である。0.5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、100質量部を超えると、長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 0.5-100 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 1-50 mass parts, Most preferably 3 to 30 parts by mass. If the amount is less than 0.5 parts by mass, the adhesion to the glass substrate may be inferior, and if it exceeds 100 parts by mass, the shelf stability may be increased.
(B)成分に対する(D)成分の質量比率((D)成分/(B)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 (D) component to the (B) component ((D) component / (B) 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.
<(E)成分>
本発明には、更に(E)成分の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硬化性封止剤組成物が得られることから、ガラス、シリカ、タルクが好ましい。
<(E) component>
In the present invention, a filler of component (E) may be further contained. 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 photocurable sealant composition having excellent barrier properties can be obtained.
前記(E)成分の平均粒径が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、光硬化性封止剤組成物の粘度が、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、(E)成分の配合量は、特に限定されないが、(A)成分100質量部に対し、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 size of the component (E) is preferably 0.001 to 100 μm, more preferably the average particle size is 0.01 to 50 μm, and particularly preferably the average particle size is 0.1 to 20 μm. If the average particle size is less than 0.001 μm, the viscosity of the photocurable sealant composition may be inferior in workability such as coating, and if it exceeds 100 μm, the cured product may have a water vapor barrier property. There is. In addition, the measuring method of an average particle diameter is a laser diffraction method. In addition, although the compounding quantity of (E) component is not specifically limited, 0.1-300 mass parts is preferable with respect to 100 mass parts of (A) component, More preferably, it is 1-200 mass parts, Especially 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、本発明の目的を損なわない範囲で、(A)成分、(B)成分以外のエチレン性不飽和化合物、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。 In contrast to the present invention, the components (A), ethylenically unsaturated compounds other than the component (B), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, penta are used within the range not impairing the object of the present invention. Polythiol compounds such as erythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), epoxy resins, tackifiers, thermoplasticity Elastomers, rubbery polymer fine particles, storage stabilizers, antioxidants, light stabilizers, adhesion aids, plasticizers, dyes, pigments, flame retardants, sensitizers, thermal radical initiators, organic solvents, heavy metal deactivators, Ion trapping agent, emulsifier, water dispersion stabilizer, antifoaming agent, mold release agent, leveling agent, wax, Oh Logie control agent, an additive such as a surfactant may be appropriate amount.
本発明に対し、(A)成分、(B)成分以外のエチレン性不飽和化合物としては、例えば、(メタ)アクリロイル基を有する単官能性、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 ethylenically unsaturated compound other than the component (A) and the component (B) include, for example, monofunctional, bifunctional, trifunctional and polyfunctional monomers having a (meth) acryloyl group. , Oligomers and the like 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、本発明の光硬化性封止剤組成物の内部応力緩和又は接着力向上させる目的で便宜用いられる。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 conveniently used for the purpose of relaxing internal stress or improving the adhesive force of the photocurable sealant composition 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硬化性封止剤組成物の内部応力緩和又は接着力向上を目的として便宜添加されてもよい。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 conveniently added for the purpose of relaxing internal stress or improving adhesive strength of the photocurable sealant composition. 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.
本発明の光硬化性封止剤組成物は、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の照射は、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のの積算光量である。 The photocurable encapsulant composition of the present invention is cured by rapid polymerization reaction by irradiation with active energy rays such as light such as ultraviolet rays. The irradiation of the active energy ray is preferably an irradiation light having a wavelength range of 150 to 750 nm, and an integrated light amount of 1 to 1 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 with an integrated light amount of 100 kJ / cm 2 , and preferably has an integrated light amount of 5 to 70 kJ / cm 2 .
本発明の光硬化性封止剤組成物は、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、貯蔵安定性に優れるので、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に好ましく用いられる。 The photocurable encapsulant composition of the present invention is a polymerized reaction that proceeds rapidly by irradiation with active energy rays such as ultraviolet rays, and a cured product having a high water vapor barrier property is obtained, and is adhered to a substrate such as glass. Since it has excellent strength and storage stability, 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 preferably used for photoelectric conversion element applications such as organic thin film solar cells.
なお、本発明における水蒸気バリア性とは、透湿度が100以下g/m2・24hであるものを意味し、この特性を有する光硬化性封止剤組成物は、ディスプレイや光電変換素子などの用途に好適に用いられる。
In addition, the water vapor barrier property in the present invention means that the moisture permeability is 100 or less g / m 2 · 24 h, and the photocurable sealant composition having this property is used for displays, photoelectric conversion elements, and the like. It is suitably used for applications.
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>
(実施例1)
本発明の(A)成分として(A−1)成分であるビスフェノールA型エポキシアクリレート(リポキシVR−90、平均分子量1100、昭和電工株式会社製)25質量部及び(A−2)成分であるエチレンオキサイドビスフェノールA型ジメタクリレート(BPE−100、新中村化学工業株式会社製)75質量部と、(B)成分として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3質量部と、(C)成分として1−ヒドロキシ−シクロヘキシル−フェニル−ケトン3質量部と、(D)成分として3−メタクリロキシプロピルメチルジメトキシシラン(製品名KBM502、信越化学株式会社製)10質量部と、(E)成分として平均粒径1.5μmのシリカを75質量部を添加し、遮光下で常温にてプラネタリーミキサーで60分混合し、光硬化性封止剤組成物である実施例1を得た。
<Preparation of composition>
(Example 1)
As component (A) of the present invention, (A-1) component bisphenol A type epoxy acrylate (Lipoxy VR-90, average molecular weight 1100, Showa Denko KK) 25 parts by mass and (A-2) component ethylene 75 parts by mass of oxide bisphenol A type dimethacrylate (BPE-100, manufactured by Shin-Nakamura Chemical Co., Ltd.), 3 parts by mass of 2-hydroxyethyl (meth) acrylate acid phosphate as component (B), and 1 as component (C) 3 parts by weight of hydroxy-cyclohexyl-phenyl-ketone, 10 parts by weight of 3-methacryloxypropylmethyldimethoxysilane (product name KBM502, manufactured by Shin-Etsu Chemical Co., Ltd.) as component (D), and average particle diameter as component (E) Add 75 parts by weight of 1.5 μm silica and planetary Mixed 60 minutes Sir, give Example 1 photocurable sealant composition.
(実施例2)
実施例1において、3−メタクリロキシプロピルメチルジメトキシシランの代わりに、3−メタクリロキシプロピルジエトキシシラン(製品名KBE502、信越化学株式会社製)を用いた以外は、実施例1と同様にして調製し、実施例2を得た。
(Example 2)
Prepared in the same manner as in Example 1 except that 3-methacryloxypropyldiethoxysilane (product name KBE502, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 3-methacryloxypropylmethyldimethoxysilane in Example 1. Example 2 was obtained.
(実施例3)
実施例1において、3−メタクリロキシプロピルメチルジメトキシシラン10質量部の代わりに5質量部にした以外は実施例1と同様にして調製し、実施例3を得た。
(Example 3)
Example 3 was prepared in the same manner as in Example 1 except that 5 parts by mass was used instead of 10 parts by mass of 3-methacryloxypropylmethyldimethoxysilane.
(実施例4)
実施例1において、ビスフェノールA型エポキシアクリレートの代わりにビスフェノールF型エポキシアクリレート(リポキシSP−1506、昭和電工株式会社製)にした以外は実施例1と同様にして調製し、実施例4を得た。
Example 4
Example 4 was prepared in the same manner as in Example 1 except that bisphenol F type epoxy acrylate (Lipoxy SP-1506, Showa Denko KK) was used instead of bisphenol A type epoxy acrylate. .
(実施例5)
実施例4において、エチレンオキサイドビスフェノールA型ジメタクリレートを除くこと以外は実施例4と同様にして調製し、実施例5を得た。
(Example 5)
Example 5 was prepared in the same manner as in Example 4 except that ethylene oxide bisphenol A type dimethacrylate was excluded.
(比較例1)
実施例1において、3−メタクリロキシプロピルメチルジメトキシシランの代わりに、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)を用いた以外は、実施例1と同様にして調製し、比較例1を得た。
(Comparative Example 1)
In Example 1, prepared in the same manner as in Example 1 except that 3-acryloxypropyltrimethoxysilane (product name KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 3-methacryloxypropylmethyldimethoxysilane. Comparative Example 1 was obtained.
(比較例2)
実施例1において、3−メタクリロキシプロピルメチルジメトキシシランの代わりに、3−メタクリロキシプロピルトリメトキシシラン(製品名KBM503、信越化学株式会社製)を用いた以外は、実施例1と同様にして調製し、比較例2を得た。
(Comparative Example 2)
In Example 1, prepared in the same manner as in Example 1 except that 3-methacryloxypropyltrimethoxysilane (product name KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 3-methacryloxypropylmethyldimethoxysilane. Comparative Example 2 was obtained.
(比較例3)
実施例1において、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の代わりに、フェノキシポリエチレングリコールアクリレート(製品名AMP−20GY、新中村化学工業株式会社製)を用いた以外は、実施例1と同様にして調製し、比較例3を得た。
(Comparative Example 3)
In Example 1, instead of 2-hydroxyethyl (meth) acrylate acid phosphate, phenoxy polyethylene glycol acrylate (product name AMP-20GY, manufactured by Shin-Nakamura Chemical Co., Ltd.) was used in the same manner as in Example 1. Comparative Example 3 was obtained.
(比較例4)
実施例1において、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の代わりに、イソシアヌル酸エチレンオキサイド変性トリアクリレート(製品名M−315、東亞合成株式会社製)を用いた以外は、実施例1と同様にして調製し、比較例4を得た。
(Comparative Example 4)
Example 1 is the same as Example 1 except that isocyanuric acid ethylene oxide-modified triacrylate (product name M-315, manufactured by Toagosei Co., Ltd.) was used instead of 2-hydroxyethyl (meth) acrylate acid phosphate. Comparative Example 4 was obtained.
(比較例5)
実施例1において、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の代わりに、ジシクロペンタニルアクリレ−ト(製品名FA−513AS、日立化成株式会社製)を用いた以外は、実施例1と同様にして調製し、比較例5を得た。
(Comparative Example 5)
In Example 1, Example 1 was used except that dicyclopentanyl acrylate (product name FA-513AS, manufactured by Hitachi Chemical Co., Ltd.) was used instead of 2-hydroxyethyl (meth) acrylate acid phosphate. In the same manner, Comparative Example 5 was obtained.
(比較例6)
実施例1において、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を除くこと以外は実施例1と同様にして調製し、比較例6を得た。
(Comparative Example 6)
A comparative example 6 was obtained in the same manner as in the example 1 except that the 2-hydroxyethyl (meth) acrylate acid phosphate was removed.
(比較例7)
実施例1において、3−メタクリロキシプロピルメチルジメトキシシランを除くこと以外は実施例1と同様にして調製し、比較例7を得た。
(Comparative Example 7)
A comparative example 7 was obtained in the same manner as in the example 1 except that the 3-methacryloxypropylmethyldimethoxysilane was removed.
(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硬化性封止剤組成物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1〜2に示す。好ましくは、ディスプレイ用途や光電変換素子用途等の封止剤用途に好適に用いられることからガラス等の基板への接着力は1.0MPa以上が好ましく、より好ましくは1.5MPa以上であることがあげられる。。
[Cross peel adhesion test]
Thickness 5 mm x width 25 mm x length 50 mm Two glass substrates bonded with each photocurable sealant composition so as to form a cross were irradiated with an integrated light amount of 30 kJ / cm 2 by an ultraviolet irradiator. Created a piece. And this test piece is pressed with a crosshead using a tensile tester, the stress required until a glass plate and a glass plate isolate | separate is measured, and a result is shown to Tables 1-2. Preferably, the adhesive force to a substrate such as glass is preferably 1.0 MPa or more, more preferably 1.5 MPa or more, because it is suitably used for sealant applications such as display applications and photoelectric conversion element applications. can give. .
[貯蔵安定性試験]
各光硬化性封止剤組成物を25℃、40℃の環境下で遮光容器中に60日間密閉保存し、下記基準に基づき評価し、その結果を表1、2に示す。
<評価基準>
○:光硬化性封止剤組成物の流動性が確認できた。
×:光硬化性封止剤組成物がゲル化して流動しなくなっていた。
[Storage stability test]
Each photocurable sealant composition was hermetically stored in a light-shielding container for 60 days in an environment of 25 ° C. and 40 ° C., evaluated based on the following criteria, and the results are shown in Tables 1 and 2.
<Evaluation criteria>
(Circle): The fluidity | liquidity of the photocurable sealing agent composition was able to be confirmed.
X: The photocurable sealing agent composition gelled and stopped flowing.
[水蒸気バリア性試験(透湿バリア性試験)]
200mm×200mm×0.2mmの枠に実施例1、2の光硬化性封止剤組成物を流し込んだ。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。実施例1の透湿度が65g/m2・24hであり、実施例2の透湿度が58g/m2・24hであった。
実施例1、2ともに透湿度が100以下g/m2・24hであったので、ディスプレイや光電変換素子などの用途に求められる水蒸気バリア性を満足した光硬化性封止剤組成物が得られたことが確認できた。
[Water vapor barrier property test (moisture permeability barrier property test)]
The photocurable sealant compositions of Examples 1 and 2 were 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. The moisture permeability of Example 1 was 65 g / m 2 · 24 h, and the moisture permeability of Example 2 was 58 g / m 2 · 24 h.
In both Examples 1 and 2, the moisture permeability was 100 or less g / m 2 · 24 h, so that a photocurable sealant composition satisfying the water vapor barrier property required for applications such as displays and photoelectric conversion elements was obtained. I was able to confirm.
本発明の光硬化性封止剤組成物は、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、貯蔵安定性に優れるので、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 photocurable encapsulant composition of the present invention is a polymerized reaction that proceeds rapidly by irradiation with active energy rays such as ultraviolet rays, and a cured product having a high water vapor barrier property is obtained, and is adhered to a substrate such as glass. Since it has excellent strength and storage stability, 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 (7)
(A)成分:(A−1)成分のエポキシ(メタ)アクリレート及び(A−2)成分のアルキレンオキサイド変性ビスフェノール(メタ)アクリレートからなる群から1以上選択される1分子中に(メタ)アクリル基を1以上有する硬化性樹脂
(B)成分:下記の一般式(1)又は(2)で表される基を有する(メタ)アクリレート
(D)成分:下記の一般式(3)で表されるケイ素化合物
(A) Component: (Meth) acrylic in one molecule selected from the group consisting of epoxy (meth) acrylate as component (A-1) and alkylene oxide-modified bisphenol (meth) acrylate as component (A-2) Curable resin (B) component having one or more groups: (meth) acrylate having a group represented by the following general formula (1) or (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013209039A JP6319549B2 (en) | 2013-10-04 | 2013-10-04 | Photocurable sealant composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013209039A JP6319549B2 (en) | 2013-10-04 | 2013-10-04 | Photocurable sealant composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2015071726A true JP2015071726A (en) | 2015-04-16 |
JP6319549B2 JP6319549B2 (en) | 2018-05-09 |
Family
ID=53014332
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2013209039A Active JP6319549B2 (en) | 2013-10-04 | 2013-10-04 | Photocurable sealant composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6319549B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020007449A (en) * | 2018-07-06 | 2020-01-16 | 株式会社コバヤシ | Photocurable composition |
WO2024075528A1 (en) * | 2022-10-03 | 2024-04-11 | Dic株式会社 | Curable composition, cured product thereof, led element, electronic device, and optical element |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60198757A (en) * | 1984-03-22 | 1985-10-08 | Daicel Chem Ind Ltd | Resin-sealed type electronic component device |
JPH0892334A (en) * | 1994-09-20 | 1996-04-09 | Mitsubishi Rayon Co Ltd | Resin composition for coating and its production |
WO2002092718A1 (en) * | 2001-05-16 | 2002-11-21 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
JP2003280004A (en) * | 2002-03-20 | 2003-10-02 | Mitsui Chemicals Inc | Resin composition for sealing liquid crystal and liquid crystal display element |
WO2011016356A1 (en) * | 2009-08-04 | 2011-02-10 | 出光興産株式会社 | Acrylate composition |
-
2013
- 2013-10-04 JP JP2013209039A patent/JP6319549B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60198757A (en) * | 1984-03-22 | 1985-10-08 | Daicel Chem Ind Ltd | Resin-sealed type electronic component device |
JPH0892334A (en) * | 1994-09-20 | 1996-04-09 | Mitsubishi Rayon Co Ltd | Resin composition for coating and its production |
WO2002092718A1 (en) * | 2001-05-16 | 2002-11-21 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
JP2003280004A (en) * | 2002-03-20 | 2003-10-02 | Mitsui Chemicals Inc | Resin composition for sealing liquid crystal and liquid crystal display element |
WO2011016356A1 (en) * | 2009-08-04 | 2011-02-10 | 出光興産株式会社 | Acrylate composition |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020007449A (en) * | 2018-07-06 | 2020-01-16 | 株式会社コバヤシ | Photocurable composition |
WO2024075528A1 (en) * | 2022-10-03 | 2024-04-11 | Dic株式会社 | Curable composition, cured product thereof, led element, electronic device, and optical element |
Also Published As
Publication number | Publication date |
---|---|
JP6319549B2 (en) | 2018-05-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6828230B2 (en) | Photocurable sealant for fuel cells, fuel cells and sealing methods | |
JP6646228B2 (en) | Curable resin composition | |
JP6718176B2 (en) | Photocurable resin composition, fuel cell and sealing method | |
JP7295440B2 (en) | Curable resin composition and cured product | |
JP6504346B2 (en) | Photocurable resin composition for suppressing short circuit between adjacent electrodes | |
WO2018190421A1 (en) | Photocurable resin composition, fuel cell using same, and sealing method | |
JP7149479B2 (en) | PHOTOCURABLE RESIN COMPOSITION, FUEL CELL USING THE SAME, AND SEALING METHOD | |
JP6319549B2 (en) | Photocurable sealant composition | |
JP7376766B2 (en) | Adhesive compositions, cured products and bonded products | |
JP6256758B2 (en) | Sealant for photoelectric conversion element | |
WO2020085081A1 (en) | Sealant for display element, cured product, vertical conductive material, and display element | |
WO2020196479A1 (en) | Resin composition and periphery-sealing agent for organic el display element | |
JP7402382B1 (en) | Sealant for liquid crystal display elements and liquid crystal display elements | |
JP6259657B2 (en) | Sealant for liquid crystal display elements | |
JP2020056810A (en) | Method for manufacturing image display device | |
KR20230020939A (en) | Sealing agent for display element, upper and lower conduction material, and display element | |
JP2020055896A (en) | Photocurable resin composition and method for forming resin cured product | |
JP6748883B2 (en) | Light delay curable resin composition, bonded body and bonding method | |
JP2021093422A (en) | Encapsulating composition | |
JP2016009584A (en) | Sealant for organic electroluminescence display device, and organic electroluminescence display device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160204 |
|
A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20160204 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160920 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20171004 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20171106 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180207 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180209 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180307 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180320 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6319549 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |