CN108699216B - Curable resin composition and sealing agent for organic electroluminescent display element - Google Patents
Curable resin composition and sealing agent for organic electroluminescent display element Download PDFInfo
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- CN108699216B CN108699216B CN201780011598.6A CN201780011598A CN108699216B CN 108699216 B CN108699216 B CN 108699216B CN 201780011598 A CN201780011598 A CN 201780011598A CN 108699216 B CN108699216 B CN 108699216B
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- resin composition
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- 239000011342 resin composition Substances 0.000 title claims abstract description 63
- 238000007789 sealing Methods 0.000 title claims description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 23
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 20
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000004450 alkenylene group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000000565 sealant Substances 0.000 claims abstract description 7
- -1 oxetane compound Chemical class 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 150000001768 cations Chemical class 0.000 claims 1
- 125000005724 cycloalkenylene group Chemical group 0.000 claims 1
- 239000010408 film Substances 0.000 description 21
- 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 16
- 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 15
- 239000000758 substrate Substances 0.000 description 15
- 238000001723 curing Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 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 6
- 230000000694 effects Effects 0.000 description 6
- 229910010272 inorganic material Inorganic materials 0.000 description 6
- 239000011147 inorganic material Substances 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- LTYMSROWYAPPGB-UHFFFAOYSA-O diphenylsulfanium Chemical compound C=1C=CC=CC=1[SH+]C1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-O 0.000 description 4
- 238000013007 heat curing Methods 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 3
- 238000010943 off-gassing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- LFKLPJRVSHJZPL-UHFFFAOYSA-N 1,2:7,8-diepoxyoctane Chemical compound C1OC1CCCCC1CO1 LFKLPJRVSHJZPL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 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
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 230000008033 biological extinction Effects 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 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
- 230000005525 hole transport Effects 0.000 description 2
- 150000002460 imidazoles Chemical class 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
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GJEZBVHHZQAEDB-SYDPRGILSA-N (1s,5r)-6-oxabicyclo[3.1.0]hexane Chemical compound C1CC[C@H]2O[C@H]21 GJEZBVHHZQAEDB-SYDPRGILSA-N 0.000 description 1
- VLTYTTRXESKBKI-UHFFFAOYSA-N (2,4-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 VLTYTTRXESKBKI-UHFFFAOYSA-N 0.000 description 1
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical class CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- NQEJEMZJOBCYOD-UHFFFAOYSA-N (4-methoxyphenyl)methyl-dimethyl-phenylazanium Chemical compound C1=CC(OC)=CC=C1C[N+](C)(C)C1=CC=CC=C1 NQEJEMZJOBCYOD-UHFFFAOYSA-N 0.000 description 1
- QKAIFCSOWIMRJG-UHFFFAOYSA-N (4-methylphenyl)-(4-propan-2-ylphenyl)iodanium Chemical compound C1=CC(C(C)C)=CC=C1[I+]C1=CC=C(C)C=C1 QKAIFCSOWIMRJG-UHFFFAOYSA-N 0.000 description 1
- YWFPXWMSGJXUFS-UPHRSURJSA-N (4z)-9-oxabicyclo[6.1.0]non-4-ene Chemical compound C1C\C=C/CCC2OC21 YWFPXWMSGJXUFS-UPHRSURJSA-N 0.000 description 1
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- USGYMDAUQBQWFU-UHFFFAOYSA-N 1,2,5,6-diepoxycyclooctane Chemical compound C1CC2OC2CCC2OC12 USGYMDAUQBQWFU-UHFFFAOYSA-N 0.000 description 1
- FQJUJAALMJSTOI-UHFFFAOYSA-N 1-(1h-imidazol-2-yl)propylurea Chemical compound NC(=O)NC(CC)C1=NC=CN1 FQJUJAALMJSTOI-UHFFFAOYSA-N 0.000 description 1
- 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
- XMDQJXIEKHMDMG-UHFFFAOYSA-N 1-methyl-6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21C XMDQJXIEKHMDMG-UHFFFAOYSA-N 0.000 description 1
- AFCZSFUPWLSMSZ-UHFFFAOYSA-N 11-oxabicyclo[8.1.0]undecane Chemical compound C1CCCCCCCC2OC21 AFCZSFUPWLSMSZ-UHFFFAOYSA-N 0.000 description 1
- VLJLXEKIAALSJE-UHFFFAOYSA-N 13-oxabicyclo[10.1.0]tridecane Chemical compound C1CCCCCCCCCC2OC21 VLJLXEKIAALSJE-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- VDAIJDKQXDCJSI-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethylurea Chemical compound CC1=NC=CN1CCNC(N)=O VDAIJDKQXDCJSI-UHFFFAOYSA-N 0.000 description 1
- HTJFSXYVAKSPNF-UHFFFAOYSA-N 2-[2-(oxiran-2-yl)ethyl]oxirane Chemical compound C1OC1CCC1CO1 HTJFSXYVAKSPNF-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- UWQPDVZUOZVCBH-UHFFFAOYSA-N 2-diazonio-4-oxo-3h-naphthalen-1-olate Chemical class C1=CC=C2C(=O)C(=[N+]=[N-])CC(=O)C2=C1 UWQPDVZUOZVCBH-UHFFFAOYSA-N 0.000 description 1
- PNPLRTWSLDSFET-UHFFFAOYSA-N 2-naphthalen-1-yl-5-phenyl-1,3,4-oxadiazole Chemical compound C1=CC=CC=C1C1=NN=C(C=2C3=CC=CC=C3C=CC=2)O1 PNPLRTWSLDSFET-UHFFFAOYSA-N 0.000 description 1
- YUVMLXFOYVPRLD-UHFFFAOYSA-N 3-(2,4-dioxo-5-propan-2-ylimidazolidin-1-yl)propanehydrazide Chemical compound CC(C)C1N(CCC(=O)NN)C(=O)NC1=O YUVMLXFOYVPRLD-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
- MLOZFLXCWGERSM-UHFFFAOYSA-N 8-oxabicyclo[5.1.0]octane Chemical compound C1CCCCC2OC21 MLOZFLXCWGERSM-UHFFFAOYSA-N 0.000 description 1
- KSMGAOMUPSQGTB-UHFFFAOYSA-N 9,10-dibutoxyanthracene Chemical compound C1=CC=C2C(OCCCC)=C(C=CC=C3)C3=C(OCCCC)C2=C1 KSMGAOMUPSQGTB-UHFFFAOYSA-N 0.000 description 1
- MELPJGOMEMRMPL-UHFFFAOYSA-N 9-oxabicyclo[6.1.0]nonane Chemical compound C1CCCCCC2OC21 MELPJGOMEMRMPL-UHFFFAOYSA-N 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- MDSLRNKVLVGFAA-UHFFFAOYSA-N C(C=C1)=CC=C1SC(C=C1)=CC=C1[S+](C1=CC=CC=C1)C1=CC=CC=C1.[AsH3] Chemical compound C(C=C1)=CC=C1SC(C=C1)=CC=C1[S+](C1=CC=CC=C1)C1=CC=CC=C1.[AsH3] MDSLRNKVLVGFAA-UHFFFAOYSA-N 0.000 description 1
- KWVNDBRCGPCJLR-UHFFFAOYSA-N C(C=C1)=CC=C1[S+](C1=CC=CC=C1)C1=CC=CC=C1.[AsH3] Chemical compound C(C=C1)=CC=C1[S+](C1=CC=CC=C1)C1=CC=CC=C1.[AsH3] KWVNDBRCGPCJLR-UHFFFAOYSA-N 0.000 description 1
- CKEAMIMZKRUKLM-UHFFFAOYSA-N COC(C=C1)=CC=C1[S+](C(C=C1)=CC=C1OC)C(C=C1)=CC=C1OC.[AsH3] Chemical compound COC(C=C1)=CC=C1[S+](C(C=C1)=CC=C1OC)C(C=C1)=CC=C1OC.[AsH3] CKEAMIMZKRUKLM-UHFFFAOYSA-N 0.000 description 1
- GMXOYEFGMAXIIU-UHFFFAOYSA-N C[N+](CC1=CC(=C(C=C1)C)C)(C1=CC=CC=C1)C Chemical compound C[N+](CC1=CC(=C(C=C1)C)C)(C1=CC=CC=C1)C GMXOYEFGMAXIIU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZFIVKAOQEXOYFY-UHFFFAOYSA-N Diepoxybutane Chemical compound C1OC1C1OC1 ZFIVKAOQEXOYFY-UHFFFAOYSA-N 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- QSBINWBNXWAVAK-PSXMRANNSA-N PE-NMe(16:0/16:0) Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(=O)OCCNC)OC(=O)CCCCCCCCCCCCCCC QSBINWBNXWAVAK-PSXMRANNSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
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- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 1
- 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
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- BFVANNVEMACRTA-UHFFFAOYSA-N [Sb+3].CCCC[P+](CCCC)(CCCC)CCCC Chemical compound [Sb+3].CCCC[P+](CCCC)(CCCC)CCCC BFVANNVEMACRTA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
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- 150000001450 anions Chemical class 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- CFPCDQPUCAECLL-UHFFFAOYSA-N antimony(3+) ethyl(triphenyl)phosphanium Chemical compound [Sb+3].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 CFPCDQPUCAECLL-UHFFFAOYSA-N 0.000 description 1
- LUAKDNCXFXZOEC-UHFFFAOYSA-N antimony(3+);triphenylsulfanium Chemical compound [Sb+3].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 LUAKDNCXFXZOEC-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 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
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AENNXXRRACDJAY-UHFFFAOYSA-N bis(2-dodecylphenyl)iodanium Chemical compound CCCCCCCCCCCCC1=CC=CC=C1[I+]C1=CC=CC=C1CCCCCCCCCCCC AENNXXRRACDJAY-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004465 cycloalkenyloxy group Chemical group 0.000 description 1
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- HYVNJCOHGOONJK-UHFFFAOYSA-N dibenzyl-methyl-phenylazanium Chemical compound C=1C=CC=CC=1C[N+](C=1C=CC=CC=1)(C)CC1=CC=CC=C1 HYVNJCOHGOONJK-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ONRGBXGMVZEZLY-UHFFFAOYSA-N dimethyl-[(4-methylphenyl)methyl]-phenylazanium Chemical compound C1=CC(C)=CC=C1C[N+](C)(C)C1=CC=CC=C1 ONRGBXGMVZEZLY-UHFFFAOYSA-N 0.000 description 1
- OWZDULOODZHVCQ-UHFFFAOYSA-N diphenyl-(4-phenylsulfanylphenyl)sulfanium Chemical compound C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC1=CC=CC=C1 OWZDULOODZHVCQ-UHFFFAOYSA-N 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
- IYPLTVKTLDQUGG-UHFFFAOYSA-N dodeca-1,11-diene Chemical compound C=CCCCCCCCCC=C IYPLTVKTLDQUGG-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 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
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 125000006502 nitrobenzyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- PSIKPHJLTVSQFO-UHFFFAOYSA-N propanedihydrazide Chemical compound NNC(=O)CC(=O)NN PSIKPHJLTVSQFO-UHFFFAOYSA-N 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
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 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
- 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
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- 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
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/871—Self-supporting sealing arrangements
- H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
- Epoxy Resins (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Sealing Material Composition (AREA)
Abstract
The purpose of the present invention is to provide a curable resin composition which can suppress the generation of outgas and has excellent coatability. Another object of the present invention is to provide a sealant for an organic electroluminescent display element, which contains the curable resin composition. The present invention is a curable resin composition containing a cationically polymerizable compound and a cationic polymerization initiator, wherein the cationically polymerizable compound contains at least 1 selected from the group consisting of a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3). In the formula (1-1), R1A bond, a straight-chain or branched alkylene group having 1 to 18 carbon atoms, or a straight-chain or branched alkenylene group having 2 to 18 carbon atoms; r2And R3Each independently represents hydrogen or a straight or branched alkyl group having 1 to 18 carbon atoms. In the formula (1-2), R4Is a straight-chain or branched alkylene group having 3 to 18 carbon atoms or a straight-chain or branched alkenylene group having 3 to 18 carbon atoms; r5And R6Each independently represents hydrogen or a straight or branched alkyl group having 1 to 18 carbon atoms. In the formula (1-3), R7And R8Each independently is a linear or branched alkylene group having 1 to 18 carbon atoms or a linear or branched alkenylene group having 2 to 18 carbon atoms; r9～R12Each independently represents hydrogen or a straight or branched alkyl group having 1 to 18 carbon atoms.
Description
Technical Field
The present invention relates to a curable resin composition which can suppress the generation of outgas and has excellent coatability. The present invention also relates to a sealant for an organic electroluminescent display element, which contains the curable resin composition.
Background
In recent years, research has been conducted on electronic devices using organic thin film elements such as organic electroluminescent display elements (organic EL display elements) and organic thin film solar cell elements. The organic thin film element can be easily produced by vacuum deposition, solution coating, or the like, and therefore has excellent productivity.
An organic EL display device has a thin-film structure in which an organic light-emitting material layer is sandwiched between a pair of electrodes facing each other. By injecting electrons from one electrode to the organic light emitting material layer and injecting holes from the other electrode to the organic light emitting material layer, the electrons and the holes are combined in the organic light emitting material layer and self-luminescence is performed. Compared with a liquid crystal display element or the like which requires a backlight, the liquid crystal display device has advantages that visibility is good, thinning can be further achieved, and direct-current low-voltage driving can be performed.
However, such an organic EL display element has a problem that when the organic light emitting material layer or the electrode is exposed to the outdoor air, its light emitting characteristics are rapidly deteriorated and its lifetime is shortened. Therefore, in order to improve stability and durability, a sealing technique for blocking an organic light emitting material layer and an electrode from moisture and oxygen in the atmosphere is indispensable for an organic EL display element.
Patent document 1 discloses a method in which, in a top emission type organic EL display device or the like, a photocurable adhesive is filled between organic EL display device substrates, and light is irradiated to seal the organic EL display device substrates. However, such a conventional photocurable adhesive has a problem that outgassing occurs upon light irradiation, and thus the element is deteriorated or the applicability is deteriorated.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2001-357973
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a curable resin composition which can suppress the generation of outgas and has excellent coatability. Another object of the present invention is to provide a sealant for an organic electroluminescent display element, which contains the curable resin composition.
Means for solving the problems
The present invention is a curable resin composition containing a cationically polymerizable compound and a cationic polymerization initiator, wherein the cationically polymerizable compound contains at least 1 selected from the group consisting of a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3).
[ solution 1]
In the formula (1-1), R1A bond, a straight-chain or branched alkylene group having 1 to 18 carbon atoms, or a straight-chain or branched alkenylene group having 2 to 18 carbon atoms; r2And R3Each independently represents hydrogen or a straight or branched alkyl group having 1 to 18 carbon atoms. In the formula (1-2), R4Is a straight-chain or branched alkylene group having 3 to 18 carbon atoms or a straight-chain or branched alkenylene group having 3 to 18 carbon atoms; r5And R6Each independently represents hydrogen or a straight or branched alkyl group having 1 to 18 carbon atoms. In the formula (1-3), R7And R8Each independently is a linear or branched alkylene group having 1 to 18 carbon atoms or a linear or branched alkenylene group having 2 to 18 carbon atoms; r9～R12Each independently represents hydrogen or a straight or branched alkyl group having 1 to 18 carbon atoms.
The present invention is described in detail below.
The inventor finds that: the use of a specific cationically polymerizable compound enables to obtain a curable resin composition which can suppress the generation of outgas and has excellent coatability, and the present invention has been completed.
The curable resin composition of the present invention contains a cationically polymerizable compound.
The cationically polymerizable compound contains at least 1 kind selected from the group consisting of the compound represented by the formula (1-1), the compound represented by the formula (1-2) and the compound represented by the formula (1-3) (hereinafter, also referred to as "epoxy compound according to the present invention"). By containing the epoxy compound of the present invention, the curable resin composition of the present invention can suppress the generation of outgas and has excellent coatability. Further, by containing the epoxy compound of the present invention, the obtained curable resin composition has excellent flexibility after curing, and can be applied to flexible electronic devices.
R in the above formula (1-1) is selected from the viewpoint of compatibility with other components and hardness of a cured product1R in the above formula (1-2)4And R in the above formula (1-3)7And R8Preferably a linear or branched alkylene group having 1 to 18 carbon atoms, more preferably a linear or branched alkylene group having 3 to 12 carbon atoms.
Examples of the compound represented by the formula (1-1) include 1, 3-butadiene diepoxide, 1, 5-hexadiene diepoxide, 1, 7-octadiene diepoxide, 1, 9-decadiene diepoxide, 1, 11-dodecadiene diepoxide, and the like.
Examples of the compound represented by the formula (1-2) include 1, 2-epoxycyclopentane, 1, 2-epoxycyclohexane, 1, 2-epoxycycloheptane, 1, 2-epoxycyclooctane, 1, 2-epoxycyclodecane, 1, 2-epoxycyclododecane, 1-methyl-1, 2-epoxycyclopentane, 5, 6-epoxy-1-cyclooctene and the like.
Examples of the compound represented by the formula (1-3) include 1, 2, 5, 6-diepoxycyclooctane, and the like.
Examples of commercially available products among the epoxy compounds of the present invention include reagents manufactured by Tokyo chemical industries, Ltd.
Among them, the cationically polymerizable compound preferably contains a compound represented by the formula (1-1) above, and more preferably contains 1, 7-octadiene diepoxide, from the viewpoint that the obtained curable resin composition is particularly excellent in curability and flexibility after curing.
The curable resin composition of the present invention may contain other cationically polymerizable compounds within a range not impairing the object of the present invention.
Examples of the other cationically polymerizable compound include other epoxy compounds such as a compound having 2 or more cycloalkenyloxy groups in 1 molecule, a bisphenol a type epoxy resin, and a bisphenol F type epoxy resin; oxetane compounds, vinyl ether compounds, and the like. Among these, from the viewpoint of more excellent curability of the obtained curable resin composition, a compound having 2 or more oxyalkylene groups in 1 molecule is preferable, and a compound having 2 or more oxycyclohexenyl groups in 1 molecule is more preferable.
Examples of the compound having 2 or more cyclohexene oxide groups in the molecule of 1 include 3 ', 4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate.
When the other cationically polymerizable compound is contained, the lower limit of the content of the epoxy compound in the present invention is preferably 10 parts by weight, and the upper limit is preferably 90 parts by weight, based on 100 parts by weight of the entire cationically polymerizable compound. When the content of the epoxy compound of the present invention is in this range, the obtained curable resin composition is more excellent in coatability, outgas-suppressing effect and flexibility. The lower limit of the content of the epoxy compound in the present invention is more preferably 20 parts by weight, the upper limit is more preferably 80 parts by weight, and the upper limit is more preferably 50 parts by weight.
The curable resin composition of the present invention contains a cationic polymerization initiator.
Examples of the cationic polymerization initiator include a thermal cationic polymerization initiator which generates a protonic acid or a lewis acid by heating, and a photo cationic polymerization initiator which generates a protonic acid or a lewis acid by light irradiation, and may be of an ionic acid-generating type or a nonionic acid-generating type.
As the thermal cationic polymerization initiator, BF is preferred4 -、PF6 -、SbF6 -Or (BX)4)-(wherein X represents a phenyl group substituted with at least 2 or more fluorine groups or trifluoromethyl groups) as a counter anion, and a sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt or an iodonium salt, more preferably a sulfonium salt.
Examples of the sulfonium salt include triphenylsulfonium boron tetrafluoride, triphenylsulfonium antimony hexafluoride, triphenylsulfonium arsenic hexafluoride, tris (4-methoxyphenyl) sulfonium arsenic hexafluoride, and diphenyl (4-phenylthiophenyl) sulfonium arsenic hexafluoride.
Examples of the phosphonium salt include ethyltriphenylphosphonium antimony hexafluoride, tetrabutylphosphonium antimony hexafluoride and the like.
Examples of the quaternary ammonium salts include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyldibenzylammonium hexafluoroantimonate hexafluorophosphate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3, 4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N, antimony N-dimethyl-N-benzylanilinium hexafluoride, boron N, N-diethyl-N-benzylanilinium tetrafluoride, antimony N, N-dimethyl-N-benzylpyridinium hexafluoride, N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid, and the like.
As the above thermal cationic polymerization initiator, commercially available ones such as San-Aid SI-60, San-Aid SI-80, San-Aid SI-B3, San-Aid SI-B3A, San-Aid SI-B4 (all manufactured by Sanxin chemical Industries Co., Ltd.), CXC-1612, CXC-1738 and CXC-1821 (all manufactured by King Industries Co., Ltd.) can be mentioned.
As an ionic photoacid-generating polymerization initiator among the above photocationic polymerization initiatorsHair agents, for example, those having an anionic moiety consisting of BF4 -、PF6 -、SbF6 -Or (BX)4)-(wherein X represents a phenyl group substituted with at least 2 or more fluorine or trifluoromethyl), an aromatic iodonium salt, an aromatic diazonium salt, an aromatic ammonium salt, or a (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt.
Examples of the aromatic sulfonium salt include bis (4- (diphenylsulfonium) phenyl) sulfide bishexafluoro phosphate, bis (4- (diphenylsulfonium) phenyl) sulfide bishexafluoroantimonate, bis (4- (diphenylsulfonium) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonium) 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, and the like, Bis (4- (2-hydroxyethoxy)) phenylsulfone) phenyl) sulfide bishexafluorophosphate, bis (4- (2-hydroxyethoxy)) phenylsulfone) phenyl) sulfide bishexafluoroantimonate, bis (4- (2-hydroxyethoxy)) phenylsulfone) phenyl) sulfide bistetrafluoroborate, bis (4- (2-hydroxyethoxy)) phenylsulfone) phenyl) sulfide tetrakis (pentafluorophenyl) borate, and the like.
Examples of the aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate, etc.
Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.
Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
Examples of the (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (ii) hexafluorophosphate, (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (ii) hexafluoroantimonate, (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (ii) tetrafluoroborate, and (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (ii) tetrakis (pentafluorophenyl) borate.
Examples of the nonionic photoacid generating polymerization initiator among the above photocationic polymerization initiators include nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenol sulfonic acid esters, diazonaphthoquinones, and N-hydroxyimide sulfonic acid esters.
Examples of commercially available products among the above-mentioned photo cation polymerization initiators include DTS-200 (manufactured by Green chemical Co., Ltd.); UVI6990 and UVI6974 (both manufactured by Union Carbide Co., Ltd.); SP-150 and SP-170 (both manufactured by ADEKA Co., Ltd.); FC-508, FC-512 (both 3M); IRGACURE290(BASF corporation); PI2074 (Rhodia).
The polymerization initiators described in both the thermal cationic polymerization initiator and the photo cationic polymerization initiator may be used as the thermal cationic polymerization initiator or as the photo cationic polymerization initiator.
The lower limit of the content of the cationic polymerization initiator is preferably 0.01 part by weight, and the upper limit is preferably 10 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. By setting the content of the cationic polymerization initiator to 0.01 parts by weight or more, the curability of the obtained curable resin composition becomes more excellent. By setting the content of the cationic polymerization initiator to 10 parts by weight or less, the curing reaction of the obtained curable resin composition does not become too fast, the workability becomes more excellent, and the cured product can be made more uniform. The lower limit of the content of the cationic polymerization initiator is more preferably 0.05 part by weight, and the upper limit is more preferably 5 parts by weight.
The curable resin composition of the present invention may contain a sensitizer. The sensitizer has an effect of further improving the polymerization initiation efficiency of the cationic polymerization initiator and further promoting the curing reaction of the curable resin composition of the present invention.
Examples of the sensitizer include anthracene compounds such as 9, 10-dibutoxyanthracene; thioxanthone compounds such as 2, 4-diethylthioxanthone; 2, 2-dimethoxy-1, 2-diphenylethan-1-one, benzophenone, 2, 4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4 '-bis (dimethylamino) benzophenone, 4-benzoyl-4' -methyldiphenyl sulfide and the like.
The content of the sensitizer is preferably 0.05 parts by weight or less, and preferably 3 parts by weight or more, per 100 parts by weight of the cationically polymerizable compound. The sensitizing agent is contained in an amount of 0.05 part by weight or more, whereby the sensitizing effect can be further exerted. By setting the content of the sensitizer to 3 parts by weight or less, light can be propagated to a deep portion without causing excessive absorption. A more preferable lower limit of the content of the sensitizer is 0.1 part by weight, and a more preferable upper limit is 1 part by weight.
The curable resin composition of the present invention may contain a thermal curing agent. Examples of the heat-curing agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamide, guanidine derivatives, modified aliphatic polyamines, and addition products of various amines and epoxy resins.
Examples of the hydrazide compound include 1, 3-bis (hydrazinocarbonylethyl-5-isopropylhydantoin), sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, malonic dihydrazide 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 '-bis (2-methyl-1-imidazolylethyl) urea, N' - (2-methyl-1-imidazolylethyl) adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4, 5-dihydroxymethylimidazole.
Examples of the acid anhydride include tetrahydrophthalic anhydride and ethylene glycol bis (anhydrotrimellitate).
These heat-curing agents may be used alone, or two or more of them may be used in combination.
Examples of commercially available products among the above-mentioned heat-curing agents include, for example, SDH (manufactured by japan fine chemical industries); ADH (Dazu chemical Co.); amicure VDH, Amicure VDH-J, and Amicure UDH (all manufactured by Ajinomoto Fine-technique).
The lower limit of the content of the heat-curing agent is preferably 0.5 part by weight, and the upper limit is preferably 30 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. When the content of the thermosetting agent is 0.5 parts by weight or more, the thermosetting property of the obtained curable resin composition becomes more excellent. When the content of the thermosetting agent is 30 parts by weight or less, the storage stability of the obtained curable resin composition becomes more excellent, and the moisture resistance of the cured product becomes more excellent. The lower limit of the content of the thermosetting agent is more preferably 1 part by weight, and the upper limit is more preferably 15 parts by weight.
The curable resin composition of the present invention may contain a stabilizer for the purpose of improving storage stability and the like.
Examples of the stabilizer include amine compounds such as benzylamine and the like, and aminophenol type epoxy resins.
The lower limit of the content of the stabilizer is preferably 0.001 part by weight, and the upper limit is preferably 2 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. When the content of the stabilizer is in this range, the effect of suppressing the inhibition of curing and improving the storage stability of the obtained curable resin composition becomes more excellent. The lower limit of the content of the stabilizer is more preferably 0.05 part by weight, and the upper limit is more preferably 1 part by weight.
The curable resin composition of the present invention may contain a silane coupling agent. The silane coupling agent has an effect of improving the adhesion of the curable resin composition of the present invention to a substrate or the like.
Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-isocyanatopropyltrimethoxysilane. These silane coupling agents may be used alone, or two or more of them may be used in combination.
The lower limit of the content of the silane coupling agent is preferably 0.1 part by weight, and the upper limit is preferably 10 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. When the content of the silane coupling agent is in this range, the effect of suppressing bleeding due to an excess silane coupling agent and improving the adhesiveness of the resulting curable resin composition becomes more excellent. The lower limit of the content of the silane coupling agent is more preferably 0.5 part by weight, and the upper limit is more preferably 5 parts by weight.
The curable resin composition of the present invention may contain a surface modifier within a range not impairing the object of the present invention. The surface modifier can improve the flatness of the coating film of the curable resin composition of the present invention.
Examples of the surface modifier include a surfactant and a leveling agent.
Examples of the surface modifier include silicone-based, acrylic, and fluorine-based surface modifiers.
Examples of commercially available surface modifiers include BYK-300, BYK-302 and BYK-331 (all of BYK Chemie Japan); UVX-272 (manufactured by Nanzi chemical Co., Ltd.); surflon S-611 (manufactured by AGC SEIMI CHEMICAL).
The curable resin composition of the present invention may contain a compound or an ion exchange resin that reacts with an acid generated in the curable resin composition in order to improve the durability of the device electrode, within a range that does not impair the object of the present invention.
Examples of the compound that reacts with the generated acid include compounds that neutralize the acid, such as alkali metal carbonates or bicarbonates, or alkaline earth metal carbonates or bicarbonates. Specifically, for example, calcium carbonate, calcium hydrogen carbonate, sodium hydrogen carbonate, or the like can be used.
As the ion exchange resin, any of cation exchange type, anion exchange type, and amphoteric ion exchange type resins can be used, and particularly, cation exchange type or amphoteric ion exchange type capable of adsorbing chloride ions is preferable.
The sealing agent for an organic EL display element of the present invention preferably does not contain a solvent because of the possibility of problems such as deterioration of the organic light-emitting material layer and generation of outgas due to the remaining solvent.
When a solvent is used for adjusting the viscosity or the like, the content of the solvent is preferably 1 wt% or less, more preferably 0.1 wt% or less.
The curable resin composition of the present invention may contain, as necessary, various known additives such as a curing retarder, a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, an ultraviolet absorber, an antioxidant, and a drying agent, within a range not to impair the object of the present invention.
Examples of the method for producing the curable resin composition of the present invention include a method of mixing a cationically polymerizable compound, a cationic polymerization initiator, and, if necessary, an additive such as a silane coupling agent, using a mixer such as a homogenizer, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three-roll mill.
The lower limit of the overall viscosity of the curable resin composition of the present invention measured at 25 ℃ and 50rpm using an E-type viscometer is 5 mPas, and the upper limit thereof is 200 mPas. When the viscosity is within this range, the curable resin composition obtained has more excellent ink jet coatability, and is more suitable as an in-plane sealing agent for organic EL display elements. The viscosity is more preferably 8 mPas at the lower limit and 30 mPas at the upper limit.
The curable resin composition of the present invention is suitably used for sealing, bonding, coating, etc. of electronic devices, and is more suitably used as a sealing agent for electronic devices. Among them, the sealing agent is particularly suitable for use as a sealing agent for an organic EL display element.
Further, a sealant for an organic EL display element comprising the curable resin composition of the present invention is also one aspect of the present invention.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a curable resin composition which can suppress the generation of outgas and has excellent coatability can be provided. Further, according to the present invention, a sealant for an organic electroluminescent display element comprising the curable resin composition can be provided.
Detailed Description
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
(examples 1 to 9 and comparative examples 1 to 5)
The curable resin compositions of examples 1 to 9 and comparative examples 1 to 5 were prepared by uniformly stirring and mixing the respective materials at a stirring speed of 3000rpm using a homomixer type stirrer mixer (manufactured by PRIMIX, "HOMODISPERER L type") in the mixing ratios described in tables 1 and 2.
< evaluation >
The curable resin compositions obtained in examples and comparative examples were evaluated as follows. The results are shown in tables 1 and 2.
(1) Viscosity of the oil
The viscosity of each of the curable resin compositions obtained in examples and comparative examples was measured at 25 ℃ and 50rpm using an E-type VISCOMETER (manufactured by Toyobo industries, Ltd. "VISCOMETER TV-22").
(2) Coatability
0.1mL of each of the curable resin compositions obtained in examples and comparative examples was applied to a glass substrate using a pipette, and the diameter of the spread after 1 minute was measured. The coatability was evaluated by regarding a case where the diameter was 15mm or more as "very good", regarding a case where the diameter was 12mm or more and less than 15mm as "o", regarding a case where the diameter was 10mm or more and less than 12mm as "Δ", and regarding a case where the diameter was less than 10mm as "x".
(3) Curing Properties
Each of the curable resin compositions obtained in examples and comparative examples was irradiated with ultraviolet light at 1500mJ/cm using an ultraviolet irradiation apparatus (manufactured by Quark Technology, "QEL-15 SQ 3W")2The cured product was cured by irradiation with ultraviolet rays of 395 nm. The exothermic amount before and after curing was measured by using a DSC apparatus (manufactured by RIGAKU, "Thermo Plus2/DSC 8230"), and the reaction rate of the epoxy group was derived from the following formula. The curable resin composition obtained in example 8 was cured by heating for 30 minutes at 100 ℃ instead of irradiating with ultraviolet light.
Reaction rate (%) of epoxy group of 100 × (exothermic amount before curing-exothermic amount after curing)/exothermic amount before curing
The curability was evaluated by saying "very good" for the case where the reactivity of the epoxy group was 95% or more, good "for the case where the reactivity was 90% or more and less than 95%, good" for the case where the reactivity was 70% or more and less than 90%, and "x" for the case where the reactivity was less than 70%.
The "heat generation amount before curing" refers to a heat generation amount when an unreacted curable resin composition is reacted by heating at a high temperature and completely cured, and the "heat generation amount after curing" refers to a heat generation amount generated by a reaction of residual functional groups of the cured curable resin composition.
(4) Flexibility
Each of the curable resin compositions obtained in examples and comparative examples was sandwiched between two sheets of PET resin at a thickness of 100 μm, and an ultraviolet irradiation apparatus (Quark Techn) was usedManufactured by Olympy Inc. 'QEL-15 SQ 3W') at 1500mJ/cm2The curable resin composition was cured by irradiation with ultraviolet rays of 395nm to prepare a test film having a thickness of 100 μm. The curable resin composition obtained in example 8 was cured by heating at 100 ℃ for 30 minutes instead of ultraviolet irradiation to prepare a test film.
The flexibility was evaluated by marking the case where the resin film was not broken as "o" and the case where the resin film was broken as "x" when the obtained test film was bent to a curvature of 1cm in diameter.
(5) Low outgassing property
Each of the curable resin compositions obtained in examples and comparative examples was measured at 100mg and sealed in a vial, and the content was measured at 1500mJ/cm using an ultraviolet irradiation apparatus (manufactured by Quark Technology, "QEL-15 SQ 3W")2The curable resin composition was cured by irradiation with ultraviolet rays of 395 nm. Further, the vial was heated in an oven at a constant temperature of 85 ℃ for 100 hours, and the vaporized component in the vial was measured by a gas chromatography mass spectrometer (JMS-Q1050, manufactured by Nippon electronic Co., Ltd.). The curable resin composition obtained in example 8 was cured by heating at 100 ℃ for 30 minutes instead of ultraviolet irradiation.
The low outgassing property was evaluated by marking "O" for the case where the amount of the gasified component was less than 50ppm, marking "A" for the case where the amount of the gasified component was 50ppm or more and less than 100ppm, and marking "X" for the case where the amount of the gasified component was 100ppm or more.
(6) Display performance of organic EL display element
(production of a substrate having a laminate comprising organic light-emitting Material layers)
On a glass substrate (length 30mm, width 30mm, thickness 0.7mm)
The ITO electrode was formed into a film to obtain a substrate. Ultrasonic cleaning the substrate with acetone, alkaline water solution, ion exchange water, and isopropanolAfter washing for 15 minutes, the plate was washed with boiled isopropyl alcohol for 10 minutes, and further subjected to pretreatment with a UV-ozone cleaner (NL-UV 253, manufactured by Nippon laser electronics Co., Ltd.).
Next, the substrate was fixed to a substrate holder of a vacuum deposition apparatus, 200mg of N, N '-bis (1-naphthyl) -N, N' -diphenylbenzidine (. alpha. -NPD) was charged into a bisque-fired crucible, and tris (8-quinolinolato) aluminum (Alq) was charged into a different bisque-fired crucible3)200mg, the pressure in the vacuum chamber was reduced to 1X 10-4Pa. Thereafter, the crucible containing the alpha-NPD is heated to convert the alpha-NPD to
Is deposited on a substrate at a deposition rate to form a film having a thickness
The hole transport layer of (1). Then, the alloy is charged with Alq3Is heated in a crucible to
The deposition rate of (2) is set to a film thickness
The organic light emitting material layer of (1). Thereafter, the substrate on which the hole transport layer and the organic light-emitting material layer were formed was transferred to another vacuum deposition apparatus, and 200mg of lithium fluoride was charged into a tungsten resistance heating boat in the vacuum deposition apparatus, and 1.0g of an aluminum wire was charged into another tungsten boat. Thereafter, the pressure in the evaporator of the vacuum evaporation apparatus was reduced to 2 × 10-4Pa is up to
The deposition rate of (3) is such that lithium fluoride is formed into a film
Then, in order
At a rate of forming aluminum into a film
The inside of the evaporator was returned to normal pressure by nitrogen gas, and the substrate provided with the laminate having the organic light-emitting material layers was taken out.
(covering with inorganic Material film A)
A mask having an opening is provided so as to cover the entire laminate in the resulting substrate on which the laminate is disposed, and the inorganic material film a is formed by a plasma CVD method.
The plasma CVD method was performed under the following conditions: SiH is used as the raw material gas4Gas and nitrogen gas, the respective flow rates being SiH4The gas was 10sccm, the nitrogen gas was 200sccm, the RF power was 10W (frequency: 2.45GHz), the temperature in the chamber was 100 ℃, and the pressure in the chamber was 0.9 Torr.
The thickness of the inorganic material film a formed was about 1 μm.
(formation of resin protective film)
The curable resin compositions obtained in examples and comparative examples were applied to a glass substrate at an ejection rate of 80pL by an inkjet system using an inkjet ejection apparatus (manufactured by microdot, "nanopowder 300"). The coating thickness was adjusted to 20 μm or less during coating. Next, an ultraviolet irradiation apparatus (manufactured by Quark Technology, "QEL-15 SQ 3W") was used at 1500mJ/cm2The curable resin composition was irradiated with ultraviolet rays of 395nm and then heated at 80 ℃ for 30 minutes to be cured, thereby forming a resin protective film. The curable resin composition obtained in example 8 was cured by heating at 100 ℃ for 30 minutes instead of ultraviolet irradiation.
(covering with inorganic Material film B)
After the resin protective film is formed, a mask having an opening is provided so as to cover the entire resin protective film, and an inorganic material film B is formed by a plasma CVD method, whereby an organic EL display element is obtained.
The plasma CVD method was performed under the following conditions: used as raw material gasSiH4Gas and nitrogen gas, the respective flow rates being SiH4The gas was 10sccm, the nitrogen gas was 200sccm, the RF power was 10W (frequency: 2.45GHz), the temperature in the chamber was 100 ℃, and the pressure in the chamber was 0.9 Torr.
The thickness of the inorganic material film B formed was about 1 μm.
(light-emitting state of organic EL display element)
The organic EL display device obtained was exposed to a temperature of 85 ℃ and a humidity of 85% for 100 hours, and then a voltage of 10V was applied to observe the light emission state (presence or absence of light emission and dark spots) of the device by visual observation. The case where the light was uniformly emitted without dark spots and without peripheral extinction was marked as "o"; the case where dark spots and peripheral extinction were confirmed was designated as "Δ"; the case where the non-light-emitting portion was significantly enlarged was evaluated as "x".
[ Table 1]
[ Table 2]
Industrial applicability
According to the present invention, a curable resin composition which can suppress the generation of outgas and has excellent coatability can be provided. Further, according to the present invention, a sealant for an organic electroluminescent display element comprising the curable resin composition can be provided.
Claims (4)
1. A sealing agent for an organic electroluminescent display element, comprising a curable resin composition containing a cationically polymerizable compound and a cationic polymerization initiator,
the cation polymerizable compound contains a compound represented by the following formula (1-1),
the content of the solvent in the sealant for the organic electroluminescent display element is less than 0.1 wt%,
a viscosity of 5 to 200 mPas as measured with an E-type viscometer at 25 ℃ and 50rpm,
in the formula (1-1), R1A bond, a straight-chain or branched alkylene group having 1 to 18 carbon atoms, or a straight-chain or branched alkenylene group having 2 to 18 carbon atoms; r2And R3Each independently represents hydrogen or a straight or branched alkyl group having 1 to 18 carbon atoms.
2. The sealing agent for an organic electroluminescent display element according to claim 1, wherein the cationically polymerizable compound further comprises another cationically polymerizable compound,
the content of the compound represented by the formula (1-1) is 10 parts by weight or more and 90 parts by weight or less in 100 parts by weight of the entire cationically polymerizable compound.
3. The sealing agent for an organic electroluminescent display element according to claim 2, wherein the other cationically polymerizable compound contains at least one selected from the group consisting of a compound having 2 or more cycloalkenylene oxide groups in 1 molecule, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, an oxetane compound, and a vinyl ether compound.
4. The sealing agent for an organic electroluminescent display element according to claim 1 or 2, wherein the viscosity is 5 mPas or more and 30 mPas or less as measured with an E-type viscometer at 25 ℃ and 50 rpm.
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| PCT/JP2017/028025 WO2018030232A1 (en) | 2016-08-08 | 2017-08-02 | Curable resin composition and sealing agent for organic electroluminescent display elements |
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| KR102431016B1 (en) * | 2016-09-16 | 2022-08-09 | 세키스이가가쿠 고교가부시키가이샤 | Encapsulant for organic electroluminescent display elements |
| WO2019188794A1 (en) * | 2018-03-30 | 2019-10-03 | 積水化学工業株式会社 | Sealant for organic el display element |
| CN112074957A (en) * | 2018-04-09 | 2020-12-11 | 积水化学工业株式会社 | Sealing agent for organic EL display element |
| WO2019203123A1 (en) * | 2018-04-20 | 2019-10-24 | 積水化学工業株式会社 | Sealant for organic el display element and top emission type organic el display element |
| WO2020110859A1 (en) * | 2018-11-28 | 2020-06-04 | 積水化学工業株式会社 | Curable resin composition, cured product and organic el display element |
| EP4074681A4 (en) * | 2019-12-11 | 2023-01-25 | Mitsubishi Gas Chemical Company, Inc. | Compound, method for producing same, resin composition, resin sheet, multilayer printed wiring board, and semiconductor device |
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| JP7025209B2 (en) | 2022-02-24 |
| WO2018030232A1 (en) | 2018-02-15 |
| JP2022078065A (en) | 2022-05-24 |
| TW201816007A (en) | 2018-05-01 |
| KR20190035599A (en) | 2019-04-03 |
| CN108699216A (en) | 2018-10-23 |
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| CN114716648A (en) | 2022-07-08 |
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