CN113166371B - Sealing agent for organic EL display element - Google Patents
Sealing agent for organic EL display element Download PDFInfo
- Publication number
- CN113166371B CN113166371B CN202080006414.9A CN202080006414A CN113166371B CN 113166371 B CN113166371 B CN 113166371B CN 202080006414 A CN202080006414 A CN 202080006414A CN 113166371 B CN113166371 B CN 113166371B
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- China
- Prior art keywords
- organic
- display element
- sealant
- weight
- parts
- Prior art date
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- 238000007789 sealing Methods 0.000 title description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 98
- 239000000565 sealant Substances 0.000 claims abstract description 80
- 239000004593 Epoxy Substances 0.000 claims abstract description 57
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 38
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 37
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 21
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 20
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 20
- 150000001768 cations Chemical class 0.000 claims description 13
- FNYWFRSQRHGKJT-UHFFFAOYSA-N 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane Chemical compound C1OCC1(CC)COCC1(CC)COC1 FNYWFRSQRHGKJT-UHFFFAOYSA-N 0.000 claims description 5
- LFKLPJRVSHJZPL-UHFFFAOYSA-N 1,2:7,8-diepoxyoctane Chemical compound C1OC1CCCCC1CO1 LFKLPJRVSHJZPL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- USGYMDAUQBQWFU-UHFFFAOYSA-N 1,2,5,6-diepoxycyclooctane Chemical compound C1CC2OC2CCC2OC12 USGYMDAUQBQWFU-UHFFFAOYSA-N 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 15
- 238000010943 off-gassing Methods 0.000 abstract description 6
- -1 phenylene diglycidyl Chemical group 0.000 description 63
- 239000000758 substrate Substances 0.000 description 41
- 239000003795 chemical substances by application Substances 0.000 description 29
- 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 18
- 239000000463 material Substances 0.000 description 18
- 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 17
- 229920001187 thermosetting polymer Polymers 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003607 modifier Substances 0.000 description 10
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 229910010272 inorganic material Inorganic materials 0.000 description 8
- 239000011147 inorganic material Substances 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 238000002161 passivation Methods 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- UNOJSBGFGBDVGH-UHFFFAOYSA-N 1-cyclopenta-2,4-dien-1-ylidenepropan-2-ylbenzene Chemical compound C1(=CC=CC=C1)C(C)C=C1C=CC=C1 UNOJSBGFGBDVGH-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- LTYMSROWYAPPGB-UHFFFAOYSA-O diphenylsulfanium Chemical compound C=1C=CC=CC=1[SH+]C1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-O 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DOHVUQIYUWSVFX-UHFFFAOYSA-N 2-[4-[4-(2-hydroxyethoxy)phenyl]sulfanylphenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1SC1=CC=C(OCCO)C=C1 DOHVUQIYUWSVFX-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 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
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 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 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 2
- 239000012953 triphenylsulfonium Substances 0.000 description 2
- 229960000834 vinyl ether Drugs 0.000 description 2
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-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
- NQEJEMZJOBCYOD-UHFFFAOYSA-N (4-methoxyphenyl)methyl-dimethyl-phenylazanium Chemical compound C1=CC(OC)=CC=C1C[N+](C)(C)C1=CC=CC=C1 NQEJEMZJOBCYOD-UHFFFAOYSA-N 0.000 description 1
- QKAIFCSOWIMRJG-UHFFFAOYSA-N (4-methylphenyl)-(4-propan-2-ylphenyl)iodanium Chemical compound C1=CC(C(C)C)=CC=C1[I+]C1=CC=C(C)C=C1 QKAIFCSOWIMRJG-UHFFFAOYSA-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
- HIYIGPVBMDKPCR-UHFFFAOYSA-N 1,1-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1(COC=C)CCCCC1 HIYIGPVBMDKPCR-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 description 1
- FQJUJAALMJSTOI-UHFFFAOYSA-N 1-(1h-imidazol-2-yl)propylurea Chemical compound NC(=O)NC(CC)C1=NC=CN1 FQJUJAALMJSTOI-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-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
- OBSKXJSZGYXFFB-UHFFFAOYSA-N 1-benzylpyridin-1-ium-2-carbonitrile Chemical compound N#CC1=CC=CC=[N+]1CC1=CC=CC=C1 OBSKXJSZGYXFFB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- RQJCIXUNHZZFMB-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxypropoxy)propane Chemical compound C=COCC(C)OCC(C)OC=C RQJCIXUNHZZFMB-UHFFFAOYSA-N 0.000 description 1
- FOWNZLLMQHBVQT-UHFFFAOYSA-N 1-ethenoxy-2-[2-(2-ethenoxypropoxy)propoxy]propane Chemical compound C=COCC(C)OCC(C)OCC(C)OC=C FOWNZLLMQHBVQT-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-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
- MCBXLJCOMLRSQK-UHFFFAOYSA-N 2-(4-sulfanylphenoxy)ethanol Chemical compound OCCOC1=CC=C(S)C=C1 MCBXLJCOMLRSQK-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- RQZUWSJHFBOFPI-UHFFFAOYSA-N 2-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COCC1CO1 RQZUWSJHFBOFPI-UHFFFAOYSA-N 0.000 description 1
- FVCHRIQAIOHAIC-UHFFFAOYSA-N 2-[1-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COC(C)COCC1CO1 FVCHRIQAIOHAIC-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- 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
- VAXWRFJBZKAQFI-UHFFFAOYSA-N 3-[3-(3-hydrazinyl-3-oxopropyl)-2,4-dioxo-5-propan-2-ylimidazolidin-1-yl]propanehydrazide Chemical compound CC(C)C1N(CCC(=O)NN)C(=O)N(CCC(=O)NN)C1=O VAXWRFJBZKAQFI-UHFFFAOYSA-N 0.000 description 1
- BIDWUUDRRVHZLQ-UHFFFAOYSA-N 3-ethyl-3-(2-ethylhexoxymethyl)oxetane Chemical compound CCCCC(CC)COCC1(CC)COC1 BIDWUUDRRVHZLQ-UHFFFAOYSA-N 0.000 description 1
- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 1
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- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-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
- RRXFVFZYPPCDAW-UHFFFAOYSA-N 4-(7-oxabicyclo[4.1.0]heptan-4-ylmethoxymethyl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2OC2CC1COCC1CC2OC2CC1 RRXFVFZYPPCDAW-UHFFFAOYSA-N 0.000 description 1
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 1
- OXQXGKNECHBVMO-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound C1C(C(=O)O)CCC2OC21 OXQXGKNECHBVMO-UHFFFAOYSA-N 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- MOOIXEMFUKBQLJ-UHFFFAOYSA-N [1-(ethenoxymethyl)cyclohexyl]methanol Chemical compound C=COCC1(CO)CCCCC1 MOOIXEMFUKBQLJ-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
- 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
- 239000000654 additive Substances 0.000 description 1
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- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 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
- 150000001412 amines Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical compound N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- QNFNZVLBTGUIQY-UHFFFAOYSA-N bis(2,3,4,5,6-pentafluorophenoxy)borinic acid Chemical compound FC=1C(F)=C(F)C(F)=C(F)C=1OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F QNFNZVLBTGUIQY-UHFFFAOYSA-N 0.000 description 1
- AENNXXRRACDJAY-UHFFFAOYSA-N bis(2-dodecylphenyl)iodanium Chemical compound CCCCCCCCCCCCC1=CC=CC=C1[I+]C1=CC=CC=C1CCCCCCCCCCCC AENNXXRRACDJAY-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012663 cationic photopolymerization Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 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
- 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 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OWZDULOODZHVCQ-UHFFFAOYSA-N diphenyl-(4-phenylsulfanylphenyl)sulfanium Chemical compound C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC1=CC=CC=C1 OWZDULOODZHVCQ-UHFFFAOYSA-N 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- NPEWZDADCAZMNF-UHFFFAOYSA-N gold iron Chemical compound [Fe].[Au] NPEWZDADCAZMNF-UHFFFAOYSA-N 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
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BLGWXSOTAXXXDE-UHFFFAOYSA-N n'-[1-(1h-imidazol-2-yl)propyl]hexanediamide Chemical compound NC(=O)CCCCC(=O)NC(CC)C1=NC=CN1 BLGWXSOTAXXXDE-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 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
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 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
- GAMLUOSQYHLFCT-UHFFFAOYSA-N triethoxy-[3-[(3-ethyloxetan-3-yl)methoxy]propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1(CC)COC1 GAMLUOSQYHLFCT-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000005591 trimellitate group Chemical group 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
- ULNJZOIDTANZKR-UHFFFAOYSA-N tris[4-(4-acetylphenyl)sulfanylphenyl]sulfanium Chemical compound C1=CC(C(=O)C)=CC=C1SC1=CC=C([S+](C=2C=CC(SC=3C=CC(=CC=3)C(C)=O)=CC=2)C=2C=CC(SC=3C=CC(=CC=3)C(C)=O)=CC=2)C=C1 ULNJZOIDTANZKR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
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
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
-
- 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
-
- 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
- C08G59/22—Di-epoxy compounds
-
- 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
- C08G59/68—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 catalysts used
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
Abstract
The purpose of the present invention is to provide a sealant for an organic EL display element, which has excellent low outgassing properties and coatability, and which can provide an organic EL display element having excellent light extraction efficiency. The sealant for an organic EL display element of the present invention contains a cation-polymerizable compound and a cation-polymerization initiator, wherein the cation-polymerizable compound contains a cycloolefin oxide-type alicyclic epoxy compound and a fluorene-type epoxy compound.
Description
Technical Field
The present invention relates to a sealant for an organic EL display element, which has excellent low outgassing and coatability and can provide an organic EL display element having excellent light extraction efficiency.
Background
An organic electroluminescent (hereinafter also referred to as "organic EL") display element has a laminate structure in which an organic light-emitting material layer is sandwiched between a pair of electrodes that face each other, and electrons are injected from one electrode into the organic light-emitting material layer, and holes are injected from the other electrode into the organic light-emitting material layer, whereby the electrons and holes combine in the organic light-emitting material layer to emit light. In this way, the organic EL display element emits light, and therefore has advantages in that it is excellent in visibility, can be made thinner, and can be driven at a low dc voltage, as compared with a liquid crystal display element or the like that requires a backlight.
The organic light-emitting material layers and electrodes constituting the organic EL display element have a problem that their characteristics are easily deteriorated by moisture, oxygen, or the like. Therefore, in order to obtain a practical organic EL display element, it is necessary to isolate the organic light-emitting material layer and the electrode from the atmosphere to achieve a long lifetime. As a method of isolating the organic light-emitting material layer and the electrode from the atmosphere, sealing the organic EL display element with a sealant is performed (for example, patent document 1). In sealing an organic EL display element with a sealant, in general, in order to sufficiently suppress the transmission of moisture, oxygen, or the like, a method is used in which an inorganic material film called a passivation film is provided on a laminate having an organic light-emitting material layer, and the inorganic material film is sealed with the sealant.
In recent years, instead of a bottom emission type organic EL display element in which light emitted from an organic light emitting material layer is extracted from a substrate surface side where a light emitting element is formed, a top emission type organic EL display element in which light is extracted from an upper surface side of an organic light emitting layer has been attracting attention. This mode has an advantage of being advantageous in that the aperture ratio (Japanese: open ratio) is high and the low-voltage drive is achieved, and thus the lifetime is advantageously prolonged. In such a top emission type organic EL display element, since the upper surface side of the light emitting layer needs to be transparent, sealing is performed by laminating a transparent moisture-proof substrate such as glass on the upper surface side of the light emitting element with a transparent sealing layer interposed therebetween (for example, patent document 2). However, in the case of a top emission type organic EL display element, even when a material having sufficiently high transparency is used as a transparent moisture-proof substrate or a sealant, there is a problem in that: due to the difference in refractive index between the electrode, the passivation film, and the sealant, the extraction efficiency of light emitted from the laminate may be deteriorated. In addition, the conventional sealant has problems such as deterioration of the element due to outgas, and poor coatability.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2007-115692
Patent document 2: japanese patent laid-open No. 2009-051980
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a sealant for an organic EL display element, which has excellent low outgassing properties and coatability, and which can provide an organic EL display element having excellent light extraction efficiency.
Means for solving the problems
The present invention provides a sealant for an organic EL display element, which contains a cation-polymerizable compound and a cation-polymerization initiator, wherein the cation-polymerizable compound contains a cycloolefin oxide-type alicyclic epoxy compound and a fluorene-type epoxy compound.
The present invention is described in detail below.
The present inventors studied: the use of a cycloolefin oxide type alicyclic epoxy compound as a cationically polymerizable compound in a sealant for an organic EL display element improves coatability and prevents outgas. However, the sealant using such a cycloolefin oxide type alicyclic epoxy compound has an excellent effect of preventing generation of outgas, but has a large refractive index difference from the electrode and the passivation film, and therefore has a problem in that light extraction efficiency is lowered due to reflection at the interface between the electrode, the passivation film and the sealant. Accordingly, the present inventors studied the use of the cycloolefin oxide type alicyclic epoxy compound and the fluorene type epoxy compound in combination as a cationically polymerizable compound. As a result, it has been found that a sealant for an organic EL display element which has low outgas and excellent coatability and can give an organic EL display element having excellent light extraction efficiency can be obtained, and the present invention has been completed.
The sealant for an organic EL display element of the present invention contains a cationically polymerizable compound.
The cation polymerizable compound contains a cycloolefin oxide type alicyclic epoxy compound. The sealing agent for an organic EL display element of the present invention is excellent in low outgas and coatability by containing the cycloolefin oxide type alicyclic epoxy compound.
Examples of the alicyclic epoxy compound include 3',4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate and bis (3, 4-epoxycyclohexylmethyl) ether.
Examples of the commercially available cycloolefin oxide type alicyclic epoxy compound include Celloxide 2021P (manufactured by Daicel Co., ltd.).
The content of the cycloolefin oxide type alicyclic epoxy compound in 100 parts by weight of the whole of the cationically polymerizable compound is preferably 10 parts by weight, more preferably 90 parts by weight. When the content of the cycloolefin oxide type alicyclic epoxy compound is 10 parts by weight or more, the obtained sealing agent for an organic EL display element is further excellent in low outgas and coatability. The content of the cycloolefin oxide type alicyclic epoxy compound is 90 parts by weight or less, whereby the light extraction efficiency of the obtained organic EL display element is further improved. The content of the cycloolefin oxide type alicyclic epoxy compound is more preferably 15 parts by weight, still more preferably 70 parts by weight, still more preferably 20 parts by weight, still more preferably 65 parts by weight, and particularly preferably 60 parts by weight.
The cation polymerizable compound contains a fluorene type epoxy compound. The fluorene-type epoxy compound is contained, so that the difference in refractive index between the sealing agent for an organic EL display element of the present invention and the electrode or passivation film is small, and as a result, the obtained organic EL display element has excellent light extraction efficiency.
The fluorene-type epoxy compound may be any epoxy compound having a fluorene skeleton, and various fluorene-type epoxy compounds may be appropriately selected from the viewpoints of viscosity, refractive index, photocurability, and the like.
The fluorene-type epoxy compound has a preferable lower limit of 200 and a preferable upper limit of 400 in terms of epoxy equivalent. When the epoxy equivalent of the fluorene-type epoxy compound is in this range, the resulting sealant for an organic EL display element is more excellent in adhesion, low outgas and coatability.
In the present specification, the epoxy equivalent of the fluorene-type epoxy compound means (molecular weight of the fluorene-type epoxy compound)/(number of epoxy groups in the molecule of the fluorene-type epoxy compound 1).
Examples of commercial products of the fluorene-type epoxy compounds include fluorene-type epoxy compounds manufactured by Xinshi ChemteX, fluorene-type epoxy compounds manufactured by Nagase ChemteX, and fluorene-type epoxy compounds manufactured by Osaka Gas Chemicals.
As the fluorene type epoxy compound manufactured by Nippon iron gold chemical Co., ltd., for example, ESF-300 and the like are mentioned.
As the fluorene-based epoxy compound manufactured by Nagase ChemteX, for example, oncoat EX-1010 and the like are mentioned.
Examples of the fluorene-containing epoxy compound manufactured by Osaka Gas Chemicals include OGSOL PG-100 and EG-200.
These fluorene-type epoxy compounds may be used alone or in combination of 2 or more.
The content of the fluorene-type epoxy compound in 100 parts by weight of the entire cationically polymerizable compound is preferably 10 parts by weight, and the upper limit is preferably 80 parts by weight. By setting the content of the fluorene-type epoxy compound to 10 parts by weight or more, the light extraction efficiency of the obtained organic EL display element becomes more excellent. When the content of the fluorene-type epoxy compound is 80 parts by weight or less, the obtained sealant for an organic EL display element is further excellent in low outgas and coatability. The content of the fluorene-type epoxy compound is more preferably 15 parts by weight, still more preferably 75 parts by weight, still more preferably 20 parts by weight, and still more preferably 70 parts by weight. In addition, from the viewpoint of further improving the light extraction efficiency of the obtained organic EL display element, the preferable lower limit of the content of the fluorene-type epoxy compound is 30 parts by weight, the more preferable lower limit is 35 parts by weight, and the more preferable lower limit is 40 parts by weight.
The cation polymerizable compound may contain other cation polymerizable compounds in addition to the cycloolefin oxide type alicyclic epoxy compound and the fluorene type epoxy compound.
Examples of the other cationically polymerizable compound include epoxy compounds other than the cycloolefin oxide type alicyclic epoxy compound and the fluorene type epoxy compound, oxetane compounds, vinyl ether compounds, and the like.
Examples of the other epoxy compounds include 1, 7-octadiene diepoxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, phenyl glycidyl ether, and phenylene diglycidyl ether.
Examples of the oxetane compound include 3-ethyl-3- (((3-ethyloxetan-3-yl) methoxy) methyl) oxetane, 3-ethyl-3- ((2-ethylhexyl oxy) methyl) oxetane, 3-ethyl-3- ((3- (triethoxysilyl) propoxy) methyl) oxetane, phenol novolac oxetane, and 1, 4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene.
Examples of the vinyl ether compound include benzyl vinyl ether, cyclohexanedimethanol monovinyl ether, dicyclopentadiene vinyl ether, 1, 4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol divinyl ether, and tripropylene glycol divinyl ether.
Among them, the other cationically polymerizable compound is preferably selected from 3-ethyl-3- (((3-ethyloxetan-3-yl) methoxy) methyl) oxetan and 1,2:7, 8-Diepoxyoctane and 1,2: at least 1 of 5, 6-diepoxycyclooctane, more preferably 3-ethyl-3- (((3-ethyloxetan-3-yl) methoxy) methyl) oxetane.
When the cation polymerizable compound contains the other cation polymerizable compound, the content of the other cation polymerizable compound in 100 parts by weight of the cation polymerizable compound is preferably 10 parts by weight, and the upper limit is preferably 50 parts by weight. When the content of the other cationically polymerizable compound is in this range, the resulting sealant for an organic EL display element is more excellent in adhesion and coatability. The more preferable upper limit of the content of the other cationically polymerizable compound is 45 parts by weight, and the more preferable upper limit is 40 parts by weight.
In the case where the cation polymerizable compound includes the other cation polymerizable compound, the preferable lower limit of the total content of the cycloolefin oxide type alicyclic epoxy compound and the other cation polymerizable compound in 100 parts by weight of the cation polymerizable compound is 20 parts by weight. The total content of the cycloolefin oxide type alicyclic epoxy compound and the other cationically polymerizable compound is 20 parts by weight or more, whereby the obtained sealant for an organic EL display element is further excellent in coatability. The total content of the cycloolefin oxide type alicyclic epoxy compound and the other cationically polymerizable compound is more preferably 30 parts by weight, and still more preferably 40 parts by weight.
The sealant for an organic EL display element of the present invention contains a cationic polymerization initiator.
Examples of the cationic polymerization initiator include a thermal cationic polymerization initiator and a photo cationic polymerization initiator.
Examples of the thermal cationic polymerization initiator include: the anionic part being formed by BF 4 - 、PF 6 - 、SbF 6 - Or (BX) 4 ) - (wherein X represents a phenyl group substituted with at least 2 or more fluorine groups or trifluoromethyl groups), a sulfonium salt, a phosphonium salt, an ammonium salt, a diazonium salt, an iodonium salt, or the like. Among them, sulfonium salts are preferable.
Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate and triphenylsulfonium hexafluoroantimonate.
Examples of the phosphonium salts include ethyltriphenyl phosphonium hexafluoroantimonate and tetrabutyl phosphonium hexafluoroantimonate.
Examples of the ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyl dibenzylammonium hexafluorophosphate, methylphenyl dibenzylammonium hexafluoroantimonate, methylphenyl dibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzyl ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3, 4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N-dimethyl-N-benzylanilinium hexafluoroantimonate, N-diethyl-N-benzylanilinium tetrafluoroborate, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N-diethylpyridinium triflate, and the like.
Examples of the commercial products of the thermal cationic polymerization initiator include thermal cationic polymerization initiators manufactured by Sanxinhua chemical Industries, thermal cationic polymerization initiators manufactured by King Industries, and the like.
Examples of the thermal cationic polymerization initiator manufactured by the Sanxinafoate chemical industry Co., ltd include San-air SI-60, san-air SI-80, san-air SI-B3A, san-air SI-B4, and the like.
Examples of the thermal cationic polymerization initiator manufactured by King Industries include CXC-1612 and CXC-1821.
The photo-cation polymerization initiator is not particularly limited as long as it is a polymerization initiator that generates a protonic acid or a lewis acid by irradiation with light, and may be an ionic photo-acid generator or a nonionic photo-acid generator.
Examples of the anionic moiety of the above-mentioned ionic photoacid-generating type photo-cationic polymerization initiator include BF 4 - 、PF 6 - 、SbF 6 - 、(BX 4 ) - (wherein X represents a phenyl group substituted with at least 2 or more fluorine groups or trifluoromethyl groups). Further, as the above-mentioned anionic moiety, PF can be also mentioned m (C n F 2n+1 ) 6-m - (wherein, m is an integer of 0 to 5, and n is an integer of 1 to 6), and the like.
Examples of the above-mentioned cationic photopolymerization initiator capable of producing an ionic photoacid include: aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salts, and the like having the above anionic moiety.
Examples of the aromatic sulfonium salt include bis (4- (diphenylsulfonium) phenyl) sulfide bis hexafluorophosphate, bis (4- (diphenylsulfonium) phenyl) sulfide bis hexafluoroantimonate, bis (4- (diphenylsulfonium) phenyl) sulfide bis tetrafluoroborate, bis (4- (diphenylsulfonium) phenyl) sulfide bis (pentafluorophenyl) borate, diphenyl-4- (phenylsulfanyl) phenyl sulfonium hexafluorophosphate, diphenyl-4- (phenylsulfanyl) phenyl sulfonium hexafluoroantimonate, diphenyl-4- (phenylsulfanyl) phenyl sulfonium tetrafluoroborate, diphenyl-4- (phenylsulfanyl) phenyl sulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis (4- (2-hydroxyethoxy) phenyl) sulfide bis hexafluorophosphate, bis (4- (2-hydroxyethoxy) phenyl) sulfide bis hexafluoroantimonate, bis (4- (2-hydroxyethoxy) phenyl) sulfonium bis (4-hydroxyethoxy) phenyl) sulfide bis (4-phenylsulfonium) tetrafluoroborate), bis (4- (2-hydroxyethoxy)) phenylsulfonium) phenyl) sulfide tetrakis (pentafluorophenyl) borate, tris (4- (4-acetylphenyl) thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate, and the like. Among them, triarylsulfonium tetrakis (pentafluorophenyl) borate such as triphenylsulfonium tetrakis (pentafluorophenyl) borate is preferable.
Examples of the aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) 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 hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, and 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate.
Examples of the aromatic diazonium salt include phenyl diazonium hexafluorophosphate, phenyl diazonium hexafluoroantimonate, phenyl diazonium tetrafluoroborate, and phenyl diazonium tetrakis (pentafluorophenyl) borate.
Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
Examples of the (2, 4-cyclopentadienyl-1-yl) ((1-methylethyl) benzene) -Fe salt include (2, 4-cyclopentadienyl-1-yl) ((1-methylethyl) benzene) -Fe (II) hexafluorophosphate, (2, 4-cyclopentadienyl-1-yl) ((1-methylethyl) benzene) -Fe (II) hexafluoroantimonate, (2, 4-cyclopentadienyl-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrafluoroborate, and (2, 4-cyclopentadienyl-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrakis (pentafluorophenyl) borate.
Examples of the photo-cation polymerization initiator of the nonionic photoacid generator include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, and N-hydroxyimide sulfonic acid ester.
Examples of the commercial products of the photo-cationic polymerization initiator include photo-cationic polymerization initiators made by Midori chemical company, photo-cationic polymerization initiators made by Union Carbide company, photo-cationic polymerization initiators made by ADEKA company, photo-cationic polymerization initiators made by 3M company, photo-cationic polymerization initiators made by BASF company, photo-cationic polymerization initiators made by Solvay company, and photo-cationic polymerization initiators made by San-Apro company.
As the photo cation polymerization initiator manufactured by Midori chemical Co., ltd, DTS-200 and the like can be mentioned, for example.
Examples of the photo-cation polymerization initiator manufactured by Union Carbide include UVI6990 and UVI 6974.
Examples of the photo-cation polymerization initiator manufactured by ADEKA corporation include SP-150 and SP-170.
Examples of the photo-cation polymerization initiator manufactured by 3M company include FC-508 and FC-512.
Examples of the photo-cation polymerization initiator manufactured by BASF include IRGACURE261 and IRGACURE 290.
Examples of the photo-cation polymerization initiator manufactured by Solvay include PI 2074.
As the photo-cation polymerization initiator, for example, CPI-100P, CPI-200K, CPI-210S, manufactured by San-Apro Co.
Among the cationic polymerization initiators, quaternary ammonium salts (hereinafter, also referred to as "borate quaternary ammonium salts") whose counter anions are borate-based (Japanese-24-system) are preferably used.
The counter anion of the borate quaternary ammonium salt is preferably BF 4 - Or (BX) 4 ) - (wherein X represents a phenyl group substituted with at least 2 or more fluorine groups or trifluoromethyl groups).
The content of the cationic polymerization initiator is preferably limited to 0.05 parts by weight, and the content is preferably limited to 10 parts by weight, based on 100 parts by weight of the cationic polymerizable compound. When the content of the cationic polymerization initiator is within this range, the obtained sealant for an organic EL display element is further excellent in curability, storage stability, and moisture resistance of the cured product. The lower limit of the content of the cationic polymerization initiator is more preferably 0.1 part by weight, and the upper limit is more preferably 5 parts by weight.
The sealant for an organic EL display element of the present invention may contain a thermosetting agent.
Examples of the thermosetting agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamide, guanidine derivatives, modified aliphatic polyamines, and addition products of various amines and epoxy resins.
Examples of the hydrazide compound include 1, 3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
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 '-bis (2-methyl-1-imidazolylethyl) urea, N' - (2-methyl-1-imidazolylethyl) -adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4, 5-dihydroxymethylimidazole.
Examples of the acid anhydride include tetrahydrophthalic anhydride and ethylene glycol bis (dehydrated trimellitate).
These thermosetting agents may be used alone or in combination of 2 or more.
Examples of the commercial products of the thermosetting agent include thermosetting agents manufactured by Severe chemical company and thermosetting agents manufactured by Ajinomoto Fine-Techno company.
Examples of the thermosetting agent manufactured by the above-mentioned chemical company include SDH and ADH.
Examples of the thermosetting agent manufactured by Ajinomoto Fine-Techno Co., ltd include AMICURE VDH, AMICURE VDH-J, and AMICURE UDH.
The content of the thermosetting agent is preferably limited to 0.5 parts by weight, and the content is preferably limited to 30 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. When the content of the thermosetting agent is 0.5 parts by weight or more, the thermosetting property of the obtained sealing agent for an organic EL display element becomes more excellent. When the content of the thermosetting agent is 30 parts by weight or less, the resulting sealant for an organic EL display element is more excellent in storage stability and the cured product is more excellent in moisture resistance. The more preferable lower limit of the content of the above-mentioned thermosetting agent is 1 part by weight, and the more preferable upper limit is 15 parts by weight.
The sealant for an organic EL display element of the present invention preferably contains a stabilizer. By containing the stabilizer, the sealing agent for an organic EL display element of the present invention is more excellent in storage stability.
As the stabilizer, an aromatic amine compound is preferably used.
Examples of the aromatic amine compound include benzylamine and aminophenol type epoxy resins.
Examples of the aminophenol type epoxy resin include triglycidyl-p-aminophenol.
Among them, benzylamine is preferable.
These stabilizers may be used alone or in combination of 2 or more.
The content of the stabilizer is preferably limited to 0.001 parts by weight, and the content of the stabilizer is preferably limited to 2 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. When the content of the stabilizer is within this range, the obtained sealant for an organic EL display element has more excellent storage stability while maintaining excellent curability. The more preferable lower limit of the content of the above stabilizer is 0.005 parts by weight, and the more preferable upper limit is 1 part by weight.
The sealant for an organic EL display element of the present invention may contain a silane coupling agent. The silane coupling agent has an effect of improving the adhesion between the sealing agent for an organic EL display element of the present invention and a substrate or the like.
Examples of the silane coupling agent include 3-aminopropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, and 3-isocyanatopropyl trimethoxysilane. These silane coupling agents may be used alone or in combination of 2 or more.
The content of the silane coupling agent is preferably limited to 0.1 part by weight, and the content is preferably limited to 10 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. When the content of the silane coupling agent is within this range, the remaining silane coupling agent is prevented from bleeding out, and the effect of improving the adhesion is further improved. The more preferable lower limit of the content of the above silane coupling agent is 0.5 parts by weight, and the more preferable upper limit is 5 parts by weight.
From the viewpoint of low outgassing, the preferable upper limit of the content of the silane coupling agent is 0.5 parts by weight, more preferably 0.1 parts by weight, and still more preferably 0.01 parts by weight, based on 100 parts by weight of the cationically polymerizable compound.
The sealant for an organic EL display element of the present invention may further contain a surface modifier within a range that does not hinder the object of the present invention. By containing the surface modifier, the flatness of the coating film of the sealing agent for an organic EL display element of the present invention can be improved.
Examples of the surface modifier include a surfactant and a leveling agent.
Examples of the surface modifier include silicone-based, acrylic-based, and fluorine-based surface modifiers.
Examples of the commercial products of the surface modifier include a surface modifier manufactured by BYK-Chemie Japan, a surface modifier manufactured by AGC SEIMI CHEMICAL, and the like.
Examples of the surface modifier manufactured by BYK-Chemie Japan include BYK-330, BYK-340 and BYK-345.
Examples of the surface modifier manufactured by AGC SEIMI CHEMICAL include Surflon S-611.
In order to improve the durability of the element electrode, the sealing agent for an organic EL display element of the present invention may contain a compound or an ion exchange resin that reacts with an acid generated in the sealing agent for an organic EL display element within a range that does not hinder the object of the present invention.
Examples of the compound that reacts with the acid produced above include a substance that neutralizes the acid, such as an alkali metal carbonate or bicarbonate, or an alkaline earth metal carbonate or bicarbonate. Specifically, for example, calcium carbonate, calcium bicarbonate, sodium carbonate, sodium bicarbonate, and the like are used.
As the ion exchange resin, any of a cation exchange type, an anion exchange type, and a zwitterionic exchange type can be used, but a cation exchange type or a zwitterionic exchange type capable of adsorbing chloride ions is particularly preferable.
The sealant for an organic EL display element of the present invention may contain a solvent for the purpose of adjusting viscosity or the like, but since the residual solvent may cause problems such as degradation of the organic light-emitting material layer or outgas, it is preferable that the solvent is not contained or the content of the solvent is 0.05 wt% or less.
The sealant for an organic EL display element of the present invention may contain various known additives such as a curing retarder, a reinforcing agent, a softener, a plasticizer, a viscosity modifier, an ultraviolet absorber, and an antioxidant, if necessary.
The preferable upper limit of the viscosity of the sealant for an organic EL display element of the present invention measured using an E-type viscometer at 25℃and 2.5rpm is 250 Pa.s. When the viscosity is 250pa·s or less, the obtained sealant for an organic EL display element is excellent in coatability. The preferable upper limit of the viscosity is 100pa·s, and the more preferable upper limit is 10pa·s.
The preferable lower limit of the viscosity is 5 mPas.
The viscosity can be measured using a cone plate of CP1 using, for example, VISCOMETER TV-22 (manufactured by east machine industry Co., ltd.) as an E-type VISCOMETER.
The lower limit of the refractive index of the sodium D-line at 25 ℃ of the cured product of the sealant for an organic EL display element of the present invention is preferably 1.55. When the refractive index is in this range, the refractive index difference between the electrode and the passivation film becomes small, and as a result, the light extraction efficiency of the obtained organic EL display element becomes excellent. The lower limit of the refractive index is more preferably 1.56.
The "refractive index of sodium D line" can be measured using an abbe refractometer.
Further, as a cured product for measuring the refractive index, for example, a measuring sheet having a length of 20mm, a width of 10mm, and a thickness of about 0.5 to 1mm can be used. The cured product for measuring the refractive index can be obtained by heating at 100℃for 30 minutes in the case of a thermosetting sealant, or by irradiating 2000mJ/cm in the case of a photo-thermosetting sealant 2 About ultraviolet rays were then heated at 100℃for 30 minutes.
The sealant for an organic EL display element of the present invention is particularly suitable as an in-plane sealant for sealing a laminate having an organic light-emitting material layer by coating.
The sealant for organic EL display element of the present invention is suitable for sealing top-emission organic EL display elements.
As a method for sealing an organic EL display element using the sealant for an organic EL display element of the present invention, for example, a method having the following steps: a step of applying the sealant for an organic EL display element of the present invention to a substrate by printing, dispensing, ink-jet method, or the like on the surface of the substrate; and curing the applied sealant for the organic EL display element by heating and/or light irradiation.
In the step of applying the sealant for an organic EL display element of the present invention to a substrate, the sealant for an organic EL display element of the present invention may be applied to the entire surface of the substrate or to a part of the substrate. The shape of the sealing portion of the sealing agent for an organic EL display element of the present invention formed by coating is not particularly limited as long as it is a shape capable of protecting the laminate having the organic light-emitting material layer from the outside air, and may be a shape entirely covering the laminate, may be a shape in which a closed pattern is formed in the peripheral portion of the laminate, or may be a shape in which an opening is partially provided in the peripheral portion of the laminate.
In the case of curing the sealant for an organic EL display element by heating, it is preferable to heat at 50 ℃ or higher and 120 ℃ or lower from the viewpoint of reducing damage to the laminate having the organic light-emitting material layer and sufficiently curing the laminate.
When the sealant for an organic EL display element of the present invention is cured by light irradiation, the sealant for an organic EL display element of the present invention can be cured by irradiation with a wavelength of 300nm or more and 400nm or less and 300mJ/cm 2 Above and 3000mJ/cm 2 The light of the accumulated light quantity below is appropriately cured.
Examples of the light source used for the irradiation of the light include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, an LED lamp, a fluorescent lamp, sunlight, and an electron beam irradiation device. These light sources may be used alone or in combination of 2 or more.
These light sources may be appropriately selected according to the absorption wavelength of the above-mentioned photo-cationic polymerization initiator.
Examples of the irradiation means of light for the sealant for an organic EL display element according to the present invention include simultaneous irradiation with various light sources, sequential irradiation with a time difference, and combined irradiation of simultaneous irradiation and sequential irradiation, and any irradiation means may be used.
The cured product obtained by the step of curing the sealant for an organic EL display element by heating and/or light irradiation may be further covered with an inorganic material film.
As the inorganic material constituting the inorganic material film, conventionally known inorganic materials can be used, and examples thereof include silicon nitride (SiN x ) Silicon oxide (SiO) x ) Etc. The inorganic material film may be composed of 1 layer, or may be composed of a plurality of layers stacked. The laminate may be coated by alternately and repeatedly laminating the inorganic material film and the resin film containing the sealing agent for an organic EL display element of the present invention.
The method of manufacturing the above-described organic EL display element may have: and a step of bonding a substrate (hereinafter, also referred to as "one substrate") coated with the sealant for an organic EL display element of the present invention to another substrate.
The substrate (hereinafter, also referred to as "one substrate") to which the sealant for an organic EL display element of the present invention is applied may be a substrate on which a laminate having an organic light-emitting material layer is formed, or may be a substrate on which the laminate is not formed.
When the one substrate is a substrate on which the laminate is not formed, the sealant for an organic EL display element of the present invention may be applied to the one substrate so as to protect the laminate from the outside air when the other substrate is attached. That is, the part to be the position of the laminate when the other substrate is bonded may be entirely coated, or the sealing agent part of the closed pattern may be formed in a shape in which the part to be the position of the laminate when the other substrate is bonded is completely incorporated.
As a method of sealing the organic EL display element, a so-called dam-fill (japanese) sealing method may be used. That is, first, a curable paste is applied to the substrate of the organic EL display element so as to surround the periphery of the display portion. Next, the sealant for an organic EL display element of the present invention is applied to the inner side of the applied curable paste, and the opposed sealing substrates are bonded while preventing the overflow of the sealant by the curable paste at the periphery. Then, a method of curing the curable paste at the periphery and the sealant for an organic EL display element of the present invention which is extruded and spread to the inside by heating and/or light irradiation can be used.
The step of curing the sealant for an organic EL display element by heating and/or light irradiation may be performed before the step of bonding the one substrate to the other substrate, or may be performed after the step of bonding the one substrate to the other substrate.
In the case where the step of curing the organic EL display element sealing agent by heating and/or light irradiation is performed before the step of bonding the one substrate to the other substrate, the sealing agent for an organic EL display element of the present invention preferably has a usable time of 1 minute or more from the time of heating and/or light irradiation until the curing reaction proceeds and adhesion is not allowed. By setting the usable time to 1 minute or longer, curing does not excessively proceed before the one base material and the other base material are bonded, and thus a higher adhesive strength can be obtained.
In the step of bonding the one substrate to the other substrate, a method of bonding the one substrate to the other substrate is not particularly limited, and bonding under a reduced pressure atmosphere is preferable.
The preferable lower limit of the vacuum degree in the reduced pressure atmosphere is 0.01kPa, and the preferable upper limit is 10kPa. By setting the vacuum degree in the reduced pressure atmosphere to this range, the bubbles in the sealant for an organic EL display element of the present invention when the one substrate and the other substrate are bonded can be removed more efficiently without taking a long time from the viewpoint of the air tightness of the vacuum apparatus and the capability of the vacuum pump.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a sealant for an organic EL display element, which has excellent low outgassing and coatability and can provide an organic EL display element having excellent light extraction efficiency, can be provided.
Detailed Description
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Examples 1 to 14 and comparative examples 1 to 3
The organic EL display element sealants of examples 1 to 14 and comparative examples 1 to 3 were prepared by stirring and mixing the materials at a stirring speed of 2000rpm using a stirrer mixer according to the blending ratios shown in tables 1 to 3. AR-250 (manufactured by THINKY Co.) was used as the stirring mixer.
< evaluation >
The sealants for organic EL display elements obtained in examples and comparative examples were evaluated as follows. The results are shown in tables 1 to 3.
(1) Viscosity of the mixture
The viscosities of the sealants for organic EL display elements obtained in examples and comparative examples were measured at 25℃and 2.5rpm using an E-type viscometer. As the E-type VISCOMETER, VISCOMETER TV-22 (manufactured by Dong machine industries Co., ltd.) was used.
The sealant for an organic EL display element obtained in comparative example 2 was solid at 25 ℃, and thus the viscosity could not be measured.
(2) Storage stability
For each of the sealants for organic EL display elements obtained in examples and comparative examples, the initial viscosity immediately after production and the viscosity after storage at 25 ℃ for 1 week were measured using an E-type viscometer, and (viscosity after storage at 25 ℃ for 1 week)/(initial viscosity) was derived as the viscosity change rate. As the E-type VISCOMETER, VISCOMETER TV-22 (manufactured by Dong machine industries Co., ltd.) was used.
The case where the viscosity change rate was less than 1.2 was designated as "verygood", the case where 1.2 or more and less than 1.5 was designated as "good", the case where 1.5 or more and less than 2.0 was designated as "delta", and the case where 2.0 or more was designated as "×", and the storage stability was evaluated.
Since the sealant for an organic EL display element obtained in comparative example 2 was solid at 25 ℃, the storage stability could not be evaluated.
(3) Coatability of coating
For 100 parts by weight of each of the organic EL display element sealants obtained in examples and comparative examples, 0.3 parts by weight of polymer beads having an average particle diameter of 10 μm was added and uniformly dispersed by a planetary stirring apparatus. As polymer beads, micropearl SP (manufactured by water chemical industry Co., ltd.) was used. 2 glass substrates having a length of 5cm and a width of 5cm were prepared, and 0.1mL of the resulting dispersion was placed on the center of one glass substrate, and the other glass substrate was stacked. A weight of 100g was placed on the other glass substrate, the sealant was extruded and spread, the weight was removed after being placed on a hot plate at 60℃for 10 minutes, and the diameter of the wet spread between the glass substrates was measured.
The coating property was evaluated by marking the diameter of 30mm or more as "excellent", 25mm or more and less than 30mm as "good", 20mm or more and less than 25mm as "delta", and less than 20mm as "X".
(4) Curability of
The epoxy group reaction rate (the reduction rate of the peak derived from the epoxy group) when the organic EL display element sealants obtained in examples and comparative examples were cured by heating at 100 ℃ for 30 minutes was measured using an infrared spectroscopic apparatus. The sealant for an organic EL display element obtained in example 13 was irradiated with UV-LED at 1500mJ/cm 2 After ultraviolet rays having a wavelength of 365nm, they were cured by heating at 90℃for 30 minutes. UMA600 (Agilent Technologies Co., ltd.) was used as the infrared spectroscopic deviceAnd (5) manufacturing).
The epoxy group reaction rate was "very good", 80% or more and less than 90% was "o", 60% or more and less than 80% was "Δ", and less than 60% was "x", and curability was evaluated.
(5) Refractive index and light extraction efficiency
A silicone rubber sheet having a thickness of 1mm was cut into a rectangle having a length of 20mm and a width of 10mm to prepare a mold. The mold was placed on a release PET film, and after filling the mold with the sealing agent for organic EL display elements obtained in examples and comparative examples, another 1 piece of release PET film was covered so as not to leave air bubbles, thereby obtaining a laminate. The obtained laminate was sandwiched between 2 glass plates and fixed, and the sealant was cured by heating in an oven at 100℃for 30 minutes, and then the PET film was peeled off, and the cured product of the sealant was taken out of the silicone rubber sheet to obtain test pieces having a length of 10mm, a width of 20mm and a thickness of 1 mm. The sealant for an organic EL display element obtained in example 13 was irradiated with ultraviolet light of 365nm wavelength at 1500mJ/cm using a UV-LED 2 After that, it was cured by heating at 90℃for 30 minutes. The refractive index of the sodium D line at 25 ℃ was measured on the obtained test piece using an abbe refractometer. NAR-4T (manufactured by ATAGO Co., ltd.) was used as the Abbe type refractometer.
In consideration of the refractive index difference between the electrode and the passivation film, the refractive index was "o" when 1.55 or more, the refractive index was "Δ" when 1.53 or more and less than 1.55, and the refractive index was "x" when less than 1.53, and the light extraction efficiency was evaluated.
(6) Low outgassing
The organic EL display element sealants obtained in examples and comparative examples were sealed in vials at a dose of 300mg and then heated at 100 ℃ for 30 minutes to cure the sealants. The sealant for an organic EL display element obtained in example 13 was irradiated with ultraviolet light of 365nm wavelength at 1500mJ/cm using a UV-LED 2 After that, it was cured by heating at 90℃for 30 minutes. In addition, the vials were added in a constant temperature oven at 85 DEG CThe vial was heated for 100 hours and the amount of vaporized components in the vial was measured using a gas chromatograph mass spectrometer. JMS-Q1050 (manufactured by Japanese electronics Co., ltd.) was used as a gas chromatograph mass spectrometer.
The amount of the gasifying component was "O" when it was less than 50ppm, the amount of the gasifying component was "delta" when it was not less than 50ppm and less than 100ppm, the amount of the gasifying component was "X" when it was not less than 100ppm, and the low outgas was evaluated.
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TABLE 3
Industrial applicability
According to the present invention, it is possible to provide a sealant for an organic EL display element, which is excellent in low outgas and coatability, and which can provide an organic EL display element excellent in light extraction efficiency.
Claims (6)
1. A sealant for an organic EL display element, characterized by comprising a cationically polymerizable compound and a cationic polymerization initiator,
the cation polymerizable compound comprises a cycloolefin oxide type alicyclic epoxy compound and a fluorene type epoxy compound,
the content of the cycloolefin oxide type alicyclic epoxy compound is 10 to 90 parts by weight, and the content of the fluorene type epoxy compound is 10 to 80 parts by weight, respectively, based on 100 parts by weight of the entire cationically polymerizable compound.
2. The sealant for an organic EL display element according to claim 1, wherein the cationically polymerizable compound contains a cationically polymerizable compound in addition to the cycloolefin oxide type alicyclic epoxy compound and the fluorene type epoxy compound.
3. The sealant for an organic EL display element according to claim 2, wherein the other cationically polymerizable compound contains at least 1 selected from the group consisting of 3-ethyl-3- (((3-ethyloxetan-3-yl) methoxy) methyl) oxetane, 1,2:7, 8-diepoxyoctane, and 1,2:5, 6-diepoxycyclooctane.
4. The sealant for an organic EL display element according to claim 3, wherein the other cationically polymerizable compound comprises 3-ethyl-3- (((3-ethyloxetan-3-yl) methoxy) methyl) oxetan.
5. The sealant for an organic EL display element according to claim 2, wherein the content of the other cationically polymerizable compound is 10 parts by weight or more and 50 parts by weight or less in 100 parts by weight of the cationically polymerizable compound.
6. The sealant for an organic EL display element according to claim 1, wherein the cationic polymerization initiator comprises a quaternary ammonium salt whose counter anion is a borate system.
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| JP2019014452 | 2019-01-30 | ||
| JP2019-014452 | 2019-01-30 | ||
| PCT/JP2020/003098 WO2020158776A1 (en) | 2019-01-30 | 2020-01-29 | Sealant for organic el display element |
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| CN113166371A CN113166371A (en) | 2021-07-23 |
| CN113166371B true CN113166371B (en) | 2024-03-29 |
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| JP (1) | JPWO2020158776A1 (en) |
| KR (1) | KR20210120976A (en) |
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|---|---|---|---|---|
| JP2016058273A (en) * | 2014-09-10 | 2016-04-21 | 積水化学工業株式会社 | Sealant for organic electroluminescent display element |
| CN105940767A (en) * | 2014-05-20 | 2016-09-14 | 积水化学工业株式会社 | Sealing agent for organic electroluminescence display element |
| CN108781489A (en) * | 2016-09-16 | 2018-11-09 | 积水化学工业株式会社 | Organic electro-luminescent display unit sealant |
| CN108957952A (en) * | 2017-05-17 | 2018-12-07 | 东京应化工业株式会社 | Solidification compound, cured film, the manufacturing method of display panel and solidfied material |
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| KR100685845B1 (en) | 2005-10-21 | 2007-02-22 | 삼성에스디아이 주식회사 | Organic eletroluminescence display device and method for fabricating of the same |
| JP5044326B2 (en) | 2007-08-28 | 2012-10-10 | パナソニック株式会社 | Epoxy resin composition and resin sealing device |
| JP6364187B2 (en) * | 2013-12-19 | 2018-07-25 | 新日鉄住金化学株式会社 | Optical epoxy resin composition and cured product thereof |
| 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 |
| JP2019065175A (en) * | 2017-09-29 | 2019-04-25 | 東京応化工業株式会社 | Curable composition, cured film, and method for producing cured product |
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- 2020-01-29 WO PCT/JP2020/003098 patent/WO2020158776A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105940767A (en) * | 2014-05-20 | 2016-09-14 | 积水化学工业株式会社 | Sealing agent for organic electroluminescence display element |
| JP2016058273A (en) * | 2014-09-10 | 2016-04-21 | 積水化学工業株式会社 | Sealant for organic electroluminescent display element |
| CN108781489A (en) * | 2016-09-16 | 2018-11-09 | 积水化学工业株式会社 | Organic electro-luminescent display unit sealant |
| CN108957952A (en) * | 2017-05-17 | 2018-12-07 | 东京应化工业株式会社 | Solidification compound, cured film, the manufacturing method of display panel and solidfied material |
Also Published As
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| JPWO2020158776A1 (en) | 2021-12-02 |
| KR20210120976A (en) | 2021-10-07 |
| CN113166371A (en) | 2021-07-23 |
| TW202037630A (en) | 2020-10-16 |
| WO2020158776A1 (en) | 2020-08-06 |
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