KR102226349B1 - Sealing agent for organic el display elements - Google Patents
Sealing agent for organic el display elements Download PDFInfo
- Publication number
- KR102226349B1 KR102226349B1 KR1020157026903A KR20157026903A KR102226349B1 KR 102226349 B1 KR102226349 B1 KR 102226349B1 KR 1020157026903 A KR1020157026903 A KR 1020157026903A KR 20157026903 A KR20157026903 A KR 20157026903A KR 102226349 B1 KR102226349 B1 KR 102226349B1
- Authority
- KR
- South Korea
- Prior art keywords
- organic
- formula
- sealing agent
- cation
- display device
- Prior art date
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- 238000007789 sealing Methods 0.000 title claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 67
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 20
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 16
- 150000001768 cations Chemical class 0.000 claims abstract description 16
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 11
- 125000003566 oxetanyl group Chemical group 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000010943 off-gassing Methods 0.000 abstract description 7
- -1 aromatic sulfonium salt Chemical class 0.000 description 37
- 238000001723 curing Methods 0.000 description 12
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 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 9
- 238000001029 thermal curing Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical class CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- UCBQKJQXUPVHFJ-UHFFFAOYSA-N 1-cyclopenta-2,4-dien-1-yl-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1C1C=CC=C1 UCBQKJQXUPVHFJ-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- 102100033806 Alpha-protein kinase 3 Human genes 0.000 description 2
- 101710082399 Alpha-protein kinase 3 Proteins 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- HYVNJCOHGOONJK-UHFFFAOYSA-N dibenzyl-methyl-phenylazanium Chemical compound C=1C=CC=CC=1C[N+](C=1C=CC=CC=1)(C)CC1=CC=CC=C1 HYVNJCOHGOONJK-UHFFFAOYSA-N 0.000 description 2
- ONRGBXGMVZEZLY-UHFFFAOYSA-N dimethyl-[(4-methylphenyl)methyl]-phenylazanium Chemical compound C1=CC(C)=CC=C1C[N+](C)(C)C1=CC=CC=C1 ONRGBXGMVZEZLY-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 2
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- VLTYTTRXESKBKI-UHFFFAOYSA-N (2,4-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 VLTYTTRXESKBKI-UHFFFAOYSA-N 0.000 description 1
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- USGYMDAUQBQWFU-UHFFFAOYSA-N 1,2,5,6-diepoxycyclooctane Chemical compound C1CC2OC2CCC2OC12 USGYMDAUQBQWFU-UHFFFAOYSA-N 0.000 description 1
- QLGYTJLZFZUDFL-UHFFFAOYSA-N 1,3-bis[1-(1h-imidazol-2-yl)propyl]urea Chemical compound N=1C=CNC=1C(CC)NC(=O)NC(CC)C1=NC=CN1 QLGYTJLZFZUDFL-UHFFFAOYSA-N 0.000 description 1
- VSHKLLPSERFSRJ-UHFFFAOYSA-N 1-(naphthalen-1-ylmethyl)pyridin-1-ium-2-carbonitrile Chemical compound N#CC1=CC=CC=[N+]1CC1=CC=CC2=CC=CC=C12 VSHKLLPSERFSRJ-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- VDAIJDKQXDCJSI-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethylurea Chemical compound CC1=NC=CN1CCNC(N)=O VDAIJDKQXDCJSI-UHFFFAOYSA-N 0.000 description 1
- TZLVUWBGUNVFES-UHFFFAOYSA-N 2-ethyl-5-methylpyrazol-3-amine Chemical compound CCN1N=C(C)C=C1N TZLVUWBGUNVFES-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KWVNDBRCGPCJLR-UHFFFAOYSA-N C(C=C1)=CC=C1[S+](C1=CC=CC=C1)C1=CC=CC=C1.[AsH3] Chemical compound C(C=C1)=CC=C1[S+](C1=CC=CC=C1)C1=CC=CC=C1.[AsH3] KWVNDBRCGPCJLR-UHFFFAOYSA-N 0.000 description 1
- CKEAMIMZKRUKLM-UHFFFAOYSA-N COC(C=C1)=CC=C1[S+](C(C=C1)=CC=C1OC)C(C=C1)=CC=C1OC.[AsH3] Chemical compound COC(C=C1)=CC=C1[S+](C(C=C1)=CC=C1OC)C(C=C1)=CC=C1OC.[AsH3] CKEAMIMZKRUKLM-UHFFFAOYSA-N 0.000 description 1
- GMXOYEFGMAXIIU-UHFFFAOYSA-N C[N+](CC1=CC(=C(C=C1)C)C)(C1=CC=CC=C1)C Chemical compound C[N+](CC1=CC(=C(C=C1)C)C)(C1=CC=CC=C1)C GMXOYEFGMAXIIU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 1
- VPSDPCXOOHMTDQ-UHFFFAOYSA-N [B+3].C(C)[N+](C1=CC=CC=C1)(CC1=CC=CC=C1)CC Chemical compound [B+3].C(C)[N+](C1=CC=CC=C1)(CC1=CC=CC=C1)CC VPSDPCXOOHMTDQ-UHFFFAOYSA-N 0.000 description 1
- GROOQLAYIIFIBG-UHFFFAOYSA-N [B+3].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound [B+3].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 GROOQLAYIIFIBG-UHFFFAOYSA-N 0.000 description 1
- BFVANNVEMACRTA-UHFFFAOYSA-N [Sb+3].CCCC[P+](CCCC)(CCCC)CCCC Chemical compound [Sb+3].CCCC[P+](CCCC)(CCCC)CCCC BFVANNVEMACRTA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 150000001412 amines Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- CFPCDQPUCAECLL-UHFFFAOYSA-N antimony(3+) ethyl(triphenyl)phosphanium Chemical compound [Sb+3].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 CFPCDQPUCAECLL-UHFFFAOYSA-N 0.000 description 1
- LUAKDNCXFXZOEC-UHFFFAOYSA-N antimony(3+);triphenylsulfanium Chemical compound [Sb+3].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 LUAKDNCXFXZOEC-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical compound N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 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
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 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
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000005825 oxyethoxy group Chemical group [H]C([H])(O[*:1])C([H])([H])O[*:2] 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- HMKGBOLFVMRQRP-UHFFFAOYSA-N tribenzyl(phenyl)azanium Chemical compound C=1C=CC=CC=1C[N+](C=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 HMKGBOLFVMRQRP-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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3236—Heterocylic compounds
- C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/06—Triglycidylisocyanurates
-
- H01L51/5246—
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/871—Self-supporting sealing arrangements
- H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Electroluminescent Light Sources (AREA)
- Epoxy Resins (AREA)
- Sealing Material Composition (AREA)
Abstract
본 발명은 아웃 가스의 발생을 억제할 수 있고, 또한, 도포성이 우수한 유기 EL 표시 소자용 밀봉제를 제공하는 것을 목적으로 한다. 본 발명은 카티온 경화성 수지와, 카티온 중합 개시제를 함유하는 유기 EL 표시 소자용 밀봉제로서, 상기 카티온 경화성 수지는, 에폭시기 또는 옥세타닐기를 갖고, 또한, 에폭시기 또는 옥세타닐기에 함유되는 것 이외의 에테르 결합, 및 에스테르 결합을 갖지 않는 것으로, E 형 점도계를 이용하여 25 ℃, 1 ∼ 100 rpm 의 조건에서 측정한 유기 EL 표시 소자용 밀봉제 전체의 점도가 80 ∼ 5000 mPa·s 인 유기 EL 표시 소자용 밀봉제이다.An object of the present invention is to provide a sealing agent for an organic EL display device that can suppress the outgassing and is excellent in coatability. The present invention is a sealing agent for an organic EL display device containing a cation curable resin and a cation polymerization initiator, wherein the cation curable resin has an epoxy group or oxetanyl group, and is contained in an epoxy group or oxetanyl group. Having no ether bonds and ester bonds other than those, the viscosity of the entire sealing agent for organic EL display devices measured at 25°C and 1 to 100 rpm using an E-type viscometer is 80 to 5000 mPa·s. It is a sealing agent for organic EL display elements.
Description
본 발명은 아웃 가스의 발생을 억제할 수 있고, 또한, 도포성이 우수한 유기 EL 표시 소자용 밀봉제에 관한 것이다. The present invention relates to a sealing agent for an organic EL display device capable of suppressing outgassing and having excellent coatability.
최근, 유기 일렉트로 루미네선스 (유기 EL) 표시 소자나 유기 박막 태양 전지 소자 등의 유기 박막 소자를 사용한 유기 광 디바이스의 연구가 진행되고 있다. 유기 박막 소자는 진공 증착이나 용액 도포 등에 의해 간편하게 제조할 수 있기 때문에 생산성도 우수하다. In recent years, studies on organic optical devices using organic thin-film elements such as organic electroluminescent (organic EL) display elements and organic thin-film solar cell elements have been conducted. The organic thin film device is also excellent in productivity because it can be manufactured simply by vacuum deposition or solution application.
유기 EL 표시 소자는, 서로 대향하는 1 쌍의 전극간에 유기 발광 재료층이 협지된 박막 구조체를 갖는다. 이 유기 발광 재료층에 일방의 전극으로부터 전자가 주입됨과 함께 타방의 전극으로부터 정공이 주입됨으로써 유기 발광 재료층 내에서 전자와 정공이 결합하여 자기 발광한다. 백라이트를 필요로 하는 액정 표시 소자 등과 비교하여 시인성이 양호하고, 보다 박형화가 가능하며, 또한, 직류 저전압 구동이 가능하다는 이점을 갖는다. An organic EL display device has a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. When electrons are injected from one electrode and holes are injected into the organic light-emitting material layer, electrons and holes are combined in the organic light-emitting material layer to emit light. Compared with a liquid crystal display device that requires a backlight, it has the advantage that visibility is good, it is possible to be thinner, and it is possible to drive a direct current low voltage.
그런데, 이와 같은 유기 EL 표시 소자는, 유기 발광 재료층이나 전극이 외기에 노출되면 그 발광 특성이 급격히 열화되어 수명이 짧아진다는 문제가 있었다. 따라서, 유기 EL 표시 소자의 안정성 및 내구성을 높이는 것을 목적으로 하여, 유기 EL 표시 소자에 있어서는, 유기 발광 재료층이나 전극을 대기 중의 수분이나 산소로부터 차단하는 밀봉 기술이 불가결하게 되어 있다. However, such an organic EL display device has a problem in that when the organic light-emitting material layer or electrode is exposed to outside air, its light-emitting characteristics are rapidly deteriorated and its lifespan is shortened. Therefore, for the purpose of improving the stability and durability of the organic EL display device, in the organic EL display device, a sealing technique for shielding the organic light-emitting material layer or electrode from moisture or oxygen in the atmosphere is indispensable.
특허문헌 1 에는, 상면 발광형 유기 EL 표시 소자에 있어서, 유기 EL 표시 소자 기판 사이에 경화성 접착제를 채우고, 광을 조사하여 밀봉하는 방법이 개시되어 있다. 그러나, 이와 같이 경화성 접착제를 사용하여 유기 EL 표시 소자 등의 표시 소자를 밀봉한 경우에는, 광 조사시나 가열시에 아웃 가스가 발생하여 소자 내에 충만되고, 소자의 열화가 촉진되는 경우가 있다는 문제가 있었다. Patent Document 1 discloses a method of filling a curable adhesive between substrates of an organic EL display device and sealing by irradiating light in a top-emitting type organic EL display device. However, in the case of sealing a display element such as an organic EL display element using a curable adhesive in this way, there is a problem that outgas is generated during light irradiation or heating to fill the element, thereby accelerating the deterioration of the element. there was.
본 발명은 아웃 가스의 발생을 억제할 수 있고, 또한, 도포성이 우수한 유기 EL 표시 소자용 밀봉제를 제공하는 것을 목적으로 한다. An object of the present invention is to provide a sealing agent for an organic EL display device that can suppress the outgassing and is excellent in coatability.
본 발명은 카티온 경화성 수지와, 카티온 중합 개시제를 함유하는 유기 EL 표시 소자용 밀봉제로서, 상기 카티온 경화성 수지는, 에폭시기 또는 옥세타닐기를 갖고, 또한, 에폭시기 또는 옥세타닐기에 함유되는 것 이외의 에테르 결합, 및 에스테르 결합을 갖지 않는 것으로, E 형 점도계를 이용하여 25 ℃, 1 ∼ 100 rpm 의 조건에서 측정한 유기 EL 표시 소자용 밀봉제 전체의 점도가 80 ∼ 5000 mPa·s 인 유기 EL 표시 소자용 밀봉제이다. The present invention is a sealing agent for an organic EL display device containing a cation curable resin and a cation polymerization initiator, wherein the cation curable resin has an epoxy group or oxetanyl group, and is contained in an epoxy group or oxetanyl group. Having no ether bonds and ester bonds other than those, the viscosity of the entire sealing agent for organic EL display devices measured at 25°C and 1 to 100 rpm using an E-type viscometer is 80 to 5000 mPa·s. It is a sealing agent for organic EL display elements.
이하에 본 발명을 상세히 서술한다. The present invention is described in detail below.
본 발명자들은 유기 EL 표시 소자의 밀봉에 경화성 접착제를 사용한 경우에 아웃 가스가 발생하는 원인이, 사용되는 경화성 수지 중에 함유되는 에테르 결합이나 에스테르 결합에 있다고 생각하였다. 즉, 경화성 수지 중에 함유되는 에테르 결합이나 에스테르 결합이, 개시제 등에서 유래하는 산에 의해 분해됨으로써 아웃 가스가 발생하고 있는 것으로 생각하였다. 그 때문에, 이와 같은 아웃 가스 발생의 원인이 되는 에테르 결합이나 에스테르 결합을 함유하지 않는 경화성 수지를 사용하는 것을 검토하였지만, 사용하는 경화성 수지의 종류에 따라서는 얻어지는 유기 EL 표시 소자용 밀봉제가 도포성이 떨어지는 것이 되는 경우가 있었다. The present inventors thought that the cause of outgassing when a curable adhesive was used for sealing an organic EL display element was due to an ether bond or an ester bond contained in the curable resin to be used. That is, it was thought that outgas was generated by decomposing the ether bond or the ester bond contained in the curable resin by an acid derived from an initiator or the like. Therefore, it has been studied to use a curable resin that does not contain an ether bond or an ester bond that causes such outgassing. However, depending on the type of curable resin to be used, the obtained sealing agent for organic EL display devices has an applicability. There was a case of falling.
그래서 본 발명자들은 경화성 수지로서, 에폭시기 또는 옥세타닐기를 갖고, 또한, 에폭시기 또는 옥세타닐기에 함유되는 것 이외의 에테르 결합, 및 에스테르 결합을 갖지 않는 특정한 카티온 경화성 수지를 사용함으로써, 아웃 가스의 발생을 억제할 수 있고, 또한, 도포성이 우수한 유기 EL 표시 소자용 밀봉제를 얻을 수 있는 것을 알아내어, 본 발명을 완성시키기에 이르렀다. Therefore, the present inventors used a specific cation-curable resin having an epoxy group or an oxetanyl group as a curable resin, and not having an ether bond and an ester bond other than those contained in the epoxy group or oxetanyl group, thereby reducing outgassing. It has been found that generation can be suppressed and a sealing agent for an organic EL display device having excellent coatability can be obtained, and the present invention has been completed.
본 발명의 유기 EL 표시 소자용 밀봉제는 카티온 경화성 수지를 함유한다. The sealing agent for an organic EL display device of the present invention contains a cation curable resin.
상기 카티온 경화성 수지는, 에폭시기 또는 옥세타닐기를 갖고, 또한, 에폭시기 또는 옥세타닐기에 함유되는 것 이외의 에테르 결합, 및 에스테르 결합을 갖지 않는 것 (이하, 「본 발명에 관련된 카티온 경화성 수지」라고도 한다) 이다. The cation-curable resin has an epoxy group or an oxetanyl group, and does not have an ether bond and an ester bond other than those contained in the epoxy group or oxetanyl group (hereinafter, ``the cation-curable resin according to the present invention It is also called').
상기 카티온 경화성 수지는 아웃 가스의 발생을 효과적으로 억제할 수 있는 점에서, 하기 식 (1) 로 나타내는 화합물 및/또는 하기 식 (2) 로 나타내는 화합물을 함유하는 것이 바람직하고, 내습성이나 경화성의 관점에서, 하기 식 (1) 로 나타내는 화합물을 함유하는 것이 보다 바람직하다. The cation-curable resin preferably contains a compound represented by the following formula (1) and/or a compound represented by the following formula (2), from the viewpoint of being able to effectively suppress the generation of outgas, and having moisture resistance and curing properties. From a viewpoint, it is more preferable to contain the compound represented by the following formula (1).
[화학식 1][Formula 1]
식 (1) 중, R1 ∼ R18 은 수소 원자, 할로겐 원자, 또는 산소 원자 혹은 할로겐 원자를 함유하고 있어도 되는 탄화수소기이고, 각각 동일하여도 되고, 상이하여도 된다.In formula (1), R 1 to R 18 are a hydrogen atom, a halogen atom, or a hydrocarbon group which may contain an oxygen atom or a halogen atom, and may be the same or different.
[화학식 2][Formula 2]
식 (2) 중, R19 ∼ R21 은 직사슬형 또는 분기사슬형의 탄소수 2 ∼ 10 의 알킬렌기이고, 각각 동일하여도 되고, 상이하여도 된다. E1 ∼ E3 은 각각 독립적으로 하기 식 (3-1) 또는 하기 식 (3-2) 로 나타내는 유기기를 나타낸다. In formula (2), R 19 to R 21 are linear or branched alkylene groups having 2 to 10 carbon atoms, and may be the same or different. Each of E 1 to E 3 independently represents an organic group represented by the following formula (3-1) or the following formula (3-2).
[화학식 3] [Formula 3]
식 (3-1) 중, R22 는 수소 원자 또는 메틸기이다. In formula (3-1), R 22 is a hydrogen atom or a methyl group.
상기 카티온 경화성 수지는 양호한 카티온 경화성을 나타내는 점에서, 상기 식 (1) 로 나타내는 화합물로서 하기 식 (4) 로 나타내는 화합물을 함유하는 것이 바람직하다. The cation-curable resin preferably contains a compound represented by the following formula (4) as the compound represented by the formula (1) from the viewpoint of exhibiting satisfactory cation curability.
[화학식 4][Formula 4]
상기 카티온 경화성 수지는 양호한 카티온 경화성을 나타내며, 경화물이 높은 유리 전이 온도를 나타내는 점에서, 상기 식 (2) 로 나타내는 화합물로서 하기 식 (5) 로 나타내는 화합물을 함유하는 것이 바람직하다. The cation-curable resin preferably contains a compound represented by the following formula (5) as the compound represented by the formula (2), since the cation-curable resin exhibits satisfactory cation curability and the cured product exhibits a high glass transition temperature.
[화학식 5] [Formula 5]
상기 카티온 경화성 수지는, 얻어지는 유기 EL 표시 소자용 밀봉제의 경화 지연성이나 점도를 용이하게 조정할 수 있는 점에서, 상기 식 (1) 로 나타내는 화합물 및 상기 식 (2) 로 나타내는 화합물의 양방을 함유하는 것이 바람직하다. 또, 상기 식 (1) 로 나타내는 화합물에 추가하여 상기 식 (2) 로 나타내는 화합물을 함유함으로써, 경화 반응이 일어날 때까지의 원료의 휘발을 억제할 수 있어, 얻어지는 유기 EL 표시 소자용 밀봉제의 도포 형상 안정성이 향상된다. The cation-curable resin has both a compound represented by the formula (1) and a compound represented by the formula (2) in that the curing retardance and viscosity of the obtained sealing agent for an organic EL display device can be easily adjusted. It is preferable to contain. In addition, by containing the compound represented by the formula (2) in addition to the compound represented by the formula (1), the volatilization of the raw material until the curing reaction occurs can be suppressed. Application shape stability is improved.
상기 카티온 경화성 수지가 식 (1) 로 나타내는 화합물 및 식 (2) 로 나타내는 화합물의 양방을 함유하는 경우, 식 (1) 로 나타내는 화합물과 식 (2) 로 나타내는 화합물의 함유 비율은, 경화 지연성 및 도포성의 관점에서, 중량비로 식 (1) 로 나타내는 화합물 : 식 (2) 로 나타내는 화합물 ＝ 1 : 99 ∼ 99 : 1 인 것이 바람직하고, 식 (1) 로 나타내는 화합물 : 식 (2) 로 나타내는 화합물 ＝ 10 : 90 ∼ 90 : 10 인 것이 보다 바람직하다. When the cation-curable resin contains both the compound represented by formula (1) and the compound represented by formula (2), the content ratio of the compound represented by formula (1) and the compound represented by formula (2) is the curing delay. From the viewpoint of property and coatability, the compound represented by the formula (1) by weight ratio: the compound represented by the formula (2) = 1: 99 to 99: 1, preferably, the compound represented by the formula (1): by the formula (2) It is more preferable that it is a represented compound = 10:90-90:10.
본 발명에 관련된 카티온 경화성 수지 중, 그 밖의 것으로는, 예를 들어, 디시클로펜타디엔디에폭사이드, 1,2,5,6-디에폭시시클로옥탄 등을 들 수 있다. Other examples of the cation-curable resin according to the present invention include dicyclopentadiene diepoxide, 1,2,5,6-diepoxycyclooctane, and the like.
본 발명의 유기 EL 표시 소자용 밀봉제는, 본 발명의 목적을 저해하지 않는 범위에서, 후술하는 충전제의 분산성을 높이는 것이나 얻어지는 유기 EL 표시 소자용 밀봉제의 점도를 적당히 조정하는 것 등을 목적으로 하여, 본 발명에 관련된 카티온 경화성 수지에 추가하여, 에폭시기 또는 옥세타닐기에 함유되는 것 이외의 에테르 결합이나 에스테르 결합을 갖는 그 밖의 카티온 경화성 수지를 함유하여도 된다. 상기 그 밖의 카티온 경화성 수지로는, 비스페놀 골격을 갖는 에폭시 수지, 노볼락 골격을 갖는 에폭시 수지, 나프탈렌 골격을 갖는 에폭시 수지, 및 디시클로펜타디엔 골격을 갖는 에폭시 수지로 이루어지는 군에서 선택되는 적어도 1 종의 에폭시 수지가 바람직하고, 비스페놀 골격을 갖는 에폭시 수지가 보다 바람직하고, 비스페놀 F 형 에폭시 수지가 더욱 바람직하다. The sealing agent for an organic EL display device of the present invention is intended to increase the dispersibility of a filler described later, or to appropriately adjust the viscosity of the obtained sealing agent for an organic EL display device, within a range that does not impair the object of the present invention. Alternatively, in addition to the cation-curable resin according to the present invention, other cation-curable resins having an ether bond or an ester bond other than those contained in an epoxy group or oxetanyl group may be contained. As the other cation-curable resin, at least one selected from the group consisting of an epoxy resin having a bisphenol skeleton, an epoxy resin having a novolac skeleton, an epoxy resin having a naphthalene skeleton, and an epoxy resin having a dicyclopentadiene skeleton. A species epoxy resin is preferable, an epoxy resin having a bisphenol skeleton is more preferable, and a bisphenol F type epoxy resin is still more preferable.
상기 그 밖의 카티온 경화성 수지를 함유하는 경우, 본 발명에 관련된 카티온 경화성 수지의 함유량은, 카티온 경화성 수지 전체 100 중량부에 대해, 바람직한 하한이 10 중량부, 바람직한 상한이 80 중량부이다. 본 발명에 관련된 카티온 경화성 수지의 함유량이 10 중량부 미만 또는 80 중량부를 초과하면, 얻어지는 유기 EL 표시 소자용 밀봉제가 도포성이 떨어지는 것이 되는 경우가 있다. 본 발명에 관련된 카티온 경화성 수지의 함유량의 보다 바람직한 하한은 20 중량부, 보다 바람직한 상한은 70 중량부이다. When the above other cation-curable resins are contained, the content of the cation-curable resin according to the present invention is preferably 10 parts by weight, and a preferable upper limit is 80 parts by weight, based on 100 parts by weight of the entire cation-curable resin. When the content of the cation curable resin according to the present invention is less than 10 parts by weight or more than 80 parts by weight, the obtained sealing agent for organic EL display elements may be inferior in coatability. A more preferable lower limit of the content of the cation-curable resin according to the present invention is 20 parts by weight, and a more preferable upper limit is 70 parts by weight.
본 발명의 유기 EL 표시 소자용 밀봉제는 카티온 중합 개시제를 함유한다. The sealing agent for an organic EL display device of the present invention contains a cation polymerization initiator.
상기 카티온 중합 개시제로는, 광 조사에 의해 프로톤산 또는 루이스산을 발생시키는 광 카티온 중합 개시제나, 가열에 의해 프로톤산 또는 루이스산을 발생시키는 열 카티온 중합 개시제를 들 수 있다. 이것들이면 특별히 한정되지 않고, 이온성 산 발생형이어도 되고, 비이온성 산 발생형이어도 된다. Examples of the cation polymerization initiator include a photocationic polymerization initiator that generates protonic acid or Lewis acid by irradiation with light, and a thermal cation polymerization initiator that generates protonic acid or Lewis acid by heating. If these are not particularly limited, the ionic acid generating type may be used or the nonionic acid generating type may be used.
상기 광 카티온 중합 개시제는, 광 조사에 의해 프로톤산 또는 루이스산을 발생시키는 것이면 특별히 한정되지 않고, 이온성 광 산 발생형이어도 되고, 비이온성 광 산 발생형이어도 된다. The photocationic polymerization initiator is not particularly limited as long as it generates protonic acid or Lewis acid by light irradiation, and may be an ionic photoacid generation type or a nonionic photoacid generation type.
상기 이온성 광 산 발생형의 광 카티온 중합 개시제로는, 예를 들어, 카티온 부분이 방향족 술포늄, 방향족 요오드늄, 방향족 디아조늄, 방향족 암모늄, 또는 (2,4-시클로펜타디엔-1-일)((1-메틸에틸)벤젠)-Fe 카티온이고, 아니온 부분이 BF4 -, PF6 -, SbF6 -, 또는 (BX4)- (단, X 는 적어도 2 개 이상의 불소 또는 트리플루오로메틸기로 치환된 페닐기를 나타낸다) 로 구성되는 오늄염 등을 들 수 있다. As the ionic photoacid generating type photocationic polymerization initiator, for example, the cation moiety is aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, or (2,4-cyclopentadiene-1 -yl) ((1-methylethyl) benzene) -Fe cation, and not the whole portion of BF 4 -, PF 6 -, SbF 6 -, or (BX 4) - (stage, X is at least two fluorine Or a phenyl group substituted with a trifluoromethyl group).
상기 방향족 술포늄염으로는, 예를 들어, 비스(4-(디페닐술포니오)페닐)술파이드비스헥사플루오로포스페이트, 비스(4-(디페닐술포니오)페닐)술파이드비스헥사플루오로안티모네이트, 비스(4-(디페닐술포니오)페닐)술파이드비스테트라플루오로보레이트, 비스(4-(디페닐술포니오)페닐)술파이드테트라키스(펜타플루오로페닐)보레이트, 디페닐-4-(페닐티오)페닐술포늄헥사플루오로포스페이트, 디페닐-4-(페닐티오)페닐술포늄헥사플루오로안티모네이트, 디페닐-4-(페닐티오)페닐술포늄테트라플루오로보레이트, 디페닐-4-(페닐티오)페닐술포늄테트라키스(펜타플루오로페닐)보레이트, 트리페닐술포늄헥사플루오로포스페이트, 트리페닐술포늄헥사플루오로안티모네이트, 트리페닐술포늄테트라플루오로보레이트, 트리페닐술포늄테트라키스(펜타플루오로페닐)보레이트, 비스(4-(디(4-(2-하이드록시에톡시))페닐술포니오)페닐)술파이드비스헥사플루오로포스페이트, 비스(4-(디(4-(2-하이드록시에톡시))페닐술포니오)페닐)술파이드비스헥사플루오로안티모네이트, 비스(4-(디(4-(2-하이드록시에톡시))페닐술포니오)페닐)술파이드비스테트라플루오로보레이트, 비스(4-(디(4-(2-하이드록시에톡시))페닐술포니오)페닐)술파이드테트라키스(펜타플루오로페닐)보레이트 등을 들 수 있다. As the aromatic sulfonium salt, for example, bis(4-(diphenylsulfonio)phenyl)sulfidebishexafluorophosphate, bis(4-(diphenylsulfonio)phenyl)sulfidebishexafluoro Roantimonate, bis(4-(diphenylsulfonio)phenyl)sulfidebistetrafluoroborate, bis(4-(diphenylsulfonio)phenyl)sulfidetetrakis(pentafluorophenyl)borate , Diphenyl-4-(phenylthio)phenylsulfoniumhexafluorophosphate, diphenyl-4-(phenylthio)phenylsulfoniumhexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfoniumtetra Fluoroborate, diphenyl-4-(phenylthio)phenylsulfonium tetrakis(pentafluorophenyl)borate, triphenylsulfoniumhexafluorophosphate, triphenylsulfoniumhexafluoroantimonate, triphenylsulfonium Tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfidebishexafluoro Phosphate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfidebishexafluoroantimonate, bis(4-(di(4-(2-hydro)) Oxyethoxy))phenylsulfonio)phenyl)sulfidebistetrafluoroborate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfidetetrakis( Pentafluorophenyl) borate, and the like.
상기 방향족 요오드늄염으로는, 예를 들어, 디페닐요오드늄헥사플루오로포스페이트, 디페닐요오드늄헥사플루오로안티모네이트, 디페닐요오드늄테트라플루오로보레이트, 디페닐요오드늄테트라키스(펜타플루오로페닐)보레이트, 비스(도데실페닐)요오드늄헥사플루오로포스페이트, 비스(도데실페닐)요오드늄헥사플루오로안티모네이트, 비스(도데실페닐)요오드늄테트라플루오로보레이트, 비스(도데실페닐)요오드늄테트라키스(펜타플루오로페닐)보레이트, 4-메틸페닐-4-(1-메틸에틸)페닐요오드늄헥사플루오로포스페이트, 4-메틸페닐-4-(1-메틸에틸)페닐요오드늄헥사플루오로안티모네이트, 4-메틸페닐-4-(1-메틸에틸)페닐요오드늄테트라플루오로보레이트, 4-메틸페닐-4-(1-메틸에틸)페닐요오드늄테트라키스(펜타플루오로페닐)보레이트 등을 들 수 있다. Examples of the aromatic iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluoro Phenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) ) Iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoro Roantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrafluoroborate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate, etc. Can be mentioned.
상기 방향족 디아조늄염으로는, 예를 들어, 페닐디아조늄헥사플루오로포스페이트, 페닐디아조늄헥사플루오로안티모네이트, 페닐디아조늄테트라플루오로보레이트, 페닐디아조늄테트라키스(펜타플루오로페닐)보레이트 등을 들 수 있다. As the aromatic diazonium salt, for example, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis (pentafluorophenyl) borate And the like.
상기 방향족 암모늄염으로는, 예를 들어, 1-벤질-2-시아노피리디늄헥사플루오로포스페이트, 1-벤질-2-시아노피리디늄헥사플루오로안티모네이트, 1-벤질-2-시아노피리디늄테트라플루오로보레이트, 1-벤질-2-시아노피리디늄테트라키스(펜타플루오로페닐)보레이트, 1-(나프틸메틸)-2-시아노피리디늄헥사플루오로포스페이트, 1-(나프틸메틸)-2-시아노피리디늄헥사플루오로안티모네이트, 1-(나프틸메틸)-2-시아노피리디늄테트라플루오로보레이트, 1-(나프틸메틸)-2-시아노피리디늄테트라키스(펜타플루오로페닐)보레이트 등을 들 수 있다. Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridiniumhexafluorophosphate, 1-benzyl-2-cyanopyridiniumhexafluoroantimonate, and 1-benzyl-2-cyano Pyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis(pentafluorophenyl)borate, 1-(naphthylmethyl)-2-cyanopyridiniumhexafluorophosphate, 1-(naph) Tylmethyl)-2-cyanopyridiniumhexafluoroantimonate, 1-(naphthylmethyl)-2-cyanopyridiniumtetrafluoroborate, 1-(naphthylmethyl)-2-cyanopyridinium Tetrakis (pentafluorophenyl) borate, etc. are mentioned.
상기 (2,4-시클로펜타디엔-1-일)((1-메틸에틸)벤젠)-Fe 염으로는, 예를 들어, (2,4-시클로펜타디엔-1-일)((1-메틸에틸)벤젠)-Fe(Ⅱ)헥사플루오로포스페이트, (2,4-시클로펜타디엔-1-일)((1-메틸에틸)벤젠)-Fe(Ⅱ)헥사플루오로안티모네이트, (2,4-시클로펜타디엔-1-일)((1-메틸에틸)벤젠)-Fe(Ⅱ)테트라플루오로보레이트, (2,4-시클로펜타디엔-1-일)((1-메틸에틸)벤젠)-Fe(Ⅱ)테트라키스(펜타플루오로페닐) 보레이트 등을 들 수 있다. As the (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt, for example, (2,4-cyclopentadien-1-yl) ((1- Methylethyl)benzene)-Fe(II)hexafluorophosphate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II)hexafluoroantimonate, ( 2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II)tetrafluoroborate, (2,4-cyclopentadien-1-yl)((1-methylethyl) )Benzene)-Fe(II)tetrakis(pentafluorophenyl)borate, etc. are mentioned.
상기 비이온성 광 산 발생형 광 카티온 중합 개시제로는, 예를 들어, 니트로벤질에스테르, 술폰산 유도체, 인산에스테르, 페놀술폰산에스테르, 디아조나프토퀴논, N-하이드록시이미드술포네이트 등을 들 수 있다. Examples of the nonionic photoacid-generating photocationic polymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate, and the like. .
상기 광 카티온 중합 개시제 중 시판되고 있는 것으로는, 예를 들어, DTS-200 (미도리 화학사 제조), UVI6990, UVI6974 (모두 유니온 카바이드사 제조), SP-150, SP-170 (모두 ADEKA 사 제조), FC-508, FC-512 (모두 3M 사 제조), IRGACURE 261, IRGACURE 290 (모두 BASF Japan 사 제조), PI2074 (로디아사 제조) 등을 들 수 있다. Among the photocationic polymerization initiators commercially available, for example, DTS-200 (manufactured by Midori Chemical), UVI6990, UVI6974 (all manufactured by Union Carbide), SP-150, SP-170 (all manufactured by ADEKA) , FC-508, FC-512 (all manufactured by 3M), IRGACURE 261, IRGACURE 290 (all manufactured by BASF Japan), PI2074 (manufactured by Rhodia), and the like.
상기 열 카티온 중합 개시제로는, 예를 들어, BF4 -, PF6 -, SbF6 -, 또는 (BX4)- (단, X 는 적어도 2 개 이상의 불소 혹은 트리플루오로메틸기로 치환된 페닐기를 나타낸다) 등을 카운터 아니온으로 하는 술포늄염, 포스포늄염, 제 4 급 암모늄염, 디아조늄염, 요오드늄염 등을 들 수 있다. 그 중에서도 술포늄염이 바람직하다. The thermal cationic polymerization initiator include, for example, BF 4 -, PF 6 - , SbF 6 -, or (BX 4) - (stage, X is a phenyl group substituted with at least a group of two or more fluorine or trifluoromethyl Is a sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt, an iodonium salt, etc. which are used as a counter anion. Among them, sulfonium salts are preferred.
상기 술포늄염으로는, 트리페닐술포늄사불화붕소, 트리페닐술포늄육불화안티몬, 트리페닐술포늄육불화비소, 트리(4-메톡시페닐)술포늄육불화비소, 디페닐(4-페닐티오페닐)술포늄육불화 비소 등을 들 수 있다. Examples of the sulfonium salt include triphenylsulfonium boron tetrafluoride, triphenylsulfonium antimony hexafluoride, triphenylsulfonium arsenic hexafluoride, tri(4-methoxyphenyl)sulfonium arsenic hexafluoride, diphenyl(4-phenylthiophenyl)sulfo And arsenic hexafluoride.
상기 포스포늄염으로는, 에틸트리페닐포스포늄육불화안티몬, 테트라부틸포스포늄육불화안티몬 등을 들 수 있다. Examples of the phosphonium salt include ethyl triphenylphosphonium antimony hexafluoride, tetrabutylphosphonium antimony hexafluoride, and the like.
상기 제 4 급 암모늄염으로는, 예를 들어, 디메틸페닐(4-메톡시벤질)암모늄헥사플루오로포스페이트, 디메틸페닐(4-메톡시벤질)암모늄헥사플루오로안티모네이트, 디메틸페닐(4-메톡시벤질)암모늄테트라키스(펜타플루오로페닐)보레이트, 디메틸페닐(4-메틸벤질)암모늄헥사플루오로헥사플루오로포스페이트, 디메틸페닐(4-메틸벤질)암모늄헥사플루오로안티모네이트, 디메틸페닐(4-메틸벤질)암모늄헥사플루오로테트라키스(펜타플루오로페닐)보레이트, 메틸페닐디벤질암모늄, 메틸페닐디벤질암모늄헥사플루오로안티모네이트헥사플루오로포스페이트, 메틸페닐디벤질암모늄테트라키스(펜타플루오로페닐)보레이트, 페닐트리벤질암모늄테트라키스(펜타플루오로페닐)보레이트, 디메틸페닐(3,4-디메틸벤질)암모늄테트라키스(펜타플루오로페닐)보레이트, N,N-디메틸-N-벤질아닐리늄육불화안티몬, N,N-디에틸-N-벤질아닐리늄사불화붕소, N,N-디메틸-N-벤질피리디늄육불화안티몬, N,N-디에틸-N-벤질피리디늄트리플루오로메탄술폰산 등을 들 수 있다. Examples of the quaternary ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, and dimethylphenyl (4-me). Oxybenzyl) ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorohexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl ( 4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyldibenzyl ammonium, methylphenyldibenzylammonium hexafluoroantimonate hexafluorophosphate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl ) Borate, phenyltribenzyl ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N,N-dimethyl-N-benzylanilinium hex Antimony fluoride, N,N-diethyl-N-benzylanilinium boron tetrafluoride, N,N-dimethyl-N-benzylpyridinium antimony hexafluoride, N,N-diethyl-N-benzylpyridinium trifluoromethane And sulfonic acid.
상기 열 카티온 중합 개시제 중 시판되고 있는 것으로는, 예를 들어, 아데카 옵톤 CP-66, 아데카 옵톤 CP-77 (모두 ADEKA 사 제조) 이나, 열 활성뿐만 아니라 광 활성도 갖고 있는 열 카티온 중합 개시제인 선에이드 SI-60, 선에이드 SI-80, 선에이드 SI-100, 선에이드 SI-110, 선에이드 SI-180 (모두 산신 화학 공업사 제조), CXC-1612, CXC-1738, CXC-1821 (모두 킹 인더스트리즈사 제조) 등을 들 수 있다. Among the thermal cation polymerization initiators that are commercially available, for example, Adeka Opton CP-66 and Adeka Opton CP-77 (all manufactured by ADEKA), but thermal cation polymerization that has photoactivity as well as thermal activity Initiators Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-100, Sun-Aid SI-110, Sun-Aid SI-180 (all manufactured by Sanshin Chemical Industries, Ltd.), CXC-1612, CXC-1738, CXC-1821 (All made by King Industries), etc. are mentioned.
상기 카티온 중합 개시제의 함유량은, 상기 카티온 경화성 수지 100 중량부에 대해, 바람직한 하한이 0.1 중량부, 바람직한 상한이 10 중량부이다. 상기 카티온 중합 개시제의 함유량이 0.1 중량부 미만이면, 카티온 중합이 충분히 진행되지 않거나, 경화 반응이 지나치게 늦어지거나 하는 경우가 있다. 상기 카티온 중합 개시제의 함유량이 10 중량부를 초과하면, 얻어지는 유기 EL 표시 소자용 밀봉제의 경화 반응이 지나치게 빨라져, 작업성이 저하되거나, 얻어지는 유기 EL 표시 소자용 밀봉제의 경화물이 불균일해지거나 하는 경우가 있다. 상기 카티온 중합 개시제의 함유량의 보다 바람직한 하한은 0.5 중량부, 보다 바람직한 상한은 5 중량부이다. The content of the cation polymerization initiator is a preferable lower limit of 0.1 parts by weight and a preferable upper limit of 10 parts by weight per 100 parts by weight of the cation curable resin. When the content of the cation polymerization initiator is less than 0.1 part by weight, the cation polymerization may not sufficiently proceed or the curing reaction may be too late. If the content of the cation polymerization initiator exceeds 10 parts by weight, the curing reaction of the obtained sealing agent for an organic EL display device becomes too fast, the workability decreases, or the cured product of the obtained sealing agent for an organic EL display device becomes non-uniform. There are cases. A more preferable lower limit of the content of the cation polymerization initiator is 0.5 parts by weight, and a more preferable upper limit is 5 parts by weight.
본 발명의 유기 EL 표시 소자용 밀봉제는 증감제를 함유하여도 된다. 상기 증감제는 상기 카티온 중합 개시제의 중합 개시 효율을 보다 향상시켜, 본 발명의 유기 EL 표시 소자용 밀봉제의 경화 반응을 보다 촉진시키는 역할을 갖는다. The sealing agent for an organic EL display device of the present invention may contain a sensitizer. The sensitizer has a role of further improving the polymerization initiation efficiency of the cation polymerization initiator and further accelerating the curing reaction of the sealing agent for an organic EL display device of the present invention.
상기 증감제로는, 예를 들어, 2,4-디에틸티오크산톤 등의 티오크산톤계 화합물이나, 2,2-디메톡시-1,2-디페닐에탄-1-온, 벤조페논, 2,4-디클로로벤조페논, o-벤조일벤조산메틸, 4,4＇-비스(디메틸아미노)벤조페논, 4-벤조일-4'메틸디페닐술파이드 등을 들 수 있다. Examples of the sensitizer include thioxanthone compounds such as 2,4-diethyl thioxanthone, 2,2-dimethoxy-1,2-diphenylethan-1-one, benzophenone, and 2 ,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis(dimethylamino)benzophenone, 4-benzoyl-4'methyldiphenyl sulfide, and the like.
상기 증감제의 함유량은, 상기 카티온 경화성 수지 100 중량부에 대해, 바람직한 하한은 0.05 중량부, 바람직한 상한은 3 중량부이다. 상기 증감제의 함유량이 0.05 중량부 미만이면, 증감 효과가 충분히 얻어지지 않는 경우가 있다. 상기 증감제의 함유량이 3 중량부를 초과하면, 흡수가 지나치게 커져 심부까지 광이 전달되지 않는 경우가 있다. 상기 증감제의 함유량의 보다 바람직한 하한은 0.1 중량부, 보다 바람직한 상한은 1 중량부이다. The content of the sensitizer is, with respect to 100 parts by weight of the cation-curable resin, a preferable lower limit is 0.05 parts by weight, and a preferable upper limit is 3 parts by weight. When the content of the sensitizer is less than 0.05 parts by weight, the sensitizing effect may not be sufficiently obtained. When the content of the sensitizer exceeds 3 parts by weight, absorption may become too large and light may not be transmitted to the deep part. A more preferable lower limit of the content of the sensitizer is 0.1 parts by weight, and a more preferable upper limit is 1 part by weight.
본 발명의 유기 EL 표시 소자용 밀봉제는, 경화물의 내습성을 향상시키는 것 등을 목적으로 하여, 충전제를 함유하는 것이 바람직하다. 특히 본 발명에 관련된 카티온 경화성 수지로서 점도가 낮은 상기 식 (1) 로 나타내는 화합물을 사용하는 경우, 도포성을 악화시키지 않고 충전제를 많이 배합할 수 있다. It is preferable that the sealing agent for an organic EL display device of the present invention contains a filler for the purpose of improving the moisture resistance of a cured product. In particular, when a compound represented by the above formula (1) having a low viscosity is used as the cation curable resin according to the present invention, a large amount of filler can be blended without deteriorating the coatability.
상기 충전제로는, 예를 들어, 탤크, 석면, 실리카, 마이카, 규조토, 스멕타이트, 벤토나이트, 탄산칼슘, 탄산마그네슘, 알루미나, 몬모릴로나이트, 산화아연, 산화철, 산화마그네슘, 산화주석, 산화티탄, 수산화마그네슘, 수산화알루미늄, 질화규소, 황산바륨, 석고, 규산칼슘, 유리비즈, 세리사이트 활성 백토, 벤토나이트, 질화알루미늄 등의 무기 필러나, 폴리에스테르 미립자, 폴리우레탄 미립자, 비닐 중합체 미립자, 아크릴 중합체 미립자 등의 유기 필러 등을 들 수 있다. 그 중에서도, 내습성을 향상시키는 효과가 우수한 점에서, 탤크가 바람직하다. Examples of the filler include talc, asbestos, silica, mica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, Inorganic fillers such as aluminum hydroxide, silicon nitride, barium sulfate, gypsum, calcium silicate, glass beads, sericite activated clay, bentonite, aluminum nitride, and organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, etc. And the like. Among them, talc is preferred because of its excellent effect of improving moisture resistance.
상기 충전제의 함유량은, 상기 카티온 경화성 수지 100 중량부에 대해, 바람직한 하한이 10 중량부, 바람직한 상한이 80 중량부이다. 상기 충전제의 함유량이 10 중량부 미만이면, 내습성을 향상시키는 효과가 충분히 발휘되지 않는 경우가 있다. 상기 충전제의 함유량이 80 중량부를 초과하면, 얻어지는 유기 EL 표시 소자용 밀봉제의 점도가 지나치게 높아져 도포성이 악화되는 경우가 있다. 상기 충전제의 함유량의 보다 바람직한 하한은 15 중량부, 보다 바람직한 상한은 70 중량부이다. The content of the filler is a preferable lower limit of 10 parts by weight and a preferable upper limit of 80 parts by weight with respect to 100 parts by weight of the cation-curable resin. When the content of the filler is less than 10 parts by weight, the effect of improving moisture resistance may not be sufficiently exhibited. When the content of the filler exceeds 80 parts by weight, the viscosity of the obtained sealing agent for an organic EL display element becomes too high, and the coating property may deteriorate. A more preferable lower limit of the content of the filler is 15 parts by weight, and a more preferable upper limit is 70 parts by weight.
본 발명의 유기 EL 표시 소자용 밀봉제는 실란 커플링제를 함유하여도 된다. 상기 실란 커플링제는, 본 발명의 유기 EL 표시 소자용 밀봉제와 기판 등의 접착성을 향상시키는 역할을 갖는다. The sealing agent for an organic EL display device of the present invention may contain a silane coupling agent. The silane coupling agent has a role of improving the adhesion between the sealing agent for an organic EL display device of the present invention and a substrate.
상기 실란 커플링제로는, 예를 들어, 3-아미노프로필트리메톡시실란, 3-메르캅토프로필트리메톡시실란, 3-글리시독시프로필트리메톡시실란, 3-이소시아네이트프로필트리메톡시실란 등을 들 수 있다. 이들 실란 커플링제는, 단독으로 사용되어도 되고, 2 종 이상이 병용되어도 된다. Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanatepropyltrimethoxysilane. Can be mentioned. These silane coupling agents may be used alone or in combination of two or more.
상기 실란 커플링제의 함유량은, 상기 카티온 경화성 수지 100 중량부에 대해, 바람직한 하한이 0.1 중량부, 바람직한 상한이 10 중량부이다. 상기 실란 커플링제의 함유량이 0.1 중량부 미만이면, 얻어지는 유기 EL 표시 소자용 밀봉제의 접착성을 향상시키는 효과가 충분히 발휘되지 않는 경우가 있다. 상기 실란 커플링제의 함유량이 10 중량부를 초과하면, 잉여 실란 커플링제가 블리드 아웃되는 경우가 있다. 상기 실란 커플링제의 함유량의 보다 바람직한 하한은 0.5 중량부, 보다 바람직한 상한은 5 중량부이다. The content of the silane coupling agent is 0.1 parts by weight in a preferable lower limit and 10 parts by weight in a preferable upper limit with respect to 100 parts by weight of the cation-curable resin. When the content of the silane coupling agent is less than 0.1 part by weight, the effect of improving the adhesion of the obtained sealing agent for organic EL display elements may not be sufficiently exhibited. When the content of the silane coupling agent exceeds 10 parts by weight, excess silane coupling agent may bleed out. A more preferable lower limit of the content of the silane coupling agent is 0.5 parts by weight, and a more preferable upper limit is 5 parts by weight.
본 발명의 유기 EL 표시 소자용 밀봉제는, 또한, 본 발명의 목적을 저해하지 않는 범위에 있어서, 열 경화제를 함유하여도 된다. 상기 열 경화제를 함유함으로써, 본 발명의 유기 EL 표시 소자용 밀봉제에 열 경화성을 부여할 수 있다. The sealing agent for an organic EL display device of the present invention may further contain a thermal curing agent within a range that does not impair the object of the present invention. By containing the thermal curing agent, it is possible to impart thermal curing properties to the sealing agent for an organic EL display device of the present invention.
상기 열 경화제는 특별히 한정되지 않고, 예를 들어, 하이드라지드 화합물, 이미다졸 유도체, 산무수물, 디시안디아미드, 구아니딘 유도체, 변성 지방족 폴리 아민, 각종 아민과 에폭시 수지의 부가 생성물 등을 들 수 있다. The thermal curing agent is not particularly limited, and examples thereof include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamides, guanidine derivatives, modified aliphatic polyamines, addition products of various amines and epoxy resins. .
상기 하이드라지드 화합물로는, 예를 들어, 1,3-비스[하이드라지노카르보노에틸-5-이소프로필히단토인] 등을 들 수 있다. Examples of the hydrazide compound include 1,3-bis[hydrazinocarbonoethyl-5-isopropylhydantoin].
상기 이미다졸 유도체로는, 예를 들어, 1-시아노에틸-2-페닐이미다졸, N-[2-(2-메틸-1-이미다졸릴)에틸]우레아, 2,4-디아미노-6-[2'-메틸이미다졸릴-(1')]-에틸-s-트리아진, N,N'-비스(2-메틸-1-이미다졸릴에틸)우레아, N,N'-(2-메틸-1-이미다졸릴에틸)-아디포아미드, 2-페닐-4-메틸-5-하이드록시메틸이미다졸, 2-페닐-4,5-디하이드록시메틸이미다졸 등을 들 수 있다. 상기 산무수물로는, 예를 들어, 테트라하이드로무수프탈산, 에틸렌글리콜-비스(안하이드로트리멜리테이트) 등을 들 수 있다. Examples of the imidazole derivatives include 1-cyanoethyl-2-phenylimidazole, N-[2-(2-methyl-1-imidazolyl)ethyl]urea, 2,4-diamino -6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, N,N'-bis(2-methyl-1-imidazolylethyl)urea, N,N'- (2-methyl-1-imidazolylethyl)-adipoamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, etc. Can be mentioned. Examples of the acid anhydride include tetrahydrophthalic anhydride and ethylene glycol-bis (anhydrotrimelitate).
이들 열 경화제는 단독으로 사용되어도 되고, 2 종류 이상이 병용되어도 된다. These thermosetting agents may be used alone or in combination of two or more.
상기 열 경화제의 함유량은, 상기 카티온 경화성 수지 100 중량부에 대해, 바람직한 하한이 0.5 중량부, 바람직한 상한이 30 중량부이다. 상기 열 경화 제의 함유량이 0.5 중량부 미만이면, 얻어지는 유기 EL 표시 소자용 밀봉제에 충분한 열 경화성을 부여할 수 없는 경우가 있다. 상기 열 경화제의 함유량이 30 중량부를 초과하면, 얻어지는 유기 EL 표시 소자용 밀봉제의 보존 안정성이 불충분해지거나, 얻어지는 유기 EL 표시 소자용 밀봉제의 경화물의 내습성이 나빠지거나 하는 경우가 있다. 상기 열 경화제의 함유량의 보다 바람직한 하한은 1 중량부, 보다 바람직한 상한은 15 중량부이다. The content of the thermal curing agent is preferably 0.5 parts by weight, and the upper limit is 30 parts by weight, based on 100 parts by weight of the cation curable resin. When the content of the thermal curing agent is less than 0.5 parts by weight, sufficient thermal curing properties may not be imparted to the obtained sealing agent for an organic EL display element. When the content of the thermal curing agent exceeds 30 parts by weight, the storage stability of the obtained sealing agent for organic EL display elements may be insufficient, or the moisture resistance of the cured product of the obtained sealing agent for organic EL display elements may deteriorate. A more preferable lower limit of the content of the thermal curing agent is 1 part by weight, and a more preferable upper limit is 15 parts by weight.
본 발명의 유기 EL 표시 소자용 밀봉제는, 본 발명의 목적을 저해하지 않는 범위에 있어서, 표면 개질제를 함유하여도 된다. 상기 표면 개질제를 함유함으로써, 본 발명의 유기 EL 표시 소자용 밀봉제에 도막의 평탄성을 부여할 수 있다. The sealing agent for an organic EL display device of the present invention may contain a surface modifier within a range that does not impair the object of the present invention. By containing the surface modifier, it is possible to impart flatness of the coating film to the sealing agent for an organic EL display device of the present invention.
상기 표면 개질제로는, 예를 들어, 계면 활성제나 레벨링제 등을 들 수 있다. Examples of the surface modifier include surfactants and leveling agents.
상기 계면 활성제나 상기 레벨링제로는, 예를 들어, 실리콘계, 아크릴계, 불소계 등의 것을 들 수 있다. Examples of the surfactant and leveling agent include silicone-based, acrylic-based, and fluorine-based surfactants.
상기 계면 활성제나 상기 레벨링제 중 시판되고 있는 것으로는, 예를 들어, BYK-345 (빅 케미·재팬사 제조), BYK-340 (빅 케미·재팬사 제조), 서프론 S-611 (AGC 세이미 케미컬사 제조) 등을 들 수 있다. Among the surfactants and leveling agents that are commercially available, for example, BYK-345 (manufactured by Big Chemie Japan), BYK-340 (manufactured by Big Chemie Japan), and Surflon S-611 (AGC Corporation) Already manufactured by Chemical Co.), etc. are mentioned.
본 발명의 유기 EL 표시 소자용 밀봉제는, 본 발명의 목적을 저해하지 않는 범위에서, 소자 전극의 내구성을 향상시키기 위해, 유기 EL 표시 소자용 밀봉제 중에 발생한 산과 반응하는 화합물 또는 이온 교환 수지를 함유하여도 된다. The sealing agent for an organic EL display device of the present invention contains a compound or an ion exchange resin that reacts with an acid generated in the sealing agent for an organic EL display device in order to improve the durability of the device electrode within a range that does not impair the object of the present invention. You may contain.
상기 발생한 산과 반응하는 화합물로는, 산과 중화되는 물질, 예를 들어, 알칼리 금속의 탄산염 혹은 탄산수소염, 또는 알칼리 토금속의 탄산염 혹은 탄산수소염 등을 들 수 있다. 구체적으로는 예를 들어, 탄산칼슘, 탄산수소칼슘, 탄산나트륨, 탄산수소나트륨 등이 사용된다. Examples of the compound reacting with the generated acid include a substance neutralized with an acid, for example, an alkali metal carbonate or hydrogen carbonate, or an alkaline earth metal carbonate or hydrogen carbonate. Specifically, for example, calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, and the like are used.
상기 이온 교환 수지로는, 양이온 교환형, 음이온 교환형, 양쪽 이온 교환형 모두 사용할 수 있지만, 특히 염화물 이온을 흡착할 수 있는 양이온 교환형 또는 양쪽이온 교환형이 바람직하다. As the ion exchange resin, a cation exchange type, an anion exchange type, and a both ion exchange type can be used. In particular, a cation exchange type or a zwitterion exchange type capable of adsorbing chloride ions is preferable.
또, 본 발명의 유기 EL 표시 소자용 밀봉제는, 본 발명의 목적을 저해하지 않는 범위에서, 필요에 따라, 경화 지연제, 보강제, 연화제, 가소제, 점도 조정제, 자외선 흡수제, 산화 방지제 등의 공지된 각종 첨가제를 함유하여도 된다. In addition, the sealing agent for an organic EL display device of the present invention is known as a curing retardant, a reinforcing agent, a softener, a plasticizer, a viscosity modifier, an ultraviolet absorber, an antioxidant, etc., if necessary, within a range that does not impair the object of the present invention. Various additives may be contained.
본 발명의 유기 EL 표시 소자용 밀봉제를 제조하는 방법으로는, 예를 들어, 호모디스퍼, 호모믹서, 만능 믹서, 플레네터리 믹서, 니더, 3 개롤 등의 혼합기를 이용하여 카티온 경화성 수지와, 카티온 중합 개시제와, 필요에 따라 첨가하는 첨가제를 혼합하는 방법 등을 들 수 있다. As a method of manufacturing the sealing agent for an organic EL display device of the present invention, for example, a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a cation curable resin using a mixer such as three rolls. Wow, a method of mixing a cation polymerization initiator and an additive added as needed, etc. are mentioned.
본 발명의 유기 EL 표시 소자용 밀봉제는, E 형 점도계를 이용하여 25 ℃, 1 ∼ 100 rpm 의 조건에서 측정한 전체의 점도의 하한이 80 mPa·s, 상한이 5000 mPa·s 이다. 상기 점도가 80 mPa·s 미만이면, 얻어지는 유기 EL 표시 소자용 밀봉제가 도포성이나 도포 후의 형상 안정성이 떨어지는 것이 되거나, 조성 불균일이 발생하여 경화물이 투명성이 떨어지는 것이 되거나 한다. 상기 점도가 5000 mPa·s 를 초과하면, 얻어지는 유기 EL 표시 소자용 밀봉제가 도포성이 떨어지는 것이 된다. 상기 점도의 바람직한 하한은 150 mPa·s, 바람직한 상한은 3000 mPa·s, 보다 바람직한 하한은 200 mPa·s, 보다 바람직한 상한은 1000 mPa·s 이다. The sealing agent for an organic EL display device of the present invention has a lower limit of 80 mPa·s and an upper limit of 5000 mPa·s measured at 25° C. and 1 to 100 rpm using an E-type viscometer. If the viscosity is less than 80 mPa·s, the resulting sealing agent for an organic EL display device may have poor coatability or shape stability after application, or a composition unevenness may occur, resulting in poor transparency of the cured product. When the viscosity exceeds 5000 mPa·s, the resulting sealing agent for organic EL display elements is poor in coating properties. A preferable lower limit of the viscosity is 150 mPa·s, a preferable upper limit is 3000 mPa·s, a more preferable lower limit is 200 mPa·s, and a more preferable upper limit is 1000 mPa·s.
또한, 상기 점도는, 예를 들어, E 형 점도계로서 VISCOMETER TV-22 (토키 산업사 제조) 를 이용하여 CP1 형 콘 플레이트로 측정할 수 있다. In addition, the viscosity can be measured with a CP1-type cone plate using, for example, VISCOMETER TV-22 (manufactured by Toki Industries, Ltd.) as an E-type viscometer.
또, E 형 점도계를 이용하여 측정할 때, 점도가 1000 mPa·s 이상 5000 mPa·s 미만이 되는 경우에는 1 rpm 의 조건에서 측정하고, 점도가 500 mPa·s 이상 1000 mPa·s 미만이 되는 경우에는 5 rpm 의 조건에서 측정하고, 점도가 200 mPa·s 이상 500 mPa·s 미만이 되는 경우에는 10 rpm 의 조건에서 측정하고, 점도가 50 mPa·s 이상 200 mPa·s 미만이 되는 경우에는 20 rpm 의 조건에서 측정하고, 점도가 50 mPa·s 미만이 되는 경우에는 100 rpm 의 조건에서 측정하는 것이 바람직하다. In addition, when measuring using an E-type viscometer, when the viscosity is 1000 mPa·s or more and less than 5000 mPa·s, it is measured under conditions of 1 rpm, and the viscosity is 500 mPa·s or more and less than 1000 mPa·s. In this case, it is measured under the conditions of 5 rpm, and when the viscosity is 200 mPa·s or more and less than 500 mPa·s, it is measured under the conditions of 10 rpm, and when the viscosity is 50 mPa·s or more and less than 200 mPa·s. It is measured under the conditions of 20 rpm, and when the viscosity becomes less than 50 mPa*s, it is preferable to measure under the conditions of 100 rpm.
본 발명에 의하면, 아웃 가스의 발생을 억제할 수 있고, 또한, 도포성이 우수한 유기 EL 표시 소자용 밀봉제를 제공할 수 있다. ADVANTAGE OF THE INVENTION According to this invention, generation|occurrence|production of outgas can be suppressed and the sealing agent for organic EL display elements excellent in coatability can be provided.
이하에 실시예를 들어 본 발명을 더욱 상세하게 설명하지만, 본 발명은 이들 실시예에만 한정되지 않는다. Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited only to these examples.
(실시예 1)(Example 1)
카티온 경화성 수지로서, 상기 식 (4) 로 나타내는 화합물 (다이셀사 제조, 「셀록사이드 8000」) 50 중량부 및 상기 식 (5) 로 나타내는 화합물 (닛산 화학사 제조, 「TEPIC-VL」) 50 중량부와, 광 카티온 중합 개시제로서 방향족 술포늄염 (미도리 화학사 제조, 「DTS-200」) 1 중량부를 혼합하여 80 ℃ 로 가열한 후, 교반 혼합기 (싱키사 제조, 「AR-250」) 를 이용하여 교반 속도 3000 rpm 으로 균일하게 교반 혼합하여, 유기 EL 표시 소자용 밀봉제를 제조하였다. As a cation curable resin, 50 parts by weight of the compound represented by the formula (4) (manufactured by Daicel, ``Celoxide 8000'') and 50 parts by weight of the compound represented by the formula (5) (manufactured by Nissan Chemical Corporation, ``TEPIC-VL'') Buwa and 1 part by weight of an aromatic sulfonium salt (manufactured by Midori Chemical Co., Ltd., "DTS-200") as a photocationic polymerization initiator were mixed and heated to 80°C, and then a stirring mixer (manufactured by Sinki, "AR-250") was used. Then, the mixture was uniformly stirred and mixed at a stirring speed of 3000 rpm to prepare a sealing agent for an organic EL display device.
(실시예 2 ∼ 7, 비교예 1 ∼ 6)(Examples 2 to 7, Comparative Examples 1 to 6)
표 1 에 기재된 각 재료를 표 1 에 기재된 배합비에 따라 실시예 1 과 동일하게 하여 교반 혼합하여, 유기 EL 표시 소자용 밀봉제를 제조하였다. Each of the materials listed in Table 1 was stirred and mixed in the same manner as in Example 1 according to the mixing ratio shown in Table 1 to prepare a sealing agent for an organic EL display device.
＜평가＞<Evaluation>
실시예 1 ∼ 7 및 비교예 1 ∼ 6 에서 얻어진 각 유기 EL 표시 소자용 밀봉제에 대하여 이하의 평가를 실시하였다. 결과를 표 1 에 나타내었다. Each of the sealing agents for organic EL display devices obtained in Examples 1 to 7 and Comparative Examples 1 to 6 was evaluated below. The results are shown in Table 1.
(점도)(Viscosity)
실시예 1 ∼ 7 및 비교예 1 ∼ 6 에서 얻어진 각 유기 EL 표시 소자용 밀봉제에 대하여, E 형 점도계 (토키 산업사 제조, 「VISCOMETER TV-22」콘 플레이트 : CP1 형) 를 이용하여 25 ℃, 1 ∼ 100 rpm 의 조건에 있어서의 점도를 측정하였다. For each of the sealing agents for organic EL display elements obtained in Examples 1 to 7 and Comparative Examples 1 to 6, using an E-type viscometer (manufactured by Toki Industries, "VISCOMETER TV-22" cone plate: CP1 type), The viscosity in the conditions of 1-100 rpm was measured.
(도포성 및 도포 형상 안정성)(Applicability and application shape stability)
디스펜서 (무사시 엔지니어링사 제조, 「SHOTMASTER300」) 를 이용하여 디스펜서 노즐을 400 ㎛, 노즐 갭을 30 ㎛, 도출압을 300 kPa 로 고정시키고, 유리 기판 위에 실시예 1 ∼ 7 및 비교예 1 ∼ 6 에서 얻어진 각 유기 EL 표시 소자용 밀봉제를 도포하였다. 도포 후, 자외선 조사 장치 (오크사 제조, 「JL-4300-3S」) 를 이용하여 자외선을 1500 mJ/㎠ 조사하고, 그 후 100 ℃ 에서 15 분간 가열함으로써 수지를 경화시켰다. 또한, 실시예 4 ∼ 6, 비교예 2, 5 에서 얻어진 유기 EL 표시 소자용 밀봉제에 대해서는, 자외선을 조사하지 않고 100 ℃ 에서 30 분간 가열 경화시켰다. 밀봉제를 도포하고 나서 경화 반응이 일어날 때까지의 중량 변화를 열중량 측정 장치 (TA-INSTRUMENTS 사 제조, 「TGA」) 를 이용하여 확인하였다. Using a dispenser (manufactured by Musashi Engineering, ``SHOTMASTER300''), the dispenser nozzle was fixed at 400 µm, the nozzle gap was 30 µm, and the relief pressure was 300 kPa, and in Examples 1 to 7 and Comparative Examples 1 to 6 on a glass substrate, The obtained sealing agent for each organic EL display element was applied. After application, ultraviolet rays were irradiated with 1500 mJ/cm 2 using an ultraviolet irradiation apparatus (manufactured by Oak Co., Ltd., "JL-4300-3S"), and then the resin was cured by heating at 100° C. for 15 minutes. In addition, about the sealing agent for organic EL display elements obtained in Examples 4-6 and Comparative Examples 2 and 5, it heat-hardened at 100 degreeC for 30 minutes, without irradiation with ultraviolet rays. The change in weight from applying the sealing agent until the curing reaction occurred was confirmed using a thermogravimetric measuring device (manufactured by TA-INSTRUMENTS, "TGA").
긁힘이나 흐름없이 도포할 수 있고, 또한, 경화 반응이 일어나기까지 중량 감소가 거의 일어나지 않은 경우를 「○」, 도포 상태가 긁힘이나 흐름이 발생한 경우나, 경화 반응이 일어날 때까지 5 ％ 미만의 중량 감소가 일어난 경우를 「△」, 도포 상태가 큰 도포 균열이나 도포 불균일이 발생하거나, 전혀 도포할 수 없거나 한 경우나, 경화 반응 일어날 때까지 5 ％ 이상의 중량 감소가 일어난 경우를 「×」로 하여 도포성 및 도포 형상 안정성을 평가하였다. It is possible to apply without scratches or flow, and when the weight loss hardly occurs until the curing reaction occurs, "○", when the coating state is scratched or flow, or until the curing reaction occurs, the weight is less than 5% When the reduction occurs, ``△'', when a large coating state occurs, coating cracks or non-uniformity of coating occur, cannot be applied at all, or when a weight reduction of 5% or more occurs until the curing reaction occurs, it is indicated by ``x''. Applicability and application shape stability were evaluated.
(아웃 가스 방지성)(Out gas prevention characteristics)
실시예 1 ∼ 7 및 비교예 1 ∼ 6 에서 얻어진 각 유기 EL 표시 소자용 밀봉제를 바이알병 중에 300 ㎎ 계량하여 봉입한 후, 자외선 조사 장치 (오크사 제조, 「JL-4300-3S」) 를 이용하여 자외선을 1500 mJ/㎠ 조사하고, 그 후 100 ℃ 에서 15 분간 가열함으로써 수지를 경화시켰다. 다시 이 바이알병을 85 ℃ 의 항온 오븐으로 100 시간 가열하고, 바이알병 중의 기화 성분을 가스 크로마토그래피 질량 분석계 (닛폰 전자사 제조, 「JMS-k9」) 를 이용하여 측정하였다. 또한, 실시예 4 ∼ 6, 비교예 2, 5 에서 얻어진 유기 EL 표시 소자용 밀봉제에 있어서는, 자외선을 조사하지 않고 100 ℃ 에서 30 분간 가열 경화시켰다. After weighing and sealing 300 mg of the sealing agent for each organic EL display device obtained in Examples 1 to 7 and Comparative Examples 1 to 6 in a vial bottle, an ultraviolet irradiation device (manufactured by Oak Co., Ltd., "JL-4300-3S") was used. The resin was cured by irradiating 1500 mJ/cm 2 with ultraviolet rays and then heating at 100°C for 15 minutes. Again, this vial bottle was heated in a constant temperature oven at 85°C for 100 hours, and the vaporized component in the vial bottle was measured using a gas chromatography mass spectrometer (manufactured by Nippon Electronics Co., Ltd., "JMS-k9"). In addition, in the sealing agent for organic EL display elements obtained in Examples 4-6 and Comparative Examples 2 and 5, it heat-hardened at 100 degreeC for 30 minutes, without irradiation with ultraviolet rays.
그 결과, 기화 성분량이 20 ppm 미만이었던 경우를 「○」, 20 ppm 이상 100 ppm 미만이었던 경우를 「△」, 100 ppm 이상이었던 경우를 「×」로 하여 아웃 가스 방지성을 평가하였다. As a result, when the amount of the vaporized component was less than 20 ppm as "○", the case where it was 20 ppm or more and less than 100 ppm was "△", and the case where it was 100 ppm or more as "x", outgassing prevention property was evaluated.
산업상 이용가능성Industrial applicability
본 발명에 의하면, 아웃 가스의 발생을 억제할 수 있고, 또한, 도포성이 우수한 유기 EL 표시 소자용 밀봉제를 제공할 수 있다. ADVANTAGE OF THE INVENTION According to this invention, generation|occurrence|production of outgas can be suppressed and the sealing agent for organic EL display elements excellent in coatability can be provided.
Claims (5)
상기 카티온 경화성 수지는 에폭시기 또는 옥세타닐기를 갖고, 또한, 에폭시기 또는 옥세타닐기에 함유되는 이외의 에테르 결합, 및 에스테르 결합을 갖지 않는 것이며,
상기 카티온 경화성 수지는 하기 식 (1) 로 나타내는 화합물 및 하기 식 (2) 로 나타내는 화합물을 함유하고,
E 형 점도계를 이용하여 25 ℃, 1 ∼ 100 rpm 의 조건에서 측정한 유기 EL 표시 소자용 밀봉제 전체의 점도가 80 ∼ 5000 mPa·s 인 것을 특징으로 하는 유기 EL 표시 소자용 밀봉제.
[화학식 1]
식 (1) 중, R1 ∼ R18 은 수소 원자, 할로겐 원자, 또는 산소 원자 혹은 할로겐 원자를 함유하고 있어도 되는 탄화수소기이고, 각각 동일하여도 되고, 상이하여도 된다.
[화학식 2]
식 (2) 중, R19 ∼ R21 은 직사슬형 또는 분기사슬형의 탄소수 2 ∼ 10 의 알킬렌기이고, 각각 동일하여도 되고, 상이하여도 된다. E1 ∼ E3 은 각각 독립적으로 하기 식 (3-1) 또는 하기 식 (3-2) 로 나타내는 유기기를 나타낸다.
[화학식 3]
식 (3-1) 중, R22 는 수소 원자 또는 메틸기이다.As a sealing agent for organic EL display elements containing a cation curable resin and a cation polymerization initiator,
The cation-curable resin has an epoxy group or an oxetanyl group, and does not have an ether bond and an ester bond other than contained in the epoxy group or oxetanyl group,
The cation-curable resin contains a compound represented by the following formula (1) and a compound represented by the following formula (2),
A sealing agent for an organic EL display device, characterized in that the viscosity of the entire sealing agent for an organic EL display device measured at 25°C and 1 to 100 rpm using an E-type viscometer is 80 to 5000 mPa·s.
[Formula 1]
In formula (1), R 1 to R 18 are a hydrogen atom, a halogen atom, or a hydrocarbon group which may contain an oxygen atom or a halogen atom, and may be the same or different.
[Formula 2]
In formula (2), R 19 to R 21 are linear or branched alkylene groups having 2 to 10 carbon atoms, and may be the same or different. Each of E 1 to E 3 independently represents an organic group represented by the following formula (3-1) or the following formula (3-2).
[Formula 3]
In formula (3-1), R 22 is a hydrogen atom or a methyl group.
식 (1) 로 나타내는 화합물로서 하기 식 (4) 로 나타내는 화합물을 함유하는 것을 특징으로 하는 유기 EL 표시 소자용 밀봉제.
[화학식 4]
A sealing agent for an organic EL display device, comprising a compound represented by the following formula (4) as a compound represented by formula (1).
[Formula 4]
식 (2) 로 나타내는 화합물로서 하기 식 (5) 로 나타내는 화합물을 함유하는 것을 특징으로 하는 유기 EL 표시 소자용 밀봉제.
[화학식 5]
A sealing agent for an organic EL display device, comprising a compound represented by the following formula (5) as a compound represented by formula (2).
[Formula 5]
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| CN107637168A (en) * | 2015-11-06 | 2018-01-26 | 积水化学工业株式会社 | Organic electro-luminescent display unit sealant |
| TWI715664B (en) * | 2015-11-10 | 2021-01-11 | 日商日產化學工業有限公司 | Long chain alkylene group-containing epoxy resin composition |
| JP7012424B2 (en) | 2016-03-25 | 2022-02-14 | 東京応化工業株式会社 | Energy-sensitive compositions, cured products and methods for producing cured products |
| WO2018074507A1 (en) * | 2016-10-19 | 2018-04-26 | 積水化学工業株式会社 | Organic el display element sealing agent, and method for producing organic el display element sealing agent |
| JP7010824B2 (en) * | 2017-06-07 | 2022-01-26 | 積水化学工業株式会社 | Encapsulant for organic EL display elements |
| WO2019004241A1 (en) * | 2017-06-28 | 2019-01-03 | 積水化学工業株式会社 | In-plane sealing agent for organic el display elements, and sealing agent set for organic el display elements |
| TWI688142B (en) * | 2017-09-01 | 2020-03-11 | 南韓商Ｌｇ化學股份有限公司 | Organic electronic device and method for preparing the same |
| CN111972046A (en) * | 2018-03-30 | 2020-11-20 | 积水化学工业株式会社 | Sealing agent for organic EL display element |
| JP2021527730A (en) * | 2018-06-12 | 2021-10-14 | エルジー・ケム・リミテッド | Sealing material composition |
| JP2021181504A (en) * | 2018-08-17 | 2021-11-25 | 日産化学株式会社 | Composition for moisture-proof seal material |
| KR20230021827A (en) * | 2021-08-06 | 2023-02-14 | (주)이녹스첨단소재 | Thermosetting liquid composition for an encapsulant of organic light emitting device |
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