WO2015178186A1 - Sealing agent for organic electroluminescence display element - Google Patents
Sealing agent for organic electroluminescence display element Download PDFInfo
- Publication number
- WO2015178186A1 WO2015178186A1 PCT/JP2015/062950 JP2015062950W WO2015178186A1 WO 2015178186 A1 WO2015178186 A1 WO 2015178186A1 JP 2015062950 W JP2015062950 W JP 2015062950W WO 2015178186 A1 WO2015178186 A1 WO 2015178186A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- organic electroluminescence
- sealing agent
- electroluminescence display
- compound represented
- examples
- Prior art date
Links
- 238000007789 sealing Methods 0.000 title claims abstract description 38
- 238000005401 electroluminescence Methods 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 24
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 19
- 239000000565 sealant Substances 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 239000012954 diazonium Substances 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 150000004714 phosphonium salts Chemical class 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 150000001989 diazonium salts Chemical class 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 15
- 125000002091 cationic group Chemical group 0.000 abstract description 9
- 238000010943 off-gassing Methods 0.000 abstract description 3
- -1 triphenylsulfonium hexafluoride antimony Chemical compound 0.000 description 48
- 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 14
- 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 14
- 239000006087 Silane Coupling Agent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 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 4
- PFHLXMMCWCWAMA-UHFFFAOYSA-N [4-(4-diphenylsulfoniophenyl)sulfanylphenyl]-diphenylsulfanium Chemical compound C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC(C=C1)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 PFHLXMMCWCWAMA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 235000019000 fluorine Nutrition 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 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
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 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
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-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
- 238000011156 evaluation 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
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- 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
- 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
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-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
- HTJPMGZZCKEJNA-UHFFFAOYSA-N 2-[3-[4-[4-[2,3-bis(2-hydroxyethoxy)phenyl]sulfanylphenyl]sulfanylphenyl]sulfanyl-2-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=CC(SC=2C=CC(SC=3C=CC(SC=4C(=C(OCCO)C=CC=4)OCCO)=CC=3)=CC=2)=C1OCCO HTJPMGZZCKEJNA-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-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
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-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
- 102100033806 Alpha-protein kinase 3 Human genes 0.000 description 1
- 101710082399 Alpha-protein kinase 3 Proteins 0.000 description 1
- UPWQRKLVJNNYRC-UHFFFAOYSA-M C(C=C1)=CC=C1[S+](C1=CC=CC=C1)C1=CC=CC=C1.[F-].F.F.F.F.F.[AsH3] Chemical compound C(C=C1)=CC=C1[S+](C1=CC=CC=C1)C1=CC=CC=C1.[F-].F.F.F.F.F.[AsH3] UPWQRKLVJNNYRC-UHFFFAOYSA-M 0.000 description 1
- LNKMXDMYWXREMQ-UHFFFAOYSA-M COC(C=C1)=CC=C1[S+](C(C=C1)=CC=C1OC)C(C=C1)=CC=C1OC.[F-].F.F.F.F.F.[AsH3] Chemical compound COC(C=C1)=CC=C1[S+](C(C=C1)=CC=C1OC)C(C=C1)=CC=C1OC.[F-].F.F.F.F.F.[AsH3] LNKMXDMYWXREMQ-UHFFFAOYSA-M 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
- SXXQJTFDIHLDDD-UHFFFAOYSA-N S.[AsH3] Chemical compound S.[AsH3] SXXQJTFDIHLDDD-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 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
- 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
- PUGNGWDLTAQHOZ-UHFFFAOYSA-J [F-].[F-].[F-].[F-].C(C)[N+](C1=CC=CC=C1)(CC1=CC=CC=C1)CC.C(C)[N+](C1=CC=CC=C1)(CC)CC1=CC=CC=C1.C(C)[N+](C1=CC=CC=C1)(CC)CC1=CC=CC=C1.C(C)[N+](C1=CC=CC=C1)(CC)CC1=CC=CC=C1 Chemical compound [F-].[F-].[F-].[F-].C(C)[N+](C1=CC=CC=C1)(CC1=CC=CC=C1)CC.C(C)[N+](C1=CC=CC=C1)(CC)CC1=CC=CC=C1.C(C)[N+](C1=CC=CC=C1)(CC)CC1=CC=CC=C1.C(C)[N+](C1=CC=CC=C1)(CC)CC1=CC=CC=C1 PUGNGWDLTAQHOZ-UHFFFAOYSA-J 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
- 229920006397 acrylic thermoplastic Polymers 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
- 150000001412 amines Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001450 anions Chemical group 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 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
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical compound N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-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
- 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
- 150000001768 cations Chemical class 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
- 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
- 239000008393 encapsulating agent Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 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
- 239000003999 initiator Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004973 liquid crystal related substance 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
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 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
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-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
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 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
- 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 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
-
- 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
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- 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
- C08G59/26—Di-epoxy compounds heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
Definitions
- the present invention relates to a sealant for organic electroluminescence display elements that can suppress the generation of outgas and is excellent in storage stability and applicability.
- organic electroluminescence (organic EL) display elements and organic thin film solar cell elements have been advanced.
- the organic thin film element can be easily produced by vacuum deposition, solution coating, or the like, and thus has excellent productivity.
- the organic EL display element 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 into the organic light emitting material layer and holes are injected from the other electrode, electrons and holes are combined in the organic light emitting material layer to perform self-light emission. Compared with a liquid crystal display element or the like that requires a backlight, the visibility is better, the thickness can be reduced, and direct current low voltage driving is possible.
- an organic EL display element has a problem that when the organic light emitting material layer and the electrode are exposed to the outside air, the light emission characteristics thereof are rapidly deteriorated and the life is shortened. Therefore, for the purpose of improving the stability and durability of the organic EL display element, in the organic EL display element, a sealing technique for shielding the organic light emitting material layer and the electrode from moisture and oxygen in the atmosphere is indispensable. Yes.
- Patent Document 1 discloses a method of filling a photocurable adhesive between organic EL display element substrates in a top emission organic EL display element or the like, and irradiating light to seal.
- a photocurable adhesive between organic EL display element substrates in a top emission organic EL display element or the like, and irradiating light to seal.
- Such conventional photocurable adhesives have a problem in that they generate outgas during light irradiation to deteriorate the device, and are inferior in storage stability and applicability.
- An object of this invention is to provide the sealing agent for organic electroluminescent display elements which can suppress generation
- the present invention is a sealing agent for an organic electroluminescence display device comprising a cationically polymerizable compound and a cationic polymerization initiator, wherein the cationically polymerizable compound comprises a compound represented by the following formula (1-1) and // For an organic electroluminescence display device containing a compound represented by the following formula (1-2) and having a viscosity of 50 to 250 mPa ⁇ s measured at 25 ° C. and 50 rpm using an E-type viscometer It is a sealant.
- the present invention is described in detail below.
- the present inventors can suppress the generation of outgas, and can obtain a sealing agent for organic electroluminescence display elements that is excellent in storage stability and coating properties.
- the headline and the present invention have been completed.
- the sealing agent for organic electroluminescence display elements of this invention contains a cationically polymerizable compound.
- the cationically polymerizable compound contains a compound represented by the above formula (1-1) and / or a compound represented by the above formula (1-2).
- the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2) are also collectively referred to as “an epoxy compound according to the present invention”.
- an epoxy compound according to the present invention By containing the epoxy compound concerning this invention, the sealing agent for organic electroluminescent display elements of this invention can suppress generation
- the cationically polymerizable compound may contain at least one of the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2). It is preferable to contain both the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2) because the stability and the coating property are all excellent. .
- the content ratio of the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2) is within this range, the effect of suppressing outgas, storage stability, and coating It will be even better for all of the properties.
- examples of the commercially available compounds include Celoxide 8000 (manufactured by Daicel), and among the compounds represented by the formula (1-2), Examples of such materials include Celoxide 2021P (manufactured by Daicel Corporation).
- the encapsulant for organic electroluminescence display elements of the present invention includes other cationic polymerizable compounds such as bisphenol A type epoxy resin and bisphenol F type epoxy resin as the cationic polymerizable compound as long as the purpose of the present invention is not impaired. Although it may contain, it is preferable not to contain another cationically polymerizable compound from a viewpoint of suppressing applicability
- the preferred lower limit of the content of the epoxy compound according to the present invention in 100 parts by weight of the whole cationic polymerizable compound is 60 parts by weight.
- the content of the epoxy compound according to the present invention is less than 60 parts by weight, applicability may be deteriorated or the effect of suppressing outgas may not be sufficiently exhibited.
- the minimum with more preferable content of the epoxy compound concerning this invention is 70 weight part.
- the sealing agent for organic electroluminescence display elements of the present invention contains a cationic polymerization initiator.
- the cationic polymerization initiator include a thermal cationic polymerization initiator that generates a protonic acid or a Lewis acid by heating, and a photocationic polymerization initiator that generates a protonic acid or a Lewis acid by light irradiation. It may be a nonionic acid generation type. Especially, it is preferable to contain a thermal cationic polymerization initiator.
- thermal cationic polymerization initiator examples include BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , or (BX 4 ) ⁇ (where X is phenyl substituted with at least two fluorine or trifluoromethyl groups.
- a sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt, or an iodonium salt, and a sulfonium salt is more preferable.
- sulfonium salts include triphenylsulfonium boron tetrafluoride, triphenylsulfonium hexafluoride antimony, triphenylsulfonium hexafluoride arsenic, tri (4-methoxyphenyl) sulfonium hexafluoride arsenic, and diphenyl (4-phenylthiophenyl). ) Sulfonium arsenic hexafluoride and the like.
- the phosphonium salt include ethyltriphenylphosphonium antimony hexafluoride and tetrabutylphosphonium antimony hexafluoride.
- Examples of the quaternary ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (penta).
- Fluorophenyl) borate dimethylphenyl (4-methylbenzyl) ammonium hexafluorohexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) ) Borate, methylphenyldibenzylammonium, methylphenyldibenzylammonium hexaf Oroantimonate hexafluorophosphate, methylphenyldibenzylammonium trakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) Borate
- thermal cationic polymerization initiators include, for example, Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-B3, Sun-Aid SI-B3A, Sun-Aid SI-B4 (all of which are Sanshin Chemical Industry Co., Ltd.). CXC1612, CXC1738, CXC1821 (all manufactured by King Industries) and the like.
- ionic photoacid generating types include, for example, that the anion moiety is BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , or (BX 4 ) ⁇ (where X is at least An aromatic sulfonium salt, an aromatic iodonium salt, an aromatic diazonium salt, an aromatic ammonium salt, or (2,4, which represents a phenyl group substituted with two or more fluorine or trifluoromethyl groups) -Cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt and the like.
- aromatic sulfonium salt examples include bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluoroantimonate, and bis (4- ( Diphenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- ( Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetraflu
- aromatic iodonium salt examples 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 hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethy
- aromatic diazonium salt examples include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.
- aromatic ammonium salt examples 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)
- Examples include -2-cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
- Examples of the (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene.
- nonionic photoacid generating type examples include, for example, nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, N-hydroxyimidosulfonate and the like. Can be mentioned.
- photocationic polymerization initiators examples include, for example, DTS-200 (manufactured by Midori Chemical Co., Ltd.), UVI6990, UVI6974 (all manufactured by Union Carbide), SP-150, SP-170 (all ADEKA), FC-508, FC-512 (all from 3M), IRGACURE290 (from BASF), PI 2074 (from Rhodia), and the like.
- the content of the cationic polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound.
- the content of the cationic polymerization initiator is less than 0.01 parts by weight, sufficient curability may not be imparted to the resulting organic electroluminescent display element sealant.
- the content of the cationic polymerization initiator exceeds 10 parts by weight, the storage stability of the obtained organic electroluminescent display element sealing agent becomes insufficient, or the obtained organic electroluminescent display element sealing agent The moisture resistance of the cured product may deteriorate.
- the minimum with more preferable content of the said cationic polymerization initiator is 0.05 weight part, and a more preferable upper limit is 5 weight part.
- the sealing agent for organic electroluminescent display elements of this invention contains a stabilizer. By containing the said stabilizer, the sealing agent for organic electroluminescent display elements of this invention becomes a thing excellent in storage stability more.
- the stabilizer examples include amine compounds such as benzylamine and aminophenol type epoxy resins.
- the content of the stabilizer is preferably 0.001 part by weight and preferably 2 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound.
- the content of the stabilizer is less than 0.001 part by weight, the effect of improving the storage stability of the obtained sealing agent for organic electroluminescence display elements may not be sufficiently exhibited.
- the content of the stabilizer exceeds 2 parts by weight, curing due to cations may be inhibited.
- the minimum with more preferable content of the said stabilizer is 0.05 weight part, and a more preferable upper limit is 1 weight part.
- the sealing agent for organic electroluminescence display elements of the present invention may contain a silane coupling agent.
- the said silane coupling agent has a role which improves the adhesiveness of the sealing agent for organic electroluminescent display elements of this invention, a board
- silane coupling agent examples include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and the like. These silane coupling agents may be used independently and 2 or more types may be used together.
- the content of the silane coupling agent is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound.
- the content of the silane coupling agent is less than 0.1 parts by weight, the effect of improving the adhesiveness of the obtained sealing agent for organic electroluminescence display elements may not be sufficiently exhibited.
- content of the said silane coupling agent exceeds 10 weight part, an excess silane coupling agent may bleed out.
- the minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 5 weight part.
- the sealing agent for organic electroluminescence display elements of the present invention may contain a thermosetting agent as long as the object of the present invention is not impaired.
- the thermosetting agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamides, guanidine derivatives, modified aliphatic polyamines, addition products of various amines and epoxy resins, and the like.
- the hydrazide compound include 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin] and the like.
- imidazole derivative examples 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) -adipamide, 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole.
- acid anhydride examples include tetrahydrophthalic anhydride, ethylene glycol bis (anhydro trimellitate), and the like. These thermosetting agents may be used alone or in combination of two or more.
- the sealing agent for organic electroluminescence display elements of the present invention may contain a surface modifier as long as the object of the present invention is not impaired.
- a surface modifier By containing the said surface modifier, the flatness of the coating film of the sealing agent for organic electroluminescent display elements of this invention can be improved.
- the surface modifier include surfactants and leveling agents.
- surfactant and the leveling agent examples include silicones, acrylics, and fluorines.
- surfactants and leveling agents examples include BYK-302, BYK-331 (both manufactured by Big Chemie Japan), UVX-272 (manufactured by Enomoto Kasei), Surflon S, and the like. -611 (manufactured by AGC Seimi Chemical Co., Ltd.).
- the sealing agent for organic electroluminescence display elements of the present invention includes an acid generated in the sealing agent for organic electroluminescence display elements in order to improve the durability of the element electrode within a range not impairing the object of the present invention.
- You may contain the compound or ion exchange resin which reacts.
- Examples of the compound that reacts with the generated acid include substances that neutralize the acid, for example, alkali metal carbonates or bicarbonates, or alkaline earth metal carbonates or bicarbonates.
- alkali metal carbonates or bicarbonates or alkaline earth metal carbonates or bicarbonates.
- calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate and the like are used.
- any of a cation exchange type, an anion exchange type, and a both ion exchange type can be used, and in particular, a cation exchange type or a both ion exchange type capable of adsorbing chloride ions. Is preferred.
- the sealing agent for organic electroluminescence display elements of the present invention is a range that does not impair the object of the present invention, and if necessary, a curing retarder, a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, an ultraviolet absorber. You may contain well-known various additives, such as an agent and antioxidant.
- Examples of the method for producing the organic electroluminescent display element sealant of the present invention include cationic polymerization using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll. Examples thereof include a method of mixing a compound, a cationic polymerization initiator, and an additive such as a silane coupling agent added as necessary.
- the sealing agent for organic electroluminescence display elements of the present invention has an overall viscosity lower limit of 50 mPa ⁇ s and an upper limit of 250 mPa ⁇ s measured using an E-type viscometer at 25 ° C. and 50 rpm.
- the viscosity is preferably 70 mPa ⁇ s or more and less than 100 mPa ⁇ s.
- Example 1 As a cationically polymerizable compound, 50 parts by weight of a compound represented by the above formula (1-1) (manufactured by Daicel, “Celoxide 8000”) and a compound represented by the above formula (1-2) (manufactured by Daicel, “ 50 parts by weight of Celoxide 2021P ”) and 0.5 parts by weight of an antimony initiator (manufactured by King Industries," CXC1612 ”) as a thermal cationic polymerization initiator, a stirring mixer (" AR-250, manufactured by Shinky Corporation). )), And the mixture was uniformly stirred and mixed at a stirring speed of 3000 rpm to prepare an organic electroluminescence display element sealant.
- a compound represented by the above formula (1-1) manufactured by Daicel, “Celoxide 8000”
- 1-2 manufactured by Daicel, “ 50 parts by weight of Celoxide 2021P ”
- an antimony initiator manufactured by King Industries
- CXC1612 thermal
- Examples 2 to 10, Comparative Examples 1 to 9 The materials described in Tables 1 and 2 were stirred and mixed in the same manner as in Example 1 according to the blending ratios described in Table 1, and organic electroluminescence displays of Examples 2 to 10 and Comparative Examples 1 to 9 were made. An element sealant was prepared.
- the viscosity of the sealing agent for organic electroluminescence display elements was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “VISCOMETER TV-22”) at 25 ° C. and 50 rpm.
- each of the organic electroluminescence display element sealants obtained in the Examples and Comparative Examples was weighed and sealed in a vial bottle, and then Examples 1 to 7 and Comparative Examples 1 to 9 were used.
- About each sealing agent for organic electroluminescent display elements obtained in Example 8 to 10 was cured by heating at 100 ° C. for 30 minutes, and each sealing agent for organic electroluminescent display elements obtained in Examples 8 to 10 was used.
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Abstract
The purpose of the present invention is to provide a sealing agent for an organic electroluminescence display element in which occurrence of outgassing can be minimized and excellent storage stability and applicability are exhibited. The present invention is a sealing agent for an organic electroluminescence display element containing a cationic polymerizable compound and a cationic polymerization initiator, wherein the cationic polymerizable compound contains a compound represented by formula (1-1) and/or a compound represented by formula (1-2), and the viscosity measured using an E-type viscometer under conditions of 25°C and 50 rpm is 50-250 mPa·s.
Description
本発明は、アウトガスの発生を抑制することができ、保存安定性及び塗布性に優れる有機エレクトロルミネッセンス表示素子用封止剤に関する。
The present invention relates to a sealant for organic electroluminescence display elements that can suppress the generation of outgas and is excellent in storage stability and applicability.
近年、有機エレクトロルミネッセンス（有機ＥＬ）表示素子や有機薄膜太陽電池素子等の有機薄膜素子を用いた有機光デバイスの研究が進められている。有機薄膜素子は真空蒸着や溶液塗布等により簡便に作製できるため、生産性にも優れる。
In recent years, research on organic optical devices using organic thin film elements such as organic electroluminescence (organic EL) display elements and organic thin film solar cell elements has been advanced. The organic thin film element can be easily produced by vacuum deposition, solution coating, or the like, and thus has excellent productivity.
有機ＥＬ表示素子は、互いに対向する一対の電極間に有機発光材料層が挟持された薄膜構造体を有する。この有機発光材料層に一方の電極から電子が注入されるとともに他方の電極から正孔が注入されることにより有機発光材料層内で電子と正孔とが結合して自己発光を行う。バックライトを必要とする液晶表示素子等と比較して視認性がよく、より薄型化が可能であり、かつ、直流低電圧駆動が可能であるという利点を有する。
The organic EL display element 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 into the organic light emitting material layer and holes are injected from the other electrode, electrons and holes are combined in the organic light emitting material layer to perform self-light emission. Compared with a liquid crystal display element or the like that requires a backlight, the visibility is better, the thickness can be reduced, and direct current low voltage driving is possible.
ところが、このような有機ＥＬ表示素子は、有機発光材料層や電極が外気に曝されるとその発光特性が急激に劣化し寿命が短くなるという問題があった。従って、有機ＥＬ表示素子の安定性及び耐久性を高めることを目的として、有機ＥＬ表示素子においては、有機発光材料層や電極を大気中の水分や酸素から遮断する封止技術が不可欠となっている。
However, such an organic EL display element has a problem that when the organic light emitting material layer and the electrode are exposed to the outside air, the light emission characteristics thereof are rapidly deteriorated and the life is shortened. Therefore, for the purpose of improving the stability and durability of the organic EL display element, in the organic EL display element, a sealing technique for shielding the organic light emitting material layer and the electrode from moisture and oxygen in the atmosphere is indispensable. Yes.
特許文献１には、上面発光型有機ＥＬ表示素子等において、有機ＥＬ表示素子基板の間に光硬化性接着剤を満たし、光を照射して封止する方法が開示されている。しかしながら、このような従来の光硬化性接着剤は、光照射時にアウトガスを発生して素子を劣化させたり、保存安定性や塗布性に劣るものであったりするという問題があった。
Patent Document 1 discloses a method of filling a photocurable adhesive between organic EL display element substrates in a top emission organic EL display element or the like, and irradiating light to seal. However, such conventional photocurable adhesives have a problem in that they generate outgas during light irradiation to deteriorate the device, and are inferior in storage stability and applicability.
本発明は、アウトガスの発生を抑制することができ、保存安定性及び塗布性に優れる有機エレクトロルミネッセンス表示素子用封止剤を提供することを目的とする。
An object of this invention is to provide the sealing agent for organic electroluminescent display elements which can suppress generation | occurrence | production of outgas and is excellent in storage stability and applicability | paintability.
本発明は、カチオン重合性化合物とカチオン重合開始剤とを含有する有機エレクトロルミネッセンス表示素子用封止剤であって、前記カチオン重合性化合物は、下記式（１－１）で表される化合物及び／又は下記式（１－２）で表される化合物を含有し、Ｅ型粘度計を用いて、２５℃、５０ｒｐｍの条件で測定した粘度が５０～２５０ｍＰａ・ｓである有機エレクトロルミネッセンス表示素子用封止剤である。
The present invention is a sealing agent for an organic electroluminescence display device comprising a cationically polymerizable compound and a cationic polymerization initiator, wherein the cationically polymerizable compound comprises a compound represented by the following formula (1-1) and // For an organic electroluminescence display device containing a compound represented by the following formula (1-2) and having a viscosity of 50 to 250 mPa · s measured at 25 ° C. and 50 rpm using an E-type viscometer It is a sealant.
以下に本発明を詳述する。
本発明者らは、特定のカチオン重合性化合物を用いることにより、アウトガスの発生を抑制することができ、保存安定性及び塗布性に優れる有機エレクトロルミネッセンス表示素子用封止剤を得ることができることを見出し、本発明を完成させるに至った。 The present invention is described in detail below.
By using a specific cationically polymerizable compound, the present inventors can suppress the generation of outgas, and can obtain a sealing agent for organic electroluminescence display elements that is excellent in storage stability and coating properties. The headline and the present invention have been completed.
本発明者らは、特定のカチオン重合性化合物を用いることにより、アウトガスの発生を抑制することができ、保存安定性及び塗布性に優れる有機エレクトロルミネッセンス表示素子用封止剤を得ることができることを見出し、本発明を完成させるに至った。 The present invention is described in detail below.
By using a specific cationically polymerizable compound, the present inventors can suppress the generation of outgas, and can obtain a sealing agent for organic electroluminescence display elements that is excellent in storage stability and coating properties. The headline and the present invention have been completed.
本発明の有機エレクトロルミネッセンス表示素子用封止剤は、カチオン重合性化合物を含有する。
上記カチオン重合性化合物は、上記式（１－１）で表される化合物及び／又は上記式（１－２）で表される化合物を含有する。以下、上記式（１－１）で表される化合物と上記式（１－２）で表される化合物とを併せて、「本発明にかかるエポキシ化合物」ともいう。本発明にかかるエポキシ化合物を含有することにより、本発明の有機エレクトロルミネッセンス表示素子用封止剤は、アウトガスの発生を抑制することができ、保存安定性及び塗布性に優れるものとなる。 The sealing agent for organic electroluminescence display elements of this invention contains a cationically polymerizable compound.
The cationically polymerizable compound contains a compound represented by the above formula (1-1) and / or a compound represented by the above formula (1-2). Hereinafter, the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2) are also collectively referred to as “an epoxy compound according to the present invention”. By containing the epoxy compound concerning this invention, the sealing agent for organic electroluminescent display elements of this invention can suppress generation | occurrence | production of outgas, and will become excellent in storage stability and applicability | paintability.
上記カチオン重合性化合物は、上記式（１－１）で表される化合物及び／又は上記式（１－２）で表される化合物を含有する。以下、上記式（１－１）で表される化合物と上記式（１－２）で表される化合物とを併せて、「本発明にかかるエポキシ化合物」ともいう。本発明にかかるエポキシ化合物を含有することにより、本発明の有機エレクトロルミネッセンス表示素子用封止剤は、アウトガスの発生を抑制することができ、保存安定性及び塗布性に優れるものとなる。 The sealing agent for organic electroluminescence display elements of this invention contains a cationically polymerizable compound.
The cationically polymerizable compound contains a compound represented by the above formula (1-1) and / or a compound represented by the above formula (1-2). Hereinafter, the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2) are also collectively referred to as “an epoxy compound according to the present invention”. By containing the epoxy compound concerning this invention, the sealing agent for organic electroluminescent display elements of this invention can suppress generation | occurrence | production of outgas, and will become excellent in storage stability and applicability | paintability.
上記カチオン重合性化合物は、上記式（１－１）で表される化合物及び上記式（１－２）で表される化合物のうち少なくとも一方を含有すればよいが、アウトガスを抑制する効果、保存安定性、及び、塗布性の全てにより優れるものとなることから、上記式（１－１）で表される化合物及び上記式（１－２）で表される化合物の両方を含有することが好ましい。
The cationically polymerizable compound may contain at least one of the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2). It is preferable to contain both the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2) because the stability and the coating property are all excellent. .
上記カチオン重合性化合物が上記式（１－１）で表される化合物及び上記式（１－２）で表される化合物の両方を含有する場合、上記式（１－１）で表される化合物と上記式（１－２）で表される化合物との含有割合は、重量比で、上記式（１－１）で表される化合物：上記式（１－２）で表される化合物＝９：１～１：４であることが好ましい。上記式（１－１）で表される化合物と上記式（１－２）で表される化合物との含有割合がこの範囲であることにより、アウトガスを抑制する効果、保存安定性、及び、塗布性の全てに更に優れるものとなる。
When the cationically polymerizable compound contains both the compound represented by the formula (1-1) and the compound represented by the formula (1-2), the compound represented by the formula (1-1) And the compound represented by the above formula (1-2) in terms of weight ratio, the compound represented by the above formula (1-1): the compound represented by the above formula (1-2) = 9 1 to 1: 4 is preferable. When the content ratio of the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2) is within this range, the effect of suppressing outgas, storage stability, and coating It will be even better for all of the properties.
上記式（１－１）で表される化合物のうち市販されているものとしては、セロキサイド８０００（ダイセル社製）が挙げられ、上記式（１－２）で表される化合物のうち市販されているものとしては、セロキサイド２０２１Ｐ（ダイセル社製）が挙げられる。
Among the compounds represented by the formula (1-1), examples of the commercially available compounds include Celoxide 8000 (manufactured by Daicel), and among the compounds represented by the formula (1-2), Examples of such materials include Celoxide 2021P (manufactured by Daicel Corporation).
本発明の有機エレクトロルミネッセンス表示素子用封止剤は、本発明の目的を阻害しない範囲で、上記カチオン重合性化合物としてビスフェノールＡ型エポキシ樹脂やビスフェノールＦ型エポキシ樹脂等のその他のカチオン重合性化合物を含有してもよいが、塗布性やアウトガスを抑制する観点から、その他のカチオン重合性化合物を含有しないことが好ましい。
The encapsulant for organic electroluminescence display elements of the present invention includes other cationic polymerizable compounds such as bisphenol A type epoxy resin and bisphenol F type epoxy resin as the cationic polymerizable compound as long as the purpose of the present invention is not impaired. Although it may contain, it is preferable not to contain another cationically polymerizable compound from a viewpoint of suppressing applicability | paintability and an outgas.
上記その他のカチオン重合性化合物の含有する場合、カチオン重合性化合物全体１００重量部中における本発明にかかるエポキシ化合物の含有量の好ましい下限は６０重量部である。本発明にかかるエポキシ化合物の含有量が６０重量部未満であると、塗布性が悪化したり、アウトガスを抑制する効果が充分に発揮されなくなったりすることがある。本発明にかかるエポキシ化合物の含有量のより好ましい下限は７０重量部である。
When the other cationic polymerizable compound is contained, the preferred lower limit of the content of the epoxy compound according to the present invention in 100 parts by weight of the whole cationic polymerizable compound is 60 parts by weight. When the content of the epoxy compound according to the present invention is less than 60 parts by weight, applicability may be deteriorated or the effect of suppressing outgas may not be sufficiently exhibited. The minimum with more preferable content of the epoxy compound concerning this invention is 70 weight part.
本発明の有機エレクトロルミネッセンス表示素子用封止剤は、カチオン重合開始剤を含有する。
上記カチオン重合開始剤としては、加熱によりプロトン酸又はルイス酸を発生する熱カチオン重合開始剤や、光照射によりプロトン酸又はルイス酸を発生する光カチオン重合開始剤が挙げられ、イオン性酸発生型であってもよいし、非イオン性酸発生型であってもよい。
なかでも、熱カチオン重合開始剤を含有することが好ましい。 The sealing agent for organic electroluminescence display elements of the present invention contains a cationic polymerization initiator.
Examples of the cationic polymerization initiator include a thermal cationic polymerization initiator that generates a protonic acid or a Lewis acid by heating, and a photocationic polymerization initiator that generates a protonic acid or a Lewis acid by light irradiation. It may be a nonionic acid generation type.
Especially, it is preferable to contain a thermal cationic polymerization initiator.
上記カチオン重合開始剤としては、加熱によりプロトン酸又はルイス酸を発生する熱カチオン重合開始剤や、光照射によりプロトン酸又はルイス酸を発生する光カチオン重合開始剤が挙げられ、イオン性酸発生型であってもよいし、非イオン性酸発生型であってもよい。
なかでも、熱カチオン重合開始剤を含有することが好ましい。 The sealing agent for organic electroluminescence display elements of the present invention contains a cationic polymerization initiator.
Examples of the cationic polymerization initiator include a thermal cationic polymerization initiator that generates a protonic acid or a Lewis acid by heating, and a photocationic polymerization initiator that generates a protonic acid or a Lewis acid by light irradiation. It may be a nonionic acid generation type.
Especially, it is preferable to contain a thermal cationic polymerization initiator.
上記熱カチオン重合開始剤としては、ＢＦ４
－、ＰＦ６
－、ＳｂＦ６
－、又は、（ＢＸ４）－（ただし、Ｘは、少なくとも２つ以上のフッ素若しくはトリフルオロメチル基で置換されたフェニル基を表す）を対アニオンとする、スルホニウム塩、ホスホニウム塩、第４級アンモニウム塩、ジアゾニウム塩、又は、ヨードニウム塩が好ましく、スルホニウム塩がより好ましい。
Examples of the thermal cationic polymerization initiator include BF 4 − , PF 6 − , SbF 6 − , or (BX 4 ) − (where X is phenyl substituted with at least two fluorine or trifluoromethyl groups. A sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt, or an iodonium salt, and a sulfonium salt is more preferable.
上記スルホニウム塩としては、トリフェニルスルホニウム四フッ化ホウ素、トリフェニルスルホニウム六フッ化アンチモン、トリフェニルスルホニウム六フッ化ヒ素、トリ（４－メトキシフェニル）スルホニウム六フッ化ヒ素、ジフェニル（４－フェニルチオフェニル）スルホニウム六フッ化ヒ素等が挙げられる。
上記ホスホニウム塩としては、エチルトリフェニルホスホニウム六フッ化アンチモン、テトラブチルホスホニウム六フッ化アンチモン等が挙げられる。
上記第４級アンモニウム塩としては、例えば、ジメチルフェニル（４－メトキシベンジル）アンモニウムヘキサフルオロホスフェート、ジメチルフェニル（４－メトキシベンジル）アンモニウムヘキサフルオロアンチモネート、ジメチルフェニル（４－メトキシベンジル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロヘキサフルオロホスフェート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロアンチモネート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロテトラキス（ペンタフルオロフェニル）ボレート、メチルフェニルジベンジルアンモニウム、メチルフェニルジベンジルアンモニウムヘキサフルオロアンチモネートヘキサフルオロホスフェート、メチルフェニルジベンジルアンモニウムトラキス（ペンタフルオロフェニル）ボレート、フェニルトリベンジルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジメチルフェニル（３，４－ジメチルベンジル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、Ｎ，Ｎ－ジメチル－Ｎ－ベンジルアニリニウム六フッ化アンチモン、Ｎ，Ｎ－ジエチル－Ｎ－ベンジルアニリニウム四フッ化ホウ素、Ｎ，Ｎ－ジメチル－Ｎ－ベンジルピリジニウム六フッ化アンチモン、Ｎ，Ｎ－ジエチル－Ｎ－ベンジルピリジニウムトリフルオロメタンスルホン酸等が挙げられる。 Examples of the sulfonium salts include triphenylsulfonium boron tetrafluoride, triphenylsulfonium hexafluoride antimony, triphenylsulfonium hexafluoride arsenic, tri (4-methoxyphenyl) sulfonium hexafluoride arsenic, and diphenyl (4-phenylthiophenyl). ) Sulfonium arsenic hexafluoride and the like.
Examples of the phosphonium salt include ethyltriphenylphosphonium antimony hexafluoride and tetrabutylphosphonium antimony hexafluoride.
Examples of the quaternary ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (penta). Fluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorohexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) ) Borate, methylphenyldibenzylammonium, methylphenyldibenzylammonium hexaf Oroantimonate hexafluorophosphate, methylphenyldibenzylammonium trakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) Borate, antimony N, N-dimethyl-N-benzylanilinium hexafluoride, N, N-diethyl-N-benzylanilinium tetrafluoride, antimony N, N-dimethyl-N-benzylpyridinium hexafluoride, N , N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid and the like.
上記ホスホニウム塩としては、エチルトリフェニルホスホニウム六フッ化アンチモン、テトラブチルホスホニウム六フッ化アンチモン等が挙げられる。
上記第４級アンモニウム塩としては、例えば、ジメチルフェニル（４－メトキシベンジル）アンモニウムヘキサフルオロホスフェート、ジメチルフェニル（４－メトキシベンジル）アンモニウムヘキサフルオロアンチモネート、ジメチルフェニル（４－メトキシベンジル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロヘキサフルオロホスフェート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロアンチモネート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロテトラキス（ペンタフルオロフェニル）ボレート、メチルフェニルジベンジルアンモニウム、メチルフェニルジベンジルアンモニウムヘキサフルオロアンチモネートヘキサフルオロホスフェート、メチルフェニルジベンジルアンモニウムトラキス（ペンタフルオロフェニル）ボレート、フェニルトリベンジルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジメチルフェニル（３，４－ジメチルベンジル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、Ｎ，Ｎ－ジメチル－Ｎ－ベンジルアニリニウム六フッ化アンチモン、Ｎ，Ｎ－ジエチル－Ｎ－ベンジルアニリニウム四フッ化ホウ素、Ｎ，Ｎ－ジメチル－Ｎ－ベンジルピリジニウム六フッ化アンチモン、Ｎ，Ｎ－ジエチル－Ｎ－ベンジルピリジニウムトリフルオロメタンスルホン酸等が挙げられる。 Examples of the sulfonium salts include triphenylsulfonium boron tetrafluoride, triphenylsulfonium hexafluoride antimony, triphenylsulfonium hexafluoride arsenic, tri (4-methoxyphenyl) sulfonium hexafluoride arsenic, and diphenyl (4-phenylthiophenyl). ) Sulfonium arsenic hexafluoride and the like.
Examples of the phosphonium salt include ethyltriphenylphosphonium antimony hexafluoride and tetrabutylphosphonium antimony hexafluoride.
Examples of the quaternary ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (penta). Fluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorohexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) ) Borate, methylphenyldibenzylammonium, methylphenyldibenzylammonium hexaf Oroantimonate hexafluorophosphate, methylphenyldibenzylammonium trakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) Borate, antimony N, N-dimethyl-N-benzylanilinium hexafluoride, N, N-diethyl-N-benzylanilinium tetrafluoride, antimony N, N-dimethyl-N-benzylpyridinium hexafluoride, N , N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid and the like.
上記熱カチオン重合開始剤のうち市販されているものとしては、例えば、サンエイドＳＩ－６０、サンエイドＳＩ－８０、サンエイドＳＩ－Ｂ３、サンエイドＳＩ－Ｂ３Ａ、サンエイドＳＩ－Ｂ４（いずれも三新化学工業社製）、ＣＸＣ１６１２、ＣＸＣ１７３８、ＣＸＣ１８２１（いずれもＫｉｎｇ Ｉｎｄｕｓｔｒｉｅｓ社製）等が挙げられる。
Commercially available thermal cationic polymerization initiators include, for example, Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-B3, Sun-Aid SI-B3A, Sun-Aid SI-B4 (all of which are Sanshin Chemical Industry Co., Ltd.). CXC1612, CXC1738, CXC1821 (all manufactured by King Industries) and the like.
上記光カチオン重合開始剤のうちイオン性光酸発生型のものとしては、例えば、アニオン部分がＢＦ４
－、ＰＦ６
－、ＳｂＦ６
－、又は、（ＢＸ４）－（但し、Ｘは、少なくとも２つ以上のフッ素又はトリフルオロメチル基で置換されたフェニル基を表す）で構成される、芳香族スルホニウム塩、芳香族ヨードニウム塩、芳香族ジアゾニウム塩、芳香族アンモニウム塩、又は、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ塩等が挙げられる。
Among the above-mentioned photocationic polymerization initiators, ionic photoacid generating types include, for example, that the anion moiety is BF 4 − , PF 6 − , SbF 6 − , or (BX 4 ) − (where X is at least An aromatic sulfonium salt, an aromatic iodonium salt, an aromatic diazonium salt, an aromatic ammonium salt, or (2,4, which represents a phenyl group substituted with two or more fluorine or trifluoromethyl groups) -Cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt and the like.
上記芳香族スルホニウム塩としては、例えば、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロホスフェート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロアンチモネート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビステトラフルオロボレート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドテトラキス（ペンタフルオロフェニル）ボレート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムヘキサフルオロホスフェート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムヘキサフルオロアンチモネート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムテトラフルオロボレート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムテトラフルオロボレート、トリフェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロホスフェート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロアンチモネート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビステトラフルオロボレート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。
Examples of the aromatic sulfonium salt include bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluoroantimonate, and bis (4- ( Diphenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- ( Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) Phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis (4- (di ( 4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluoroantimonate, Bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (di ( - (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, and the like.
上記芳香族ヨードニウム塩としては、例えば、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムテトラフルオロボレート、ジフェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、ビス（ドデシルフェニル）ヨードニウムヘキサフルオロホスフェート、ビス（ドデシルフェニル）ヨードニウムヘキサフルオロアンチモネート、ビス（ドデシルフェニル）ヨードニウムテトラフルオロボレート、ビス（ドデシルフェニル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムヘキサフルオロホスフェート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムヘキサフルオロアンチモネート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムテトラフルオロボレート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。
Examples of the aromatic iodonium salt 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 hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethyl) Such as phenyl iodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate Can be mentioned.
上記芳香族ジアゾニウム塩としては、例えば、フェニルジアゾニウムヘキサフルオロホスフェート、フェニルジアゾニウムヘキサフルオロアンチモネート、フェニルジアゾニウムテトラフルオロボレート、フェニルジアゾニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。
Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.
上記芳香族アンモニウム塩としては、例えば、１－ベンジル－２－シアノピリジニウムヘキサフルオロホスフェート、１－ベンジル－２－シアノピリジニウムヘキサフルオロアンチモネート、１－ベンジル－２－シアノピリジニウムテトラフルオロボレート、１－ベンジル－２－シアノピリジニウムテトラキス（ペンタフルオロフェニル）ボレート、１－（ナフチルメチル）－２－シアノピリジニウムヘキサフルオロホスフェート、１－（ナフチルメチル）－２－シアノピリジニウムヘキサフルオロアンチモネート、１－（ナフチルメチル）－２－シアノピリジニウムテトラフルオロボレート、１－（ナフチルメチル）－２－シアノピリジニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。
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) Examples include -2-cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
上記（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ塩としては、例えば、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）ヘキサフルオロホスフェート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）ヘキサフルオロアンチモネート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）テトラフルオロボレート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）テトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。
Examples of the (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene. ) -Fe (II) hexafluorophosphate, (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene) -Fe (II) hexafluoroantimonate, (2,4-cyclopentadiene-1 -Yl) ((1-methylethyl) benzene) -Fe (II) tetrafluoroborate, (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrakis (penta Fluorophenyl) borate and the like.
上記光カチオン重合開始剤のうち非イオン性光酸発生型のものとしては、例えば、ニトロベンジルエステル、スルホン酸誘導体、リン酸エステル、フェノールスルホン酸エステル、ジアゾナフトキノン、Ｎ－ヒドロキシイミドスホナート等が挙げられる。
Examples of the nonionic photoacid generating type among the above-mentioned photocationic polymerization initiators include, for example, nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, N-hydroxyimidosulfonate and the like. Can be mentioned.
上記光カチオン重合開始剤のうち市販されているものとしては、例えば、ＤＴＳ－２００（みどり化学社製）、ＵＶＩ６９９０、ＵＶＩ６９７４（いずれもユニオンカーバイド社製）、ＳＰ－１５０、ＳＰ－１７０（いずれもＡＤＥＫＡ社製）、ＦＣ－５０８、ＦＣ－５１２（いずれも３Ｍ社製）、ＩＲＧＡＣＵＲＥ２９０（ＢＡＳＦ社製）、ＰＩ２０７４（ローディア社製）等が挙げられる。
Examples of commercially available photocationic polymerization initiators include, for example, DTS-200 (manufactured by Midori Chemical Co., Ltd.), UVI6990, UVI6974 (all manufactured by Union Carbide), SP-150, SP-170 (all ADEKA), FC-508, FC-512 (all from 3M), IRGACURE290 (from BASF), PI 2074 (from Rhodia), and the like.
上記熱カチオン重合開始剤と上記光カチオン重合開始剤との両方に記載されているものについては、上記熱カチオン重合開始剤として用いることもでき、上記光カチオン重合開始剤として用いることもできる。
About what is described in both the said thermal cationic polymerization initiator and the said photocationic polymerization initiator, it can also be used as the said thermal cationic polymerization initiator, and can also be used as the said photocationic polymerization initiator.
上記カチオン重合開始剤の含有量は、上記カチオン重合性化合物１００重量部に対して、好ましい下限が０．０１重量部、好ましい上限が１０重量部である。上記カチオン重合開始剤の含有量が０．０１重量部未満であると、得られる有機エレクトロルミネッセンス表示素子用封止剤に充分な硬化性を付与できないことがある。上記カチオン重合開始剤の含有量が１０重量部を超えると、得られる有機エレクトロルミネッセンス表示素子用封止剤の保存安定性が不充分となったり、得られる有機エレクトロルミネッセンス表示素子用封止剤の硬化物の耐湿性が悪くなったりすることがある。上記カチオン重合開始剤の含有量のより好ましい下限は０．０５重量部、より好ましい上限は５重量部である。
The content of the cationic polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound. When the content of the cationic polymerization initiator is less than 0.01 parts by weight, sufficient curability may not be imparted to the resulting organic electroluminescent display element sealant. When the content of the cationic polymerization initiator exceeds 10 parts by weight, the storage stability of the obtained organic electroluminescent display element sealing agent becomes insufficient, or the obtained organic electroluminescent display element sealing agent The moisture resistance of the cured product may deteriorate. The minimum with more preferable content of the said cationic polymerization initiator is 0.05 weight part, and a more preferable upper limit is 5 weight part.
本発明の有機エレクトロルミネッセンス表示素子用封止剤は、安定剤を含有することが好ましい。上記安定剤を含有することにより、本発明の有機エレクトロルミネッセンス表示素子用封止剤は、より保存安定性に優れるものとなる。
It is preferable that the sealing agent for organic electroluminescent display elements of this invention contains a stabilizer. By containing the said stabilizer, the sealing agent for organic electroluminescent display elements of this invention becomes a thing excellent in storage stability more.
上記安定剤としては、例えば、ベンジルアミン等のアミン系化合物やアミノフェノール型エポキシ樹脂等が挙げられる。
Examples of the stabilizer include amine compounds such as benzylamine and aminophenol type epoxy resins.
上記安定剤の含有量は、上記カチオン重合性化合物１００重量部に対して、好ましい下限が０．００１重量部、好ましい上限が２重量部である。上記安定剤の含有量が０．００１重量部未満であると、得られる有機エレクトロルミネッセンス表示素子用封止剤の保存安定性を向上させる効果が充分に発揮されないことがある。上記安定剤の含有量が２重量部を超えると、カチオンによる硬化が阻害されることがある。上記安定剤の含有量のより好ましい下限は０．０５重量部、より好ましい上限は１重量部である。
The content of the stabilizer is preferably 0.001 part by weight and preferably 2 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound. When the content of the stabilizer is less than 0.001 part by weight, the effect of improving the storage stability of the obtained sealing agent for organic electroluminescence display elements may not be sufficiently exhibited. When the content of the stabilizer exceeds 2 parts by weight, curing due to cations may be inhibited. The minimum with more preferable content of the said stabilizer is 0.05 weight part, and a more preferable upper limit is 1 weight part.
本発明の有機エレクトロルミネッセンス表示素子用封止剤は、シランカップリング剤を含有してもよい。上記シランカップリング剤は、本発明の有機エレクトロルミネッセンス表示素子用封止剤と基板等との接着性を向上させる役割を有する。
The sealing agent for organic electroluminescence display elements of the present invention may contain a silane coupling agent. The said silane coupling agent has a role which improves the adhesiveness of the sealing agent for organic electroluminescent display elements of this invention, a board | substrate, etc.
上記シランカップリング剤としては、例えば、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－イソシアネートプロピルトリメトキシシラン等が挙げられる。これらのシランカップリング剤は、単独で用いられてもよいし、２種以上が併用されてもよい。
Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and the like. These silane coupling agents may be used independently and 2 or more types may be used together.
上記シランカップリング剤の含有量は、上記カチオン重合性化合物１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が１０重量部である。上記シランカップリング剤の含有量が０．１重量部未満であると、得られる有機エレクトロルミネッセンス表示素子用封止剤の接着性を向上させる効果が充分に発揮されないことがある。上記シランカップリング剤の含有量が１０重量部を超えると、余剰のシランカップリング剤がブリードアウトすることがある。上記シランカップリング剤の含有量のより好ましい下限は０．５重量部、より好ましい上限は５重量部である。
The content of the silane coupling agent is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound. When the content of the silane coupling agent is less than 0.1 parts by weight, the effect of improving the adhesiveness of the obtained sealing agent for organic electroluminescence display elements may not be sufficiently exhibited. When content of the said silane coupling agent exceeds 10 weight part, an excess silane coupling agent may bleed out. The minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 5 weight part.
本発明の有機エレクトロルミネッセンス表示素子用封止剤は、本発明の目的を阻害しない範囲において、熱硬化剤を含有してもよい。
上記熱硬化剤としては、例えば、ヒドラジド化合物、イミダゾール誘導体、酸無水物、ジシアンジアミド、グアニジン誘導体、変性脂肪族ポリアミン、各種アミンとエポキシ樹脂との付加生成物等が挙げられる。
上記ヒドラジド化合物としては、例えば、１，３－ビス［ヒドラジノカルボノエチル－５－イソプロピルヒダントイン］等が挙げられる。
上記イミダゾール誘導体としては、例えば、１－シアノエチル－２－フェニルイミダゾール、Ｎ－［２－（２－メチル－１－イミダゾリル）エチル］尿素、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、Ｎ，Ｎ’－ビス（２－メチル－１－イミダゾリルエチル）尿素、Ｎ，Ｎ’－（２－メチル－１－イミダゾリルエチル）－アジポアミド、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、２－フェニル－４，５－ジヒドロキシメチルイミダゾール等が挙げられる。
上記酸無水物としては、例えば、テトラヒドロ無水フタル酸、エチレングリコールービス（アンヒドロトリメリテート）等が挙げられる。
これらの熱硬化剤は、単独で用いられてもよいし、２種類以上が併用されてもよい。 The sealing agent for organic electroluminescence display elements of the present invention may contain a thermosetting agent as long as the object of the present invention is not impaired.
Examples of the thermosetting agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamides, guanidine derivatives, modified aliphatic polyamines, addition products of various amines and epoxy resins, and the like.
Examples of the hydrazide compound include 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin] and the like.
Examples of the imidazole derivative 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) -adipamide, 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole.
Examples of the acid anhydride include tetrahydrophthalic anhydride, ethylene glycol bis (anhydro trimellitate), and the like.
These thermosetting agents may be used alone or in combination of two or more.
上記熱硬化剤としては、例えば、ヒドラジド化合物、イミダゾール誘導体、酸無水物、ジシアンジアミド、グアニジン誘導体、変性脂肪族ポリアミン、各種アミンとエポキシ樹脂との付加生成物等が挙げられる。
上記ヒドラジド化合物としては、例えば、１，３－ビス［ヒドラジノカルボノエチル－５－イソプロピルヒダントイン］等が挙げられる。
上記イミダゾール誘導体としては、例えば、１－シアノエチル－２－フェニルイミダゾール、Ｎ－［２－（２－メチル－１－イミダゾリル）エチル］尿素、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、Ｎ，Ｎ’－ビス（２－メチル－１－イミダゾリルエチル）尿素、Ｎ，Ｎ’－（２－メチル－１－イミダゾリルエチル）－アジポアミド、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、２－フェニル－４，５－ジヒドロキシメチルイミダゾール等が挙げられる。
上記酸無水物としては、例えば、テトラヒドロ無水フタル酸、エチレングリコールービス（アンヒドロトリメリテート）等が挙げられる。
これらの熱硬化剤は、単独で用いられてもよいし、２種類以上が併用されてもよい。 The sealing agent for organic electroluminescence display elements of the present invention may contain a thermosetting agent as long as the object of the present invention is not impaired.
Examples of the thermosetting agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamides, guanidine derivatives, modified aliphatic polyamines, addition products of various amines and epoxy resins, and the like.
Examples of the hydrazide compound include 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin] and the like.
Examples of the imidazole derivative 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) -adipamide, 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole.
Examples of the acid anhydride include tetrahydrophthalic anhydride, ethylene glycol bis (anhydro trimellitate), and the like.
These thermosetting agents may be used alone or in combination of two or more.
本発明の有機エレクトロルミネッセンス表示素子用封止剤は、本発明の目的を阻害しない範囲において、表面改質剤を含有してもよい。上記表面改質剤を含有することにより、本発明の有機エレクトロルミネッセンス表示素子用封止剤の塗膜の平坦性を向上させることができる。
上記表面改質剤としては、例えば、界面活性剤やレベリング剤等が挙げられる。 The sealing agent for organic electroluminescence display elements of the present invention may contain a surface modifier as long as the object of the present invention is not impaired. By containing the said surface modifier, the flatness of the coating film of the sealing agent for organic electroluminescent display elements of this invention can be improved.
Examples of the surface modifier include surfactants and leveling agents.
上記表面改質剤としては、例えば、界面活性剤やレベリング剤等が挙げられる。 The sealing agent for organic electroluminescence display elements of the present invention may contain a surface modifier as long as the object of the present invention is not impaired. By containing the said surface modifier, the flatness of the coating film of the sealing agent for organic electroluminescent display elements of this invention can be improved.
Examples of the surface modifier include surfactants and leveling agents.
上記界面活性剤や上記レベリング剤としては、例えば、シリコーン系、アクリル系、フッ素系等のものが挙げられる。
上記界面活性剤や上記レベリング剤のうち市販されているものとしては、例えば、ＢＹＫ－３０２、ＢＹＫ－３３１（いずれも、ビックケミー・ジャパン社製）、ＵＶＸ－２７２（楠本化成社製）、サーフロンＳ－６１１（ＡＧＣセイミケミカル社製）等が挙げられる。 Examples of the surfactant and the leveling agent include silicones, acrylics, and fluorines.
Examples of commercially available surfactants and leveling agents include BYK-302, BYK-331 (both manufactured by Big Chemie Japan), UVX-272 (manufactured by Enomoto Kasei), Surflon S, and the like. -611 (manufactured by AGC Seimi Chemical Co., Ltd.).
上記界面活性剤や上記レベリング剤のうち市販されているものとしては、例えば、ＢＹＫ－３０２、ＢＹＫ－３３１（いずれも、ビックケミー・ジャパン社製）、ＵＶＸ－２７２（楠本化成社製）、サーフロンＳ－６１１（ＡＧＣセイミケミカル社製）等が挙げられる。 Examples of the surfactant and the leveling agent include silicones, acrylics, and fluorines.
Examples of commercially available surfactants and leveling agents include BYK-302, BYK-331 (both manufactured by Big Chemie Japan), UVX-272 (manufactured by Enomoto Kasei), Surflon S, and the like. -611 (manufactured by AGC Seimi Chemical Co., Ltd.).
本発明の有機エレクトロルミネッセンス表示素子用封止剤は、本発明の目的を阻害しない範囲で、素子電極の耐久性を向上させるために、有機エレクトロルミネッセンス表示素子用封止剤中に発生した酸と反応する化合物又はイオン交換樹脂を含有してもよい。
The sealing agent for organic electroluminescence display elements of the present invention includes an acid generated in the sealing agent for organic electroluminescence display elements in order to improve the durability of the element electrode within a range not impairing the object of the present invention. You may contain the compound or ion exchange resin which reacts.
上記発生した酸と反応する化合物としては、酸と中和する物質、例えば、アルカリ金属の炭酸塩若しくは炭酸水素塩、又は、アルカリ土類金属の炭酸塩若しくは炭酸水素塩等が挙げられる。具体的には例えば、炭酸カルシウム、炭酸水素カルシウム、炭酸ナトリウム、炭酸水素ナトリウム等が用いられる。
Examples of the compound that reacts with the generated acid include substances that neutralize the acid, for example, alkali metal carbonates or bicarbonates, or alkaline earth metal carbonates or bicarbonates. Specifically, for example, calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate and the like are used.
上記イオン交換樹脂としては、陽イオン交換型、陰イオン交換型、両イオン交換型のいずれも使用することができるが、特に塩化物イオンを吸着することのできる陽イオン交換型又は両イオン交換型が好適である。
As the ion exchange resin, any of a cation exchange type, an anion exchange type, and a both ion exchange type can be used, and in particular, a cation exchange type or a both ion exchange type capable of adsorbing chloride ions. Is preferred.
また、本発明の有機エレクトロルミネッセンス表示素子用封止剤は、本発明の目的を阻害しない範囲で、必要に応じて、硬化遅延剤、補強剤、軟化剤、可塑剤、粘度調整剤、紫外線吸収剤、酸化防止剤等の公知の各種添加剤を含有してもよい。
Moreover, the sealing agent for organic electroluminescence display elements of the present invention is a range that does not impair the object of the present invention, and if necessary, a curing retarder, a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, an ultraviolet absorber. You may contain well-known various additives, such as an agent and antioxidant.
本発明の有機エレクトロルミネッセンス表示素子用封止剤を製造する方法としては、例えば、ホモディスパー、ホモミキサー、万能ミキサー、プラネタリーミキサー、ニーダー、３本ロール等の混合機を用いて、カチオン重合性化合物と、カチオン重合開始剤と、必要に応じて添加するシランカップリング剤等の添加剤とを混合する方法等が挙げられる。
Examples of the method for producing the organic electroluminescent display element sealant of the present invention include cationic polymerization using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll. Examples thereof include a method of mixing a compound, a cationic polymerization initiator, and an additive such as a silane coupling agent added as necessary.
本発明の有機エレクトロルミネッセンス表示素子用封止剤は、Ｅ型粘度計を用いて、２５℃、５０ｒｐｍの条件で測定した全体の粘度の下限が５０ｍＰａ・ｓ、上限が２５０ｍＰａ・ｓである。上記粘度が５０ｍＰａ・ｓ未満であると、得られる有機エレクトロルミネッセンス表示素子用封止剤が塗布性に劣るものとなったり、組成ムラが発生して硬化物が透明性に劣るものとなったりする。上記粘度が２５０ｍＰａ・ｓを超えると、得られる有機エレクトロルミネッセンス表示素子用封止剤が塗布性に劣るものとなる。上記粘度は、７０ｍＰａ・ｓ以上１００ｍＰａ・ｓ未満であることが好ましい。
The sealing agent for organic electroluminescence display elements of the present invention has an overall viscosity lower limit of 50 mPa · s and an upper limit of 250 mPa · s measured using an E-type viscometer at 25 ° C. and 50 rpm. When the viscosity is less than 50 mPa · s, the obtained sealing agent for organic electroluminescence display elements is inferior in applicability or composition unevenness occurs and the cured product is inferior in transparency. . When the viscosity exceeds 250 mPa · s, the obtained sealing agent for organic electroluminescence display elements is inferior in applicability. The viscosity is preferably 70 mPa · s or more and less than 100 mPa · s.
本発明によれば、アウトガスの発生を抑制することができ、保存安定性及び塗布性に優れる有機エレクトロルミネッセンス表示素子用封止剤を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of outgas can be suppressed and the sealing compound for organic electroluminescent display elements which is excellent in storage stability and applicability | paintability can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
カチオン重合性化合物として、上記式（１－１）で表される化合物（ダイセル社製、「セロキサイド８０００」）５０重量部及び上記式（１－２）で表される化合物（ダイセル社製、「セロキサイド２０２１Ｐ」）５０重量部と、熱カチオン重合開始剤として、アンチモン系開始剤（Ｋｉｎｇ Ｉｎｄｕｓｔｒｉｅｓ社製、「ＣＸＣ１６１２」）０．５重量部とを、撹拌混合機（シンキー社製、「ＡＲ－２５０」）を用い、撹拌速度３０００ｒｐｍで均一に撹拌混合して、有機エレクトロルミネッセンス表示素子用封止剤を作製した。 Example 1
As a cationically polymerizable compound, 50 parts by weight of a compound represented by the above formula (1-1) (manufactured by Daicel, “Celoxide 8000”) and a compound represented by the above formula (1-2) (manufactured by Daicel, “ 50 parts by weight of Celoxide 2021P ") and 0.5 parts by weight of an antimony initiator (manufactured by King Industries," CXC1612 ") as a thermal cationic polymerization initiator, a stirring mixer (" AR-250, manufactured by Shinky Corporation). )), And the mixture was uniformly stirred and mixed at a stirring speed of 3000 rpm to prepare an organic electroluminescence display element sealant.
カチオン重合性化合物として、上記式（１－１）で表される化合物（ダイセル社製、「セロキサイド８０００」）５０重量部及び上記式（１－２）で表される化合物（ダイセル社製、「セロキサイド２０２１Ｐ」）５０重量部と、熱カチオン重合開始剤として、アンチモン系開始剤（Ｋｉｎｇ Ｉｎｄｕｓｔｒｉｅｓ社製、「ＣＸＣ１６１２」）０．５重量部とを、撹拌混合機（シンキー社製、「ＡＲ－２５０」）を用い、撹拌速度３０００ｒｐｍで均一に撹拌混合して、有機エレクトロルミネッセンス表示素子用封止剤を作製した。 Example 1
As a cationically polymerizable compound, 50 parts by weight of a compound represented by the above formula (1-1) (manufactured by Daicel, “Celoxide 8000”) and a compound represented by the above formula (1-2) (manufactured by Daicel, “ 50 parts by weight of Celoxide 2021P ") and 0.5 parts by weight of an antimony initiator (manufactured by King Industries," CXC1612 ") as a thermal cationic polymerization initiator, a stirring mixer (" AR-250, manufactured by Shinky Corporation). )), And the mixture was uniformly stirred and mixed at a stirring speed of 3000 rpm to prepare an organic electroluminescence display element sealant.
（実施例２～１０、比較例１～９）
表１、２に記載された各材料を、表１に記載された配合比に従い、実施例１と同様にして撹拌混合して、実施例２～１０、比較例１～９の有機エレクトロルミネッセンス表示素子用封止剤を作製した。 (Examples 2 to 10, Comparative Examples 1 to 9)
The materials described in Tables 1 and 2 were stirred and mixed in the same manner as in Example 1 according to the blending ratios described in Table 1, and organic electroluminescence displays of Examples 2 to 10 and Comparative Examples 1 to 9 were made. An element sealant was prepared.
表１、２に記載された各材料を、表１に記載された配合比に従い、実施例１と同様にして撹拌混合して、実施例２～１０、比較例１～９の有機エレクトロルミネッセンス表示素子用封止剤を作製した。 (Examples 2 to 10, Comparative Examples 1 to 9)
The materials described in Tables 1 and 2 were stirred and mixed in the same manner as in Example 1 according to the blending ratios described in Table 1, and organic electroluminescence displays of Examples 2 to 10 and Comparative Examples 1 to 9 were made. An element sealant was prepared.
＜評価＞
実施例及び比較例で得られた各有機エレクトロルミネッセンス表示素子用封止剤について以下の評価を行った。結果を表１、２に示した。 <Evaluation>
The following evaluation was performed about each sealing agent for organic electroluminescent display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
実施例及び比較例で得られた各有機エレクトロルミネッセンス表示素子用封止剤について以下の評価を行った。結果を表１、２に示した。 <Evaluation>
The following evaluation was performed about each sealing agent for organic electroluminescent display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
（１）粘度
実施例及び比較例で得られた各有機エレクトロルミネッセンス表示素子用封止剤について、Ｅ型粘度計（東機産業社製、「ＶＩＳＣＯＭＥＴＥＲ ＴＶ－２２」）を用いて、２５℃、５０ｒｐｍの条件における粘度を測定した。 (1) Viscosity About each sealing agent for organic electroluminescence display elements obtained in Examples and Comparative Examples, using an E-type viscometer (“VISCOMETER TV-22” manufactured by Toki Sangyo Co., Ltd.), The viscosity at 50 rpm was measured.
実施例及び比較例で得られた各有機エレクトロルミネッセンス表示素子用封止剤について、Ｅ型粘度計（東機産業社製、「ＶＩＳＣＯＭＥＴＥＲ ＴＶ－２２」）を用いて、２５℃、５０ｒｐｍの条件における粘度を測定した。 (1) Viscosity About each sealing agent for organic electroluminescence display elements obtained in Examples and Comparative Examples, using an E-type viscometer (“VISCOMETER TV-22” manufactured by Toki Sangyo Co., Ltd.), The viscosity at 50 rpm was measured.
（２）塗布性
ピペットを用いて実施例及び比較例で得られた各有機エレクトロルミネッセンス表示素子用封止剤０．１ｍＬをガラス基板上に塗布し、１分後に広がった直径を測定した。直径が１５ｍｍ以上だった場合を「◎」、１２ｍｍ以上１５ｍｍ未満であった場合を「○」、１０ｍｍ以上１２ｍｍ未満であった場合を「△」、１０ｍｍ未満であった場合を「×」として、塗布性を評価した。 (2) 0.1 mL of each sealing agent for organic electroluminescence display elements obtained in Examples and Comparative Examples was applied on a glass substrate using a coating pipette, and the diameter spread after 1 minute was measured. When the diameter is 15 mm or more, “と し て”, when 12 mm or more and less than 15 mm, “◯”, when 10 mm or more and less than 12 mm, “Δ”, and when less than 10 mm, “×”, The applicability was evaluated.
ピペットを用いて実施例及び比較例で得られた各有機エレクトロルミネッセンス表示素子用封止剤０．１ｍＬをガラス基板上に塗布し、１分後に広がった直径を測定した。直径が１５ｍｍ以上だった場合を「◎」、１２ｍｍ以上１５ｍｍ未満であった場合を「○」、１０ｍｍ以上１２ｍｍ未満であった場合を「△」、１０ｍｍ未満であった場合を「×」として、塗布性を評価した。 (2) 0.1 mL of each sealing agent for organic electroluminescence display elements obtained in Examples and Comparative Examples was applied on a glass substrate using a coating pipette, and the diameter spread after 1 minute was measured. When the diameter is 15 mm or more, “と し て”, when 12 mm or more and less than 15 mm, “◯”, when 10 mm or more and less than 12 mm, “Δ”, and when less than 10 mm, “×”, The applicability was evaluated.
（３）保存安定性
実施例及び比較例で得られた各有機エレクトロルミネッセンス表示素子用封止剤について、製造直後の初期粘度と、２５℃で１週間保管したときの粘度とを測定し、（２５℃、１週間保管後の粘度）／（初期粘度）を粘度変化率とし、粘度変化率が１５０％未満であるものを「◎」、１５０％以上２００％未満であるものを「○」、２００％以上４００％未満であるものを「△」、４００％を超えるものを「×」として保存安定性を評価した。
なお、有機エレクトロルミネッセンス表示素子用封止剤の粘度は、Ｅ型粘度計（東機産業社製、「ＶＩＳＣＯＭＥＴＥＲ ＴＶ－２２」）を用いて、２５℃、５０ｒｐｍの条件で測定した。 (3) Storage stability About each sealing agent for organic electroluminescent display elements obtained by the Example and the comparative example, the initial viscosity immediately after manufacture and the viscosity when stored at 25 degreeC for 1 week are measured, ( (Viscosity after storage at 25 ° C. for 1 week) / (Initial viscosity) is the rate of change in viscosity, “を” indicates that the rate of change in viscosity is less than 150%, “○” indicates that the rate is 150% or more and less than 200% Storage stability was evaluated by assigning “Δ” to 200% or more and less than 400% and “×” to exceed 400%.
In addition, the viscosity of the sealing agent for organic electroluminescence display elements was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “VISCOMETER TV-22”) at 25 ° C. and 50 rpm.
実施例及び比較例で得られた各有機エレクトロルミネッセンス表示素子用封止剤について、製造直後の初期粘度と、２５℃で１週間保管したときの粘度とを測定し、（２５℃、１週間保管後の粘度）／（初期粘度）を粘度変化率とし、粘度変化率が１５０％未満であるものを「◎」、１５０％以上２００％未満であるものを「○」、２００％以上４００％未満であるものを「△」、４００％を超えるものを「×」として保存安定性を評価した。
なお、有機エレクトロルミネッセンス表示素子用封止剤の粘度は、Ｅ型粘度計（東機産業社製、「ＶＩＳＣＯＭＥＴＥＲ ＴＶ－２２」）を用いて、２５℃、５０ｒｐｍの条件で測定した。 (3) Storage stability About each sealing agent for organic electroluminescent display elements obtained by the Example and the comparative example, the initial viscosity immediately after manufacture and the viscosity when stored at 25 degreeC for 1 week are measured, ( (Viscosity after storage at 25 ° C. for 1 week) / (Initial viscosity) is the rate of change in viscosity, “を” indicates that the rate of change in viscosity is less than 150%, “○” indicates that the rate is 150% or more and less than 200% Storage stability was evaluated by assigning “Δ” to 200% or more and less than 400% and “×” to exceed 400%.
In addition, the viscosity of the sealing agent for organic electroluminescence display elements was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “VISCOMETER TV-22”) at 25 ° C. and 50 rpm.
（４）アウトガス防止性
実施例及び比較例で得られた各有機エレクトロルミネッセンス表示素子用封止剤を、バイアル瓶中に３００ｍｇ計量して封入した後、実施例１～７及び比較例１～９で得られた各有機エレクトロルミネッセンス表示素子用封止剤については、１００℃で３０分間加熱を行うことで硬化させ、実施例８～１０で得られた各有機エレクトロルミネッセンス表示素子用封止剤については、紫外線照射装置（オーク社製、「ＪＬ－４３００－３Ｓ」）を用いて紫外線を１５００ｍＪ／ｃｍ２照射し、その後８０℃で３０分加熱して硬化させた。更に、このバイアル瓶を８５℃の恒温オーブンで１００時間加熱し、バイアル瓶中の気化成分を、ガスクロマトグラフ質量分析計（日本電子社製、「ＪＭＳ－Ｑ１０５０」）を用いて測定した。
気化成分量が３０ｐｐｍ未満であった場合を「◎」、３０ｐｐｍ以上５０ｐｐｍ未満であった場合を「○」、５０ｐｐｍ以上１００ｐｐｍ未満であった場合を「△」、１００ｐｐｍ以上であった場合を「×」としてアウトガス防止性を評価した。 (4) Outgassing prevention performance Each of the organic electroluminescence display element sealants obtained in the Examples and Comparative Examples was weighed and sealed in a vial bottle, and then Examples 1 to 7 and Comparative Examples 1 to 9 were used. About each sealing agent for organic electroluminescent display elements obtained in Example 8 to 10 was cured by heating at 100 ° C. for 30 minutes, and each sealing agent for organic electroluminescent display elements obtained in Examples 8 to 10 was used. Was irradiated with ultraviolet rays at 1500 mJ / cm 2 using an ultraviolet irradiation device (“JL-4300-3S” manufactured by Oak Co.), and then heated at 80 ° C. for 30 minutes to be cured. Furthermore, this vial was heated in a constant temperature oven at 85 ° C. for 100 hours, and the vaporized components in the vial were measured using a gas chromatograph mass spectrometer (“JMS-Q1050” manufactured by JEOL Ltd.).
The case where the amount of vaporized component was less than 30 ppm was “◎”, the case where it was 30 ppm or more and less than 50 ppm was “◯”, the case where it was 50 ppm or more and less than 100 ppm was “Δ”, and the case where it was 100 ppm or more was The outgassing prevention property was evaluated.
実施例及び比較例で得られた各有機エレクトロルミネッセンス表示素子用封止剤を、バイアル瓶中に３００ｍｇ計量して封入した後、実施例１～７及び比較例１～９で得られた各有機エレクトロルミネッセンス表示素子用封止剤については、１００℃で３０分間加熱を行うことで硬化させ、実施例８～１０で得られた各有機エレクトロルミネッセンス表示素子用封止剤については、紫外線照射装置（オーク社製、「ＪＬ－４３００－３Ｓ」）を用いて紫外線を１５００ｍＪ／ｃｍ２照射し、その後８０℃で３０分加熱して硬化させた。更に、このバイアル瓶を８５℃の恒温オーブンで１００時間加熱し、バイアル瓶中の気化成分を、ガスクロマトグラフ質量分析計（日本電子社製、「ＪＭＳ－Ｑ１０５０」）を用いて測定した。
気化成分量が３０ｐｐｍ未満であった場合を「◎」、３０ｐｐｍ以上５０ｐｐｍ未満であった場合を「○」、５０ｐｐｍ以上１００ｐｐｍ未満であった場合を「△」、１００ｐｐｍ以上であった場合を「×」としてアウトガス防止性を評価した。 (4) Outgassing prevention performance Each of the organic electroluminescence display element sealants obtained in the Examples and Comparative Examples was weighed and sealed in a vial bottle, and then Examples 1 to 7 and Comparative Examples 1 to 9 were used. About each sealing agent for organic electroluminescent display elements obtained in Example 8 to 10 was cured by heating at 100 ° C. for 30 minutes, and each sealing agent for organic electroluminescent display elements obtained in Examples 8 to 10 was used. Was irradiated with ultraviolet rays at 1500 mJ / cm 2 using an ultraviolet irradiation device (“JL-4300-3S” manufactured by Oak Co.), and then heated at 80 ° C. for 30 minutes to be cured. Furthermore, this vial was heated in a constant temperature oven at 85 ° C. for 100 hours, and the vaporized components in the vial were measured using a gas chromatograph mass spectrometer (“JMS-Q1050” manufactured by JEOL Ltd.).
The case where the amount of vaporized component was less than 30 ppm was “◎”, the case where it was 30 ppm or more and less than 50 ppm was “◯”, the case where it was 50 ppm or more and less than 100 ppm was “Δ”, and the case where it was 100 ppm or more was The outgassing prevention property was evaluated.
本発明によれば、アウトガスの発生を抑制することができ、保存安定性及び塗布性に優れる有機エレクトロルミネッセンス表示素子用封止剤を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of outgas can be suppressed and the sealing compound for organic electroluminescent display elements which is excellent in storage stability and applicability | paintability can be provided.
Claims (3)
- カチオン重合性化合物とカチオン重合開始剤とを含有する有機エレクトロルミネッセンス表示素子用封止剤であって、
前記カチオン重合性化合物は、下記式（１－１）で表される化合物及び／又は下記式（１－２）で表される化合物を含有し、
Ｅ型粘度計を用いて、２５℃、５０ｒｐｍの条件で測定した粘度が５０～２５０ｍＰａ・ｓである
ことを特徴とする有機エレクトロルミネッセンス表示素子用封止剤。
The cationically polymerizable compound contains a compound represented by the following formula (1-1) and / or a compound represented by the following formula (1-2),
A sealing agent for organic electroluminescence display elements, wherein a viscosity measured using an E-type viscometer at 25 ° C. and 50 rpm is 50 to 250 mPa · s.
- カチオン重合性化合物は、式（１－１）で表される化合物及び式（１－２）で表される化合物の両方を含有することを特徴とする請求項１記載の有機エレクトロルミネッセンス表示素子用封止剤。 2. The organic electroluminescence display device according to claim 1, wherein the cationically polymerizable compound contains both the compound represented by the formula (1-1) and the compound represented by the formula (1-2). Sealant.
- カチオン重合開始剤として、ＢＦ４ －、ＰＦ６ －、ＳｂＦ６ －、又は、（ＢＸ４）－（ただし、Ｘは、少なくとも２つ以上のフッ素若しくはトリフルオロメチル基で置換されたフェニル基を表す）を対アニオンとする、スルホニウム塩、ホスホニウム塩、第４級アンモニウム塩、ジアゾニウム塩、又は、ヨードニウム塩を含有することを特徴とする請求項１又は２記載の有機エレクトロルミネッセンス表示素子用封止剤。 As a cationic polymerization initiator, BF 4 − , PF 6 − , SbF 6 − , or (BX 4 ) − (where X represents a phenyl group substituted with at least two fluorine or trifluoromethyl groups. And a sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt or an iodonium salt. .
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| CN201580006254.7A CN105940767B (en) | 2014-05-20 | 2015-04-30 | Organic electro-luminescent display unit sealant |
| KR1020227022636A KR20220098297A (en) | 2014-05-20 | 2015-04-30 | Sealing agent for organic electroluminescence display element |
| KR1020167009505A KR102418079B1 (en) | 2014-05-20 | 2015-04-30 | Sealing agent for organic electroluminescence display element |
| JP2015524558A JP5887467B1 (en) | 2014-05-20 | 2015-04-30 | Sealant for organic electroluminescence display element |
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| WO2017094584A1 (en) * | 2015-12-02 | 2017-06-08 | 株式会社スリーボンド | Cation-curable resin composition |
| WO2017099055A1 (en) * | 2015-12-08 | 2017-06-15 | 株式会社ダイセル | Sealing composition |
| WO2017175735A1 (en) * | 2016-04-06 | 2017-10-12 | 株式会社スリーボンド | Cationic-curable resin composition |
| WO2018221363A1 (en) * | 2017-06-02 | 2018-12-06 | 積水化学工業株式会社 | Sealing agent for organic el display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2016146347A (en) | 2016-08-12 |
| JP5887467B1 (en) | 2016-03-16 |
| CN105940767B (en) | 2018-02-09 |
| KR102418079B1 (en) | 2022-07-06 |
| JPWO2015178186A1 (en) | 2017-04-20 |
| CN105940767A (en) | 2016-09-14 |
| TW201602222A (en) | 2016-01-16 |
| KR20220098297A (en) | 2022-07-11 |
| TWI636090B (en) | 2018-09-21 |
| KR20170012183A (en) | 2017-02-02 |
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