CN107852790B - Sealing agent for organic electroluminescent display element - Google Patents
Sealing agent for organic electroluminescent display element Download PDFInfo
- Publication number
- CN107852790B CN107852790B CN201680045108.XA CN201680045108A CN107852790B CN 107852790 B CN107852790 B CN 107852790B CN 201680045108 A CN201680045108 A CN 201680045108A CN 107852790 B CN107852790 B CN 107852790B
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- CN
- China
- Prior art keywords
- display element
- sealing agent
- organic electroluminescent
- electroluminescent display
- polymerizable compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000007789 sealing Methods 0.000 title claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 230000001678 irradiating effect Effects 0.000 claims abstract description 4
- 239000000565 sealant Substances 0.000 claims description 33
- 150000001768 cations Chemical class 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 26
- 230000007547 defect Effects 0.000 abstract description 9
- 230000006866 deterioration Effects 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 7
- -1 aromatic iodonium salt Chemical class 0.000 description 43
- 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 17
- 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 16
- 239000010408 film Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 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
- 238000001723 curing Methods 0.000 description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 125000003700 epoxy group Chemical group 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000007872 degassing Methods 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000010943 off-gassing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MCBXLJCOMLRSQK-UHFFFAOYSA-N 2-(4-sulfanylphenoxy)ethanol Chemical compound OCCOC1=CC=C(S)C=C1 MCBXLJCOMLRSQK-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
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 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 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 230000001681 protective effect Effects 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- 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 2
- 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
- FNYWFRSQRHGKJT-UHFFFAOYSA-N 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane Chemical compound C1OCC1(CC)COCC1(CC)COC1 FNYWFRSQRHGKJT-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 compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-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
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000013007 heat curing 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage 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
- 238000001771 vacuum deposition Methods 0.000 description 2
- 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
- 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
- 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
- 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
- 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
- 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-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
- 239000004902 Softening Agent Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-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
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
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- 238000005349 anion exchange Methods 0.000 description 1
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
- ITZGNPZZAICLKA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C2OC2CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 ITZGNPZZAICLKA-UHFFFAOYSA-N 0.000 description 1
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- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
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- 229910000019 calcium carbonate Inorganic materials 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
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- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
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- 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
- 125000006502 nitrobenzyl group Chemical group 0.000 description 1
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
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- 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
Abstract
The purpose of the present invention is to provide a sealing agent for an organic electroluminescent display element, which has excellent adhesion to a flexible substrate or the like and can suppress display defects caused by deterioration of the element. The present invention is a sealing agent for an organic electroluminescent display element, which comprises a cationically polymerizable compound and a cationic polymerization initiator, wherein the cationically polymerizable compound comprises a hydrolyzable cationically polymerizable compound having a cationically polymerizable group and an ether bond or an ester bond, and when the ether bond or the ester bond is cleaved by hydrolysis, all of the decomposition products have a cationically polymerizable group, 300mg of the sealing agent for an organic electroluminescent display element is measured and sealed in a vial, and the sealing agent is cured by heating at 100 ℃ for 30 minutes or irradiating with ultraviolet light at 1500mJ/cm2Then, the mixture was heated at 80 ℃ for 30 minutes to cure the mixture, and further heated at 85 ℃ for 100 hours, whereby the amount of outgas generated was 100ppm or less.
Description
Technical Field
The present invention relates to a sealing agent for an organic electroluminescent display element, which has excellent adhesion to a flexible substrate or the like and can suppress display defects caused by deterioration of the element.
Background
In recent years, organic optical devices using organic thin film elements such as organic electroluminescence (hereinafter also referred to as "organic EL") display elements and organic thin film solar cell elements have been studied. 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 into the organic light emitting material layer and injecting holes from the other electrode, the electrons and holes are combined in the organic light emitting material layer to perform self-luminescence. The following advantages are provided as compared with a liquid crystal display element or the like which requires a backlight: the display device has better visibility, can be further thinned, and can be driven by direct current at low voltage.
However, such an organic EL display element has the following problems: when the organic light-emitting material layer or the electrode is exposed to an external gas, its light-emitting characteristics are rapidly deteriorated, and the lifetime is shortened. Therefore, for the purpose of improving the stability and durability of the organic EL display element, a sealing technique for sealing the organic light emitting material layer and the electrode from moisture or oxygen in the atmosphere is indispensable for the organic EL display element.
Patent document 1 discloses a method of sealing a space between organic EL display element substrates by filling a sealant in an upper surface emission type organic EL display element or the like. However, the conventional sealing agent has a problem that outgassing occurs during and after curing, and thus the element is easily 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 sealing agent for an organic electroluminescent display element, which has excellent adhesion to a flexible substrate or the like and can suppress display defects caused by deterioration of the element.
Means for solving the problems
The present invention is a sealing agent for an organic electroluminescent display element, which comprises a cationically polymerizable compound and a cationic polymerization initiator, wherein the cationically polymerizable compound comprises a hydrolyzable cationically polymerizable compound having a cationically polymerizable group and an ether bond or an ester bond, and when the ether bond or the ester bond is cleaved by hydrolysis, all of the decomposition products have a cationically polymerizable group, and 300mg of the sealing agent for an organic electroluminescent display element is measured and sealed in a tubular formHeating at 100 deg.C for 30 min in a bottle to cure or irradiating with ultraviolet ray 1500mJ/cm2Then, the mixture was heated at 80 ℃ for 30 minutes to cure the mixture, and further heated at 85 ℃ for 100 hours, whereby the amount of outgas generated was 100ppm or less.
The present invention will be described in detail below.
The inventor considers that: the reason why the degassing occurs in the conventional sealing agent is that an ether bond or an ester bond of the cationically polymerizable compound contained in the sealing agent is hydrolyzed by an acid derived from a polymerization initiator or the like. Therefore, the present inventors have studied the case of using a polymerizable compound having no ether bond or ester bond as a cationically polymerizable compound, but the obtained sealant can suppress the occurrence of outgassing, but has a large cure shrinkage, and in particular, cannot sufficiently obtain adhesiveness to a flexible substrate or the like. Therefore, the inventors further conducted intensive studies and found that: the present inventors have completed the present invention by finding that a sealant for an organic EL display element, which has excellent adhesion to a flexible substrate or the like and can suppress display defects due to deterioration of the element, can be obtained by using a hydrolyzable cationically polymerizable compound having a cationically polymerizable group and an ether bond or an ester bond and having a cationically polymerizable group in all decomposed products even when the ether bond or the ester bond is cleaved by hydrolysis, and by adjusting the amount of outgas generated during and after curing to a specific value or less.
The sealing agent for organic EL display element of the present invention was measured at 300mg and sealed in a vial, and cured by heating at 100 ℃ for 30 minutes or irradiating with ultraviolet light at 1500mJ/cm2Then, the mixture was heated at 80 ℃ for 30 minutes to cure the mixture, and further heated at 85 ℃ for 100 hours, at which time the upper limit of the amount of outgas generated was 100 ppm. By setting the amount of outgas generation to 100ppm or less, the sealant for an organic EL display element of the present invention can sufficiently suppress display defects caused by deterioration of the element. The upper limit of the amount of degassing generation is preferably 50ppm, and more preferably 30 ppm.
The lower limit is not particularly limited as the amount of degassing generated is preferably smaller, but is substantially 5ppm or more.
The amount of the outgas generated can be measured by a gas chromatography mass spectrometer (e.g., JMS-Q1050 (manufactured by Nippon electronic Co., Ltd.)).
The sealant for an organic EL display element of the present invention contains a cationically polymerizable compound.
The cationically polymerizable compound contains a hydrolyzable cationically polymerizable compound (hereinafter also referred to as "hydrolyzable cationically polymerizable compound of the present invention") having a cationically polymerizable group and an ether bond or an ester bond, and when the ether bond or the ester bond is cleaved by hydrolysis, all of the decomposition products have a cationically polymerizable group. The hydrolyzable cationically polymerizable compound of the present invention has an ether bond or an ester bond, so that curing shrinkage does not become excessively large, and the obtained sealant for an organic EL display element has excellent adhesion to a flexible substrate or the like, and when the ether bond or the ester bond is cleaved by hydrolysis, all decomposed products have a cationically polymerizable group, and thus the decomposed products can be prevented from causing outgassing.
The amount of the degassing generated can be brought to the above range by using the hydrolyzable cation polymerizable compound of the present invention as the cation polymerizable compound and not using other components which cause degassing or making the content small even in the case of using the compound.
Examples of the cationically polymerizable group include an epoxy group, an oxetane group, and a vinyl ether group. Among them, epoxy groups are preferable.
Specific examples of the hydrolyzable cation polymerizable compound of the present invention include 3 ', 4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate (a compound represented by the following formula (1)), 3-ethyl-3 (((3-ethyloxetan-3-yl) methoxy) methyl) oxetane (a compound represented by the following formula (2)), 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester (a compound represented by the following formula (3)), and the like. Among them, from the viewpoint of further improving the adhesiveness of the obtained sealant for an organic EL display element to a flexible substrate or the like, an alicyclic epoxy compound having an ether bond or an ester bond is preferable, a compound represented by the following formula (1) or the following formula (2) is more preferable, and a compound represented by the following formula (1) is further preferable.
[ solution 1]
[ solution 2]
[ solution 3]
Examples of commercially available products of the hydrolyzable cation polymerizable compound of the present invention include Celloxide 2021P (manufactured by Daiiol corporation) and OXT-221 (manufactured by Toyo Synthesis Co., Ltd.).
The sealing agent for an organic EL display element of the present invention may contain, as another cationically polymerizable compound, a cationically polymerizable compound having no ether bond or ester bond, or a cationically polymerizable compound having an ether bond or ester bond but having at least a part of its decomposition product being not cationically polymerizable when the ether bond or the ester bond is cleaved by hydrolysis, within a range not hindering the object of the present invention, but it is preferable not to contain the other cationically polymerizable compound from the viewpoint of achieving both adhesiveness to a flexible substrate or the like and an effect of suppressing display defects due to deterioration of the element.
In the case where the other cationically polymerizable compound is contained, from the viewpoint of achieving both adhesiveness to a flexible substrate or the like and suppression of display defects due to deterioration of the device, the content of the hydrolyzable cationically polymerizable compound of the present invention in 100 parts by weight of the entire cationically polymerizable compound is preferably 20 parts by weight at the lower limit, more preferably 50 parts by weight at the lower limit, and still more preferably 70 parts by weight at the lower limit.
The sealant for an organic EL display element of the present invention contains a cationic polymerization initiator.
Examples of the cationic polymerization initiator include a photo cationic polymerization initiator which generates a protonic acid or a lewis acid by irradiation with light, and a thermal cationic polymerization initiator which generates a protonic acid or a lewis acid by heating. These cationic polymerization initiators are not particularly limited, and may be of an ionic acid-generating type or a nonionic acid-generating type.
Among the above-mentioned photocationic polymerization initiators, examples of the ionic photoacid-type photocationic polymerization initiator include those having an anionic moiety 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 bishexafluorophosphate, bis (4- (diphenylsulfonium) phenyl) sulfide bishexafluoroantimonate, bis (4- (diphenylsulfonium) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonium) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenyl sulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenyl sulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenyl sulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phenyl sulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis (4- (2-hydroxyethoxy)) phenyl sulfonium) phenyl) sulfide bishexafluorophosphate, Bis (4- (2-hydroxyethoxy)) phenylsulfonium) phenyl) sulfide bishexafluoroantimonate, bis (4- (2-hydroxyethoxy)) phenylsulfonium) phenyl) sulfide bistetrafluoroborate, bis (4- (2-hydroxyethoxy)) phenylsulfonium) 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 type photocationic polymerization initiator include nitrobenzyl esters, sulfonic acid derivatives, phosphate esters, phenol sulfonic acid esters, diazonaphthoquinones, and N-hydroxyimide sulfonic acid esters.
Examples of commercially available products of the above-mentioned photo cation polymerization initiator include: DTS-200(MIDORY chemical Co., Ltd.); UVI6990, UVI6974 (both manufactured by Union Carbide Corporation); SP-150 and SP-170 (both manufactured by ADEKA Co., Ltd.); FC-508, FC-512 (both 3M); IRGACURE 290(BASF corporation); PI2074 (Rhodia).
As the above thermal cationic polymerization initiator, there may be mentioned those having an anionic moiety of BF4 -、PF6 -、SbF6 -Or (BX)4)-(wherein X represents a phenyl group substituted with at least 2 or more fluorine or trifluoromethyl groups), sulfonium salt, phosphonium salt, quaternary ammonium salt, diazonium salt, iodonium salt, or the like.
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-dimethyl-N-benzylanilinium hexafluoroantimonate, N-dimethyl-N-benzylanilinium hexafluoroantimonate, Boron tetrafluoride, antimony hexafluoride, N-dimethyl-N-benzylpyridinium, N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid, and the like.
Examples of commercially available products of the above thermal cationic polymerization initiator include: San-Aid SI-60, San-Aid SI-80, San-Aid SI-B3, San-Aid SI-B3A and San-Aid SI-B4 (all manufactured by Sanxin chemical industries Co., Ltd.); CXC1612 and CXC1821 (both King Industries, Ltd.), and the like.
Among them, the cationic polymerization initiator preferably contains a quaternary ammonium salt in order to further suppress the occurrence of outgassing in the obtained sealing agent for an organic EL display element.
The lower limit of the content of the cationic polymerization initiator is preferably 0.05 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 cationic polymerization initiator is in this range, the obtained sealant for organic EL display elements is more excellent in curability and storage stability, and moisture resistance of cured products. The lower limit of the content of the cationic polymerization initiator is more preferably 0.1 part by weight, and the upper limit is more preferably 5 parts by weight.
The sealant for an organic EL display element of the present invention may further contain other components than the cationic polymerizable compound and the cationic polymerization initiator within a range not to impair the object of the present invention.
The sealing agent for an organic EL display element of the present invention may contain a silane coupling agent as the above-mentioned other component for the purpose of improving the adhesion between the sealing agent for an organic EL display element of the present invention and a substrate or the like, but preferably does not contain a silane coupling agent from the viewpoint of suppressing the occurrence of outgassing.
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.
When the silane coupling agent is contained, the upper limit of the content of the silane coupling agent is preferably 0.5 parts by weight based on 100 parts by weight of the cationically polymerizable compound. By setting the content of the silane coupling agent to 0.5 parts by weight or less, it is possible to exhibit a higher effect of improving the adhesion while suppressing the occurrence of degassing and the bleeding of the remaining silane coupling agent. The more preferable upper limit of the content of the silane coupling agent is 0.1 part by weight.
The sealing agent for an organic EL display element of the present invention may contain a stabilizer as the other component from the viewpoint of improving storage stability.
Examples of the stabilizer include amine compounds such as benzylamine.
The sealant for an organic EL display element of the present invention may contain a thermosetting agent as the other component.
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).
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 2 or more of them may be used in combination.
The sealing agent for an organic EL display element of the present invention may contain a surface modifier as the other component. The surface modifier can improve the flatness of the coating film of the sealant for organic EL display elements 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 products of the surface modifier include: BYK-302, BYK-331 (both BYK-CHEMIE JAPAN), UVX-272 (Nansuchen chemical Co., Ltd.), Surflon S-611(AGCSEMICHEMICAL Co., Ltd.), and the like.
The sealing agent for an organic EL display element of the present invention may contain, as the other component, a compound or an ion exchange resin that reacts with an acid generated in the sealing agent for an organic EL display element, in order to improve the durability of the element electrode.
Examples of the compound that reacts with the generated acid include a compound that neutralizes the acid, such as an alkali metal carbonate or bicarbonate, or an alkaline earth metal carbonate or bicarbonate. Specifically, for example, calcium carbonate, calcium hydrogen carbonate, sodium hydrogen carbonate, or the like can be used.
As the ion exchange resin, any of a cation exchange type, an anion exchange type, and an amphoteric ion exchange type can be used, and a cation exchange type or an amphoteric ion exchange type capable of adsorbing chloride ions is particularly preferable.
The sealant for an organic EL display element of the present invention may contain, as the other components, various known additives such as a curing retarder, a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, an ultraviolet absorber, and an antioxidant, as required.
Examples of the method for producing the sealant for an organic EL display element of the present invention include: a method of mixing the cationically polymerizable compound, the cationic polymerization initiator and other components added as needed using a mixer such as a homomixer, a universal mixer, a planetary mixer, a kneader or a three-roll machine.
The viscosity of the sealant for an organic EL display element of the present invention measured at 25 ℃ with an E-type viscometer is preferably 5mPa · s at the lower limit and 500mPa · s at the upper limit. When the viscosity is within this range, the coating property of the sealant for an organic EL display element of the present invention is further improved. The viscosity is more preferably 10 mPas at the lower limit and 100 mPas at the upper limit.
The viscosity can be measured, for example, by the following method: the measurement was performed using a VISCOMETER TV-22 (manufactured by eastern industries) as an E-type VISCOMETER, using a conical plate of CP1, and appropriately selecting a rotation speed of 1 to 100rpm according to the optimum torque number in each viscosity region.
The sealing agent for an organic EL display element of the present invention is particularly suitable as an in-plane sealing agent for sealing a laminate having an organic light-emitting material layer.
Effects of the invention
According to the present invention, a sealant for an organic electroluminescence display element which has excellent adhesion to a flexible substrate or the like and can suppress display defects due to deterioration of the element can be provided.
Detailed Description
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
(example 1)
100 parts by weight of a compound represented by the above formula (1) (Daxylonite, Celloxide 2021P), which is a hydrolyzable cation polymerizable compound of the present invention, and 0.5 part by weight of dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl) borate (Kingindustries, CXC-1821), which is a thermal cation polymerization initiator, were uniformly stirred and mixed at a stirring speed of 3000rpm by using a stirring mixer (THINKY, "AR-250") to prepare a sealant for an organic EL display element.
The obtained sealing agent for organic EL display element was measured at 300mg and sealed in a vial, and heated at 100 ℃ for 30 minutes to cure. The vial was further heated in a constant-temperature oven at 85 ℃ for 100 hours, and the amount of the vaporized components in the vial was measured by a gas chromatograph mass spectrometer (JMS-Q1050, manufactured by Nippon electronic Co., Ltd.). The results are shown in Table 1.
(examples 2 to 6 and comparative examples 1 to 3)
The materials shown in table 1 were mixed and stirred in the same manner as in example 1 at the mixing ratios shown in table 1 to prepare sealants for organic EL display elements of examples 2 to 6 and comparative examples 1 to 3.
The amount of outgas generated in each of the obtained organic EL display element sealants was measured in the same manner as in example 1. The results are shown in Table 1. The sealant obtained in example 2 was irradiated with ultraviolet light at 1500mJ/cm instead of heating at 100 ℃ for 30 minutes2Then, it was cured by heating at 80 ℃ for 30 minutes.
< evaluation >
The following evaluations were performed on each of the organic EL display element sealants obtained in examples and comparative examples. The results are shown in Table 1.
(1) Viscosity of the oil
The sealants for organic EL display elements obtained in examples and comparative examples were measured for viscosity at 25 ℃ using an E-type VISCOMETER (manufactured by eastern industries, inc. "VISCOMETER TV-22").
(2) Adhesion to flexible substrate
The sealing agent for each organic EL display element obtained in the example and comparative example was applied in a very small amount to the center of a 20mm × 50mm polycarbonate sheet (manufactured by TAKIRON corporation), and the same size polycarbonate sheet was superimposed thereon to spread the sealing agent. The sealants were cured in this state (the sealants obtained in examples 1 and 3 to 6 and comparative examples 1 to 3 were each cured by heating at 100 ℃ for 30 minutes, and the sealant obtained in example 2 was irradiated with ultraviolet light at 1500mJ/cm2And then heated at 80 ℃ for 30 minutes to cure the resulting composition), to obtain an adhesion test piece. The adhesion strength of the obtained adhesion test piece was measured using Ezgraph (manufactured by Shimadzu corporation). At this time, the adhesive strength was adjusted to 1.0kgf/cm2The above case was referred to as "○", and the adhesive strength was set to 0.5kgf/cm2Above and below 1.0kgf/cm2The case (2) is "△", and the adhesive strength is less than 0.5kgf/cm2The case of (2) was represented by "x", and the adhesiveness to the flexible substrate was evaluated.
(3) Curing Properties
The curing of each of the sealants for organic EL display elements obtained in examples and comparative examples was measured by using a DSC device (UMA 600, manufactured by Agilent Technologies corporation) (each of the sealants obtained in examples 1, 3 to 6 and comparative examples 1 to 3The resulting sealant was cured by heating at 100 ℃ for 30 minutes, and the sealant obtained in example 2 was irradiated with ultraviolet rays at 1500mJ/cm2And then further heated at 80 ℃ for 30 minutes to cure) and the amount of heat generated before and after curing, the reaction rate of the epoxy group is derived from the following formula.
Reaction rate (%) of epoxy group of 100 × (calorific value before curing-calorific value after curing)/calorific value before curing
Curability was evaluated by assuming that the reactivity of the epoxy group was "○" when it was 90% or more, assuming that the reactivity of the epoxy group was 70% or more and less than 90% was "△", and assuming that the reactivity of the epoxy group was less than 70% was "x".
(4) 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)
An ITO electrode was formed to a thickness of (1) and the obtained object was used as a substrate. The substrate was ultrasonically cleaned with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes, then cleaned with boiled isopropyl alcohol for 10 minutes, and then pretreated with a UV-ozone cleaner (NL-UV 253, manufactured by japan laser electronics).
Next, the substrate was fixed to a substrate holder of a vacuum deposition apparatus, 200mg of N, N '-bis (1-naphthyl) -N, N' -diphenylbenzidine (α -NPD) was charged into a bisque-fired crucible, and tris (8-quinolinolato) aluminum (Alq) was charged into another bisque-fired crucible3)200mg, the pressure in the vacuum chamber was reduced to 1X 10-4Pa., the crucible containing α -NPD was heated to evaporate α -NPD at the evaporation rate
Deposited on a substrate to a film thickness
Cavity of (2)A transport layer. Next, will be charged with Alq3Is heated to
Deposition rate of (3) 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 evaporation apparatus, and 200mg of lithium fluoride was added to a tungsten resistance-heated boat in the vacuum evaporation apparatus, and 1.0g of an aluminum wire was added to another tungsten boat. Then, the pressure in the evaporator of the vacuum evaporation apparatus was reduced to 2 × 10-4Pa, adding lithium fluoride to
Deposition rate of
Then, aluminum is added
Is formed at a high speed
The inside of the evaporator was returned to normal pressure by nitrogen gas, and the substrate on which the laminate having the organic light-emitting material layers was disposed was taken out.
(coating with inorganic Material film A)
A mask having an opening is provided so as to cover the entire laminate of 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: using SiH4Gas and nitrogen gas were used as raw material gases, and the respective flow rates were SiH4The gas was changed to 10sccm and the nitrogen gas was changed to 200sccm, the RF power was changed to 10W (frequency: 2.45GHz), the temperature in the chamber was changed to 100 ℃, and the pressure in the chamber was changed to 0.9 Torr.
The thickness of the inorganic material film a formed was about 1 μm.
(formation of resin protective film)
The sealing agent for organic EL display elements obtained in examples and comparative examples was applied onto a glass substrate by an inkjet system using an inkjet discharge device (manufactured by microdot, "nano printer 300") at a discharge rate of 80 pL. The film thickness was adjusted to 20 μm or less during coating. Next, the sealing agent for organic EL display element was cured (each of the sealing agents obtained in examples 1, 3 to 6 and comparative examples 1 to 3 was cured by heating at 100 ℃ for 30 minutes, and the sealing agent obtained in example 2 was irradiated with ultraviolet light at 1500mJ/cm2And then heated at 80 ℃ for 30 minutes to cure the resin), a resin protective film was formed.
(coating 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: using SiH4Gas and nitrogen gas were used as raw material gases, and the respective flow rates were SiH4The gas was changed to 10sccm and the nitrogen gas was changed to 200sccm, the RF power was changed to 10W (frequency: 2.45GHz), the temperature in the chamber was changed to 100 ℃, and the pressure in the chamber was changed to 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 element 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 visually observe the light emission state (light emission and presence/absence of dark spots) of the element, and the light emission state was observed uniformly without dark spots and edge extinction as "○", the light emission state was observed with no dark spots and edge extinction as "△", and the light emission state was observed with a remarkably enlarged non-light-emitting portion as "x", thereby evaluating the element.
[ Table 1]
Industrial applicability
According to the present invention, a sealant for an organic electroluminescence display element which has excellent adhesion to a flexible substrate or the like and can suppress display defects due to deterioration of the element can be provided.
Claims (5)
1. A sealant for an organic electroluminescent display element, which comprises a cationically polymerizable compound and a cationic polymerization initiator, wherein,
the cationic polymerizable compound contains a hydrolyzable cationic polymerizable compound having a cationic polymerizable group and an ether bond or an ester bond, and when the ether bond or the ester bond is cleaved by hydrolysis, all of the decomposition products have a cationic polymerizable group,
the sealing agent for organic electroluminescent display element was measured at 300mg and sealed in a vial, and cured by heating at 100 ℃ for 30 minutes or irradiating with ultraviolet light at 1500mJ/cm2Then heated at 80 ℃ for 30 minutes to cure the resin, and further heated at 85 ℃ for 100 hours, wherein the amount of outgas generated is 100ppm or less,
the viscosity of the sealing agent for the organic electroluminescent display element is 5 mPas to 500 mPas measured at 25 ℃ by using an E-type viscometer.
2. The sealing agent for an organic electroluminescent display element according to claim 1, wherein the hydrolyzable cationically polymerizable compound contains an alicyclic epoxy compound having an ether bond or an ester bond.
3. The sealing agent for an organic electroluminescent display element according to claim 2, wherein the alicyclic epoxy compound having an ether bond or an ester bond is a compound represented by the following formula (1),
4. the sealing agent for an organic electroluminescent display element according to claim 1, 2 or 3, wherein the content of the hydrolyzable cation polymerizable compound in 100 parts by weight of the total cation polymerizable compound is 20 parts by weight or more.
5. The sealant for an organic electroluminescent display element according to claim 1, 2 or 3, wherein the cationic polymerization initiator contains a quaternary ammonium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911373443.4A CN111031623A (en) | 2015-11-19 | 2016-11-01 | Sealing agent for organic electroluminescent display element |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015226637 | 2015-11-19 | ||
| JP2015-226637 | 2015-11-19 | ||
| PCT/JP2016/082407 WO2017086144A1 (en) | 2015-11-19 | 2016-11-01 | Sealing agent for organic electroluminescent display elements |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911373443.4A Division CN111031623A (en) | 2015-11-19 | 2016-11-01 | Sealing agent for organic electroluminescent display element |
Publications (2)
| Publication Number | Publication Date |
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| CN107852790A CN107852790A (en) | 2018-03-27 |
| CN107852790B true CN107852790B (en) | 2020-05-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911373443.4A Pending CN111031623A (en) | 2015-11-19 | 2016-11-01 | Sealing agent for organic electroluminescent display element |
| CN201680045108.XA Active CN107852790B (en) | 2015-11-19 | 2016-11-01 | Sealing agent for organic electroluminescent display element |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201911373443.4A Pending CN111031623A (en) | 2015-11-19 | 2016-11-01 | Sealing agent for organic electroluminescent display element |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP6530767B2 (en) |
| KR (1) | KR20180084633A (en) |
| CN (2) | CN111031623A (en) |
| TW (1) | TWI726934B (en) |
| WO (1) | WO2017086144A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| KR102167216B1 (en) * | 2017-09-01 | 2020-10-20 | 주식회사 엘지화학 | Method for preparing organic electronic device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010686A (en) * | 2010-09-30 | 2011-04-13 | 烟台德邦电子材料有限公司 | Double-solidification system fast-flowing underfill and preparation method thereof |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992010073A1 (en) * | 1990-11-30 | 1992-06-11 | Idemitsu Kosan Company Limited | Organic electroluminescence device |
| JP2001357973A (en) | 2000-06-15 | 2001-12-26 | Sony Corp | Display device |
| JP3876630B2 (en) * | 2001-03-01 | 2007-02-07 | 東亞合成株式会社 | Curable composition |
| KR20040019098A (en) * | 2001-08-03 | 2004-03-04 | 디에스엠 엔.브이 | Curable compositions for display devices |
| US7569260B2 (en) * | 2003-08-21 | 2009-08-04 | Asahi Kasei Chemicals Corporation | Photosensitive composition and cured products thereof |
| JP2007326988A (en) * | 2006-06-09 | 2007-12-20 | Chisso Corp | Epoxy resin composition |
| JP2009019077A (en) * | 2007-07-10 | 2009-01-29 | Kyocera Chemical Corp | Curable composition, adhesive for display element, and bonding method |
| JP2012241118A (en) * | 2011-05-20 | 2012-12-10 | Showa Denko Kk | Thermosetting resin composition and optical element |
| JP2013170223A (en) * | 2012-02-21 | 2013-09-02 | Sekisui Chem Co Ltd | Curable resin composition for vapor deposition, resin protection film, and organic optical device |
| JP5916220B2 (en) * | 2012-07-19 | 2016-05-11 | 日本化薬株式会社 | Energy ray curable resin composition and cured product thereof |
| WO2014017524A1 (en) * | 2012-07-26 | 2014-01-30 | 電気化学工業株式会社 | Resin composition |
| JP5967654B2 (en) * | 2012-11-28 | 2016-08-10 | 日本化薬株式会社 | Resin composition and cured product thereof (2) |
| JP6336967B2 (en) * | 2013-04-26 | 2018-06-06 | 三洋化成工業株式会社 | Adhesive for low polarity resin and molded product using the same |
| JP6214343B2 (en) * | 2013-10-30 | 2017-10-18 | キヤノン株式会社 | Sealant for inkjet recording head and inkjet recording head |
| JP6549984B2 (en) * | 2014-02-27 | 2019-07-24 | 積水化学工業株式会社 | Curable resin composition for sealing an organic electroluminescence display device, curable resin sheet for sealing an organic electroluminescence display device, and an organic electroluminescence display device |
| JP5887467B1 (en) * | 2014-05-20 | 2016-03-16 | 積水化学工業株式会社 | Sealant for organic electroluminescence display element |
-
2016
- 2016-11-01 CN CN201911373443.4A patent/CN111031623A/en active Pending
- 2016-11-01 WO PCT/JP2016/082407 patent/WO2017086144A1/en active Application Filing
- 2016-11-01 KR KR1020177036421A patent/KR20180084633A/en not_active Application Discontinuation
- 2016-11-01 JP JP2016567694A patent/JP6530767B2/en active Active
- 2016-11-01 CN CN201680045108.XA patent/CN107852790B/en active Active
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010686A (en) * | 2010-09-30 | 2011-04-13 | 烟台德邦电子材料有限公司 | Double-solidification system fast-flowing underfill and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI726934B (en) | 2021-05-11 |
| JP2019147963A (en) | 2019-09-05 |
| KR20180084633A (en) | 2018-07-25 |
| TW201730269A (en) | 2017-09-01 |
| CN107852790A (en) | 2018-03-27 |
| JPWO2017086144A1 (en) | 2018-06-07 |
| WO2017086144A1 (en) | 2017-05-26 |
| JP6530767B2 (en) | 2019-06-12 |
| CN111031623A (en) | 2020-04-17 |
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