TWI726934B - Sealant for organic electroluminescent display element - Google Patents
Sealant for organic electroluminescent display element Download PDFInfo
- Publication number
- TWI726934B TWI726934B TW105135637A TW105135637A TWI726934B TW I726934 B TWI726934 B TW I726934B TW 105135637 A TW105135637 A TW 105135637A TW 105135637 A TW105135637 A TW 105135637A TW I726934 B TWI726934 B TW I726934B
- Authority
- TW
- Taiwan
- Prior art keywords
- display element
- sealant
- cationic polymerizable
- polymerizable compound
- organic
- Prior art date
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- 239000000565 sealant Substances 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 48
- 125000002091 cationic group Chemical group 0.000 claims abstract description 26
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 19
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 238000007789 sealing Methods 0.000 claims description 25
- 238000010943 off-gassing Methods 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 27
- 230000006866 deterioration Effects 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 7
- -1 aromatic sulfonium salt Chemical class 0.000 description 55
- 239000010408 film Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 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
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910010272 inorganic material Inorganic materials 0.000 description 6
- 239000011147 inorganic material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 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
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000007738 vacuum evaporation 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
- 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
- 238000005342 ion exchange Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000007740 vapor deposition Methods 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
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- CNOHWNUIQSHFEJ-UHFFFAOYSA-N 1-cyclopenta-2,4-dien-1-yl-2-propan-2-ylbenzene;iron Chemical compound [Fe].CC(C)C1=CC=CC=C1C1C=CC=C1 CNOHWNUIQSHFEJ-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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 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
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 150000007517 lewis acids Chemical class 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
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000002994 raw material Substances 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
- 238000012360 testing method Methods 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
- VASOMTXTRMYSKD-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boronic acid Chemical class OB(O)C1=C(F)C(F)=C(F)C(F)=C1F VASOMTXTRMYSKD-UHFFFAOYSA-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
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- QLGYTJLZFZUDFL-UHFFFAOYSA-N 1,3-bis[1-(1h-imidazol-2-yl)propyl]urea Chemical compound N=1C=CNC=1C(CC)NC(=O)NC(CC)C1=NC=CN1 QLGYTJLZFZUDFL-UHFFFAOYSA-N 0.000 description 1
- VSHKLLPSERFSRJ-UHFFFAOYSA-N 1-(naphthalen-1-ylmethyl)pyridin-1-ium-2-carbonitrile Chemical compound N#CC1=CC=CC=[N+]1CC1=CC=CC2=CC=CC=C12 VSHKLLPSERFSRJ-UHFFFAOYSA-N 0.000 description 1
- OBSKXJSZGYXFFB-UHFFFAOYSA-N 1-benzylpyridin-1-ium-2-carbonitrile Chemical compound N#CC1=CC=CC=[N+]1CC1=CC=CC=C1 OBSKXJSZGYXFFB-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- VDAIJDKQXDCJSI-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethylurea Chemical compound CC1=NC=CN1CCNC(N)=O VDAIJDKQXDCJSI-UHFFFAOYSA-N 0.000 description 1
- FJNLCHNQVJVCPY-UHFFFAOYSA-N 2-n-methoxy-2-n-methyl-4-n,6-n-dipropyl-1,3,5-triazine-2,4,6-triamine Chemical compound CCCNC1=NC(NCCC)=NC(N(C)OC)=N1 FJNLCHNQVJVCPY-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 102100033806 Alpha-protein kinase 3 Human genes 0.000 description 1
- 101710082399 Alpha-protein kinase 3 Proteins 0.000 description 1
- QTPJYKUVEHDXHX-UHFFFAOYSA-N C(C(C1=CC=CC=C1)=CS1)=C1[As](C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C(C(C1=CC=CC=C1)=CS1)=C1[As](C1=CC=CC=C1)C1=CC=CC=C1 QTPJYKUVEHDXHX-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
- ZYOUJMRZDQJUMP-UHFFFAOYSA-N CCC(C=1NC=CN1)NCCCCCCN Chemical compound CCC(C=1NC=CN1)NCCCCCCN ZYOUJMRZDQJUMP-UHFFFAOYSA-N 0.000 description 1
- CKEAMIMZKRUKLM-UHFFFAOYSA-N COC(C=C1)=CC=C1[S+](C(C=C1)=CC=C1OC)C(C=C1)=CC=C1OC.[AsH3] Chemical compound COC(C=C1)=CC=C1[S+](C(C=C1)=CC=C1OC)C(C=C1)=CC=C1OC.[AsH3] CKEAMIMZKRUKLM-UHFFFAOYSA-N 0.000 description 1
- GMXOYEFGMAXIIU-UHFFFAOYSA-N C[N+](CC1=CC(=C(C=C1)C)C)(C1=CC=CC=C1)C Chemical compound C[N+](CC1=CC(=C(C=C1)C)C)(C1=CC=CC=C1)C GMXOYEFGMAXIIU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 1
- VPSDPCXOOHMTDQ-UHFFFAOYSA-N [B+3].C(C)[N+](C1=CC=CC=C1)(CC1=CC=CC=C1)CC Chemical compound [B+3].C(C)[N+](C1=CC=CC=C1)(CC1=CC=CC=C1)CC VPSDPCXOOHMTDQ-UHFFFAOYSA-N 0.000 description 1
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- TUGFXUOVYDXKJG-UHFFFAOYSA-N [Fe+2].C1(C=CC=C1)C1=C(C=CC=C1)C(C)C Chemical compound [Fe+2].C1(C=CC=C1)C1=C(C=CC=C1)C(C)C TUGFXUOVYDXKJG-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
- 239000006096 absorbing agent Substances 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
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
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- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- KUBDAUORBIPBFS-UHFFFAOYSA-N antimony(3+) benzyl-dimethyl-phenylazanium Chemical compound [Sb+3].C=1C=CC=CC=1[N+](C)(C)CC1=CC=CC=C1 KUBDAUORBIPBFS-UHFFFAOYSA-N 0.000 description 1
- CFPCDQPUCAECLL-UHFFFAOYSA-N antimony(3+) ethyl(triphenyl)phosphanium Chemical compound [Sb+3].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 CFPCDQPUCAECLL-UHFFFAOYSA-N 0.000 description 1
- LUAKDNCXFXZOEC-UHFFFAOYSA-N antimony(3+);triphenylsulfanium Chemical compound [Sb+3].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 LUAKDNCXFXZOEC-UHFFFAOYSA-N 0.000 description 1
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- 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
- 238000009835 boiling Methods 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
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
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- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 1
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- 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
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 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-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-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
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
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- 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
- H10K59/873—Encapsulations
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
- Polyethers (AREA)
- Epoxy Resins (AREA)
- Sealing Material Composition (AREA)
Abstract
本發明之目的在於提供一種對於可撓性基板等之接著性亦優異、且能夠抑制由元件之劣化所引起之顯示不良的有機電激發光顯示元件用密封劑。 The object of the present invention is to provide a sealant for an organic electroluminescent display element that is excellent in adhesiveness to flexible substrates and the like, and can suppress display defects caused by the deterioration of the element.
本發明之有機電激發光顯示元件用密封劑係含有陽離子聚合性化合物與陽離子聚合起始劑者，且上述陽離子聚合性化合物含有下述水解性陽離子聚合性化合物，即具有陽離子聚合性基與醚鍵或酯鍵，且於該醚鍵或該酯鍵藉由水解而被切斷之情形時，所有分解物具有陽離子聚合性基；於稱量300mg並封入至小瓶中，於100℃加熱30分鐘而使之硬化，或照射紫外線1500mJ/cm2後，於80℃加熱30分鐘而使之硬化，進而於85℃加熱100小時之時，釋氣產生量為100ppm以下。 The sealant for an organic electroluminescent display element of the present invention contains a cationic polymerizable compound and a cationic polymerization initiator, and the cationically polymerizable compound contains the following hydrolyzable cationic polymerizable compound, that is, has a cationic polymerizable group and an ether Bond or ester bond, and when the ether bond or the ester bond is cleaved by hydrolysis, all the decomposed products have cationic polymerizable groups; weighed 300mg and sealed in a vial, heated at 100°C for 30 minutes When it is cured, or irradiated with ultraviolet rays of 1500mJ/cm 2 , it is cured by heating at 80°C for 30 minutes, and then heated at 85°C for 100 hours, the outgas generation amount is 100 ppm or less.
Description
本發明係關於一種對於可撓性基板等之接著性亦優異、且能夠抑制由元件之劣化所引起之顯示不良的有機電激發光顯示元件用密封劑。 The present invention relates to a sealant for an organic electroluminescent display element that is excellent in adhesiveness to flexible substrates and the like, and can suppress display defects caused by the deterioration of the element.
近年來，業界不斷進行使用有有機電激發光(以下，亦稱為「有機EL」)顯示元件或有機薄膜太陽電池元件等有機薄膜元件之有機光學裝置之研究。有機薄膜元件由於可藉由真空蒸鍍或溶液塗佈等簡便地製作，故而生產性亦優異。 In recent years, the industry has continuously conducted research on organic optical devices that use organic thin-film devices such as organic electroluminescent (hereinafter, also referred to as "organic EL") display devices or organic thin-film solar cell devices. The organic thin-film device can be easily manufactured by vacuum evaporation, solution coating, etc., and therefore has excellent productivity.
有機EL顯示元件具有於相互對向之一對電極間夾持有有機發光材料層之薄膜構造體。於該有機發光材料層中自一電極注入電子，並且自另一電極注入電洞，藉此於有機發光材料層內電子與電洞結合而進行自發光。與需要背光裝置之液晶顯示元件等相比，具有視認性良好、可更薄型化、且可進行直流低電壓驅動之優點。 The organic EL display element has a thin film structure in which an organic light-emitting material layer is sandwiched between a pair of electrodes facing each other. In the organic light-emitting material layer, electrons are injected from one electrode, and holes are injected from the other electrode, so that the electrons and holes in the organic light-emitting material layer are combined to perform self-luminescence. Compared with liquid crystal display elements that require a backlight, it has the advantages of good visibility, thinner thickness, and DC low-voltage drive.
然而，此種有機EL顯示元件存在若有機發光材料層或電極暴露於外部氣體中，則其發光特性會急劇地劣化而壽命縮短之問題。因此，為了提高有機EL顯示元件之穩定性及耐久性，於有機EL顯示元件中，將 有機發光材料層或電極與大氣中之水分或氧阻隔開之密封技術變得必不可少。 However, this type of organic EL display element has a problem that if the organic light-emitting material layer or the electrode is exposed to external air, the light-emitting characteristics of the organic light-emitting material are rapidly deteriorated and the life span is shortened. Therefore, in order to improve the stability and durability of organic EL display elements, in organic EL display elements, The sealing technology for the organic light-emitting material layer or electrode to block the moisture or oxygen in the atmosphere becomes indispensable.
於專利文獻1中揭示有於頂面發光型有機EL顯示元件等中，於有機EL顯示元件基板之間充滿密封劑而進行密封之方法。然而，習知之密封劑有於硬化時及硬化後產生釋氣而容易使元件劣化之問題。 Patent Document 1 discloses a method of filling and sealing the organic EL display element substrates with a sealing agent in a top surface emission type organic EL display element or the like. However, the conventional sealant has the problem of outgassing during and after hardening, which easily degrades the device.
[先前技術文獻] [Prior Technical Literature]
[專利文獻] [Patent Literature]
專利文獻1：日本特開2001-357973號公報 Patent Document 1: Japanese Patent Application Publication No. 2001-357973
本發明之目的在於提供一種對於可撓性基板等之接著性亦優異、且能夠抑制由元件之劣化所引起之顯示不良的有機電激發光顯示元件用密封劑。 The object of the present invention is to provide a sealant for an organic electroluminescent display element that is excellent in adhesiveness to flexible substrates and the like, and can suppress display defects caused by the deterioration of the element.
本發明係一種有機電激發光顯示元件用密封劑，其係含有陽離子聚合性化合物與陽離子聚合起始劑者，且上述陽離子聚合性化合物含有下述水解性陽離子聚合性化合物，即具有陽離子聚合性基與醚鍵或酯鍵，且於該醚鍵或該酯鍵藉由水解而被切斷之情形時，所有分解物具有陽離子聚合性基；於稱量300mg並封入至小瓶中，於100℃加熱30分鐘而使之硬化，或照射紫外線1500mJ/cm2後，於80℃加熱30分鐘而使之硬化，進而於85℃加熱100小時之時，釋氣產生量為100ppm以下。 The present invention is a sealant for organic electroluminescent display elements, which contains a cationic polymerizable compound and a cationic polymerization initiator, and the above-mentioned cationic polymerizable compound contains the following hydrolyzable cationic polymerizable compound, that is, has cationic polymerizability When the ether bond or the ester bond is cleaved by hydrolysis, all the decomposition products have a cationic polymerizable group; weigh 300mg and seal it in a vial at 100°C It is cured by heating for 30 minutes, or irradiated with ultraviolet rays of 1500mJ/cm 2 and then heated at 80°C for 30 minutes to cure, and then heated at 85°C for 100 hours, the outgassing generation is 100 ppm or less.
以下，對本發明進行詳細說明。 Hereinafter, the present invention will be described in detail.
本發明者認為，習知之密封劑之釋氣產生之原因為密封劑中所含之陽離子聚合性化合物之醚鍵或酯鍵藉由源自聚合起始劑等之酸而進行水解。因此，本發明者對作為陽離子聚合性化合物使用不具有醚鍵及酯鍵者進行了研究，所獲得之密封劑雖然能夠抑制釋氣之產生，但硬化收縮較大，尤其無法充分地獲得對於可撓性基板等之接著性。因此，本發明者進而進行努力研究，結果發現，藉由使用具有下述水解性陽離子聚合性化合物，即陽離子聚合性基與醚鍵或酯鍵、且於該醚鍵或酯鍵藉由水解而被切斷之情形時所有分解物亦具有陽離子聚合性基，且使硬化時及硬化後之釋氣產生量成為特定值以下，而能夠獲得對於可撓性基板等之接著性亦優異、且能夠抑制由元件之劣化所引起之顯示不良的有機EL顯示元件用密封劑，從而完成本發明。 The inventor believes that the cause of outgassing of the conventional sealant is that the ether bond or ester bond of the cationic polymerizable compound contained in the sealant is hydrolyzed by an acid derived from a polymerization initiator or the like. Therefore, the present inventors studied the use of a cationic polymerizable compound that does not have an ether bond or an ester bond. Although the obtained sealant can suppress the generation of outgassing, the curing shrinkage is large, and in particular, it cannot be sufficiently obtained. Adhesion to flexible substrates, etc. Therefore, the inventors of the present invention conducted further studies and found that by using a hydrolyzable cationically polymerizable compound, that is, a cationically polymerizable group and an ether bond or an ester bond, and the ether bond or ester bond is hydrolyzed When it is cut, all the decomposed products also have cationic polymerizable groups, and the amount of outgassing during and after curing is reduced to a specific value or less, and the adhesiveness to flexible substrates can be obtained. The sealant for an organic EL display element that suppresses display failures caused by the deterioration of the element, thereby completing the present invention.
關於本發明之有機EL顯示元件用密封劑，於稱量300mg並封入至小瓶中，於100℃加熱30分鐘而使之硬化，或照射紫外線1500mJ/cm2後，於80℃加熱30分鐘而使之硬化，進而於85℃加熱100小時之時，釋氣產生量之上限為100ppm。藉由上述釋氣產生量為100ppm以下，本發明之有機EL顯示元件用密封劑能夠充分地抑制由元件之劣化所引起之顯示不良。上述釋氣產生量之較佳之上限為50ppm，更佳之上限為30ppm。 Regarding the sealant for an organic EL display element of the present invention, weigh 300 mg and seal it in a vial, heat it at 100°C for 30 minutes to harden it, or irradiate it with ultraviolet rays of 1500mJ/cm 2 and then heat it at 80°C for 30 minutes. The upper limit of the amount of outgassing produced is 100 ppm when it is further heated at 85°C for 100 hours. With the above-mentioned outgas generation amount being 100 ppm or less, the sealing agent for an organic EL display element of the present invention can sufficiently suppress display defects caused by the deterioration of the element. The preferable upper limit of the above-mentioned outgas generation amount is 50 ppm, and the more preferable upper limit is 30 ppm.
上述釋氣產生量越少越佳，並無特別下限，但實質上成為5ppm以上。 The amount of outgassing described above is preferably as small as possible, and there is no particular lower limit, but it is substantially 5 ppm or more.
再者，上述釋氣產生量可使用氣相層析質譜分析計(例如JMS-Q1050(日本電子公司製造)等)而進行測定。 In addition, the above-mentioned outgas generation amount can be measured using a gas chromatography mass spectrometer (for example, JMS-Q1050 (manufactured by JEOL Ltd.), etc.).
本發明之有機EL顯示元件用密封劑含有陽離子聚合性化合 物。上述陽離子聚合性化合物含有如下水解性陽離子聚合性化合物(以下，亦稱為「本發明之水解性陽離子聚合性化合物」)，其具有陽離子聚合性基與醚鍵或酯鍵，且於該醚鍵或該酯鍵藉由水解而被切斷之情形時，所有分解物具有陽離子聚合性基。本發明之水解性陽離子聚合性化合物係藉由具有醚鍵或酯鍵，硬化收縮不會變得過大，且所獲得之有機EL顯示元件用密封劑對於可撓性基板等之接著性優異者，又，藉由在該醚鍵或該酯鍵藉由水解而被切斷之情形時所有分解物具有陽離子聚合性基，能夠防止該分解物成為產生釋氣之原因。 The sealant for organic EL display elements of the present invention contains a cationic polymerizable compound Things. The above-mentioned cationically polymerizable compound contains the following hydrolyzable cationically polymerizable compound (hereinafter also referred to as "the hydrolyzable cationically polymerizable compound of the present invention"), which has a cationically polymerizable group and an ether bond or an ester bond, and the ether bond Or when the ester bond is cleaved by hydrolysis, all the decomposition products have cationically polymerizable groups. The hydrolyzable cationically polymerizable compound of the present invention has an ether bond or an ester bond, the curing shrinkage does not become too large, and the obtained sealant for an organic EL display element has excellent adhesion to flexible substrates, etc. In addition, when the ether bond or the ester bond is cleaved by hydrolysis, all the decomposition products have cationically polymerizable groups, so that the decomposition products can be prevented from becoming a cause of outgassing.
作為上述陽離子聚合性化合物，使用本發明之水解性陽離子聚合性化合物，且不使用如成為產生釋氣之原因之其他成分，或即便於使用之情形時亦將含量設為少量，藉此可將上述釋氣產生量設為上述範圍。 As the above-mentioned cationically polymerizable compound, the hydrolyzable cationically polymerizable compound of the present invention is used, and other components that cause outgassing are not used, or the content is set to a small amount even in the case of use, whereby The above-mentioned outgas generation amount is set to the above-mentioned range.
作為上述陽離子聚合性基，例如可列舉：環氧基、氧雜環丁基、乙烯醚基等。其中，較佳為環氧基。 As said cationically polymerizable group, an epoxy group, an oxetanyl group, a vinyl ether group, etc. are mentioned, for example. Among them, epoxy groups are preferred.
作為本發明之水解性陽離子聚合性化合物，具體而言，例如可列舉：3,4-環氧環己羧酸-3',4'-環氧環己基甲酯(下述式(1)表示之化合物)、3-乙基-3(((3-乙基氧雜環丁烷-3-基)甲氧基)甲基)氧雜環丁烷(下述式(2)表示之化合物)、4,5-環氧環己烷-1,2-二羧酸二環氧丙酯(下述式(3)表示之化合物)等。其中，就所獲得之有機EL顯示元件用密封劑成為對於可撓性基板等之接著性更優異者而言，較佳為具有醚鍵或酯鍵之脂環式環氧化合物，更佳為下述式(1)或下述式(2)表示之化合物，進而較佳為下述式(1)表示之化合物。 As the hydrolyzable cationically polymerizable compound of the present invention, specifically, for example, 3,4-epoxycyclohexanoic acid-3',4'-epoxycyclohexyl methyl ester (represented by the following formula (1) The compound), 3-ethyl-3(((3-ethyloxetan-3-yl)methoxy)methyl)oxetane (the compound represented by the following formula (2)) , 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester (compound represented by the following formula (3)), etc. Among them, in terms of the obtained sealant for organic EL display elements having more excellent adhesiveness to flexible substrates, etc., an alicyclic epoxy compound having an ether bond or an ester bond is preferred, and the following is more preferred The compound represented by the above formula (1) or the following formula (2) is more preferably a compound represented by the following formula (1).
作為本發明之水解性陽離子聚合性化合物中之市售者，例如可列舉：Celloxide 2021P(Daicel公司製造)、OXT-221(東亞合成公司製造)等。 As a commercially available one among the hydrolyzable cationically polymerizable compounds of the present invention, for example, Celloxide 2021P (manufactured by Daicel), OXT-221 (manufactured by Toagosei Co., Ltd.), etc. can be cited.
本發明之有機EL顯示元件用密封劑於不會阻礙本發明之目的之範圍內，可含有不具有醚鍵及酯鍵之陽離子聚合性化合物、或雖然具有醚鍵或酯鍵但於該醚鍵或該酯鍵藉由水解而被切斷之情形時至少一部分分解物不具有陽離子聚合性之陽離子聚合性化合物作為其他陽離子聚合性化合物，但就同時實現對於可撓性基板等之接著性與抑制由元件之劣化所引起之顯示不良之效果之觀點而言，較佳為不含上述其他陽離子聚合性化 合物。 The sealing agent for an organic EL display element of the present invention may contain a cationic polymerizable compound that does not have an ether bond or an ester bond, or may contain an ether bond or an ester bond but the ether bond Or when the ester bond is cleaved by hydrolysis, at least a part of the decomposition product does not have cationically polymerizable cationically polymerizable compounds as other cationically polymerizable compounds, but at the same time achieves adhesion and suppression to flexible substrates, etc. From the viewpoint of poor display effect caused by the deterioration of the device, it is preferable not to contain the above-mentioned other cationic polymerization Compound.
於含有上述其他陽離子聚合性化合物之情形時，就同時實現對於可撓性基板等之接著性與抑制由元件之劣化所引起之顯示不良之效果之觀點而言，全部陽離子聚合性化合物100重量份中之本發明之水解性陽離子聚合性化合物之含量之較佳之下限為20重量份，更佳之下限為50重量份，進而較佳之下限為70重量份。 In the case of containing the above-mentioned other cationic polymerizable compounds, from the viewpoint of simultaneously achieving the adhesion to flexible substrates and the like and the effect of suppressing display defects caused by the deterioration of the device, 100 parts by weight of the total cationic polymerizable compound The lower limit of the content of the hydrolyzable cationically polymerizable compound of the present invention is preferably 20 parts by weight, more preferably 50 parts by weight, and still more preferably 70 parts by weight.
本發明之有機EL顯示元件用密封劑含有陽離子聚合起始劑。作為上述陽離子聚合起始劑，可列舉：藉由光照射產生質子酸或路易斯酸之光陽離子聚合起始劑、或藉由加熱產生質子酸或路易斯酸之熱陽離子聚合起始劑。只要為該等，則並無特別限定，可為離子性酸產生型，亦可為非離子性酸產生型。 The sealing agent for organic EL display elements of the present invention contains a cationic polymerization initiator. Examples of the cationic polymerization initiator include photocationic polymerization initiators that generate proton acid or Lewis acid by light irradiation, or thermal cationic polymerization initiators that generate proton acid or Lewis acid by heating. As long as it is these, it will not specifically limit, It may be an ionic acid-generating type, and may be a nonionic acid-generating type.
上述光陽離子聚合起始劑之中，作為離子性光酸產生型之光陽離子聚合起始劑，例如可列舉陰離子部分由BF4 -、PF6 -、SbF6 -、或(BX4)-(其中，X表示經至少2個以上之氟或三氟甲基取代之苯基)所構成之芳香族鋶鹽、芳香族錪鹽、芳香族重氮鎓鹽、芳香族銨鹽、或(2,4-環戊二烯-1-基)((1-甲基乙基)苯)-鐵鹽等。 Among the above photo-cationic polymerization initiator, a photo-cationic ionic photoacid generator type of the polymerization initiator, for example, in part by the anion BF 4 -, PF 6 -, SbF 6 -, or (BX 4) - ( Where X represents an aromatic sulfonium salt, aromatic iodonium salt, aromatic diazonium salt, aromatic ammonium salt, or (2, 4-cyclopentadien-1-yl)((1-methylethyl)benzene)-iron salt and the like.
作為上述芳香族鋶鹽，例如可列舉：雙(4-(二苯基鋶基)苯基)硫醚雙六氟磷酸鹽、雙(4-(二苯基鋶基)苯基)硫醚雙六氟銻酸鹽、雙(4-(二苯基鋶基)苯基)硫醚雙四氟硼酸鹽、雙(4-(二苯基鋶基)苯基)硫醚四(五氟苯基)硼酸鹽、二苯基-4-(苯硫基)苯基鋶六氟磷酸鹽、二苯基-4-(苯硫基)苯基鋶六氟銻酸鹽、二苯基-4-(苯硫基)苯基鋶四氟硼酸鹽、二苯基-4-(苯硫基)苯基鋶四(五氟苯基)硼酸鹽、三苯基鋶六氟磷酸鹽、三苯基鋶六氟銻酸鹽、三苯基 鋶四氟硼酸鹽、三苯基鋶四(五氟苯基)硼酸鹽、雙(4-(二(4-(2-羥基乙氧基))苯基鋶基)苯基)硫醚雙六氟磷酸鹽、雙(4-(二(4-(2-羥基乙氧基))苯基鋶基)苯基)硫醚雙六氟銻酸鹽、雙(4-(二(4-(2-羥基乙氧基))苯基鋶基)苯基)硫醚雙四氟硼酸鹽、雙(4-(二(4-(2-羥基乙氧基))苯基鋶基)苯基)硫醚四(五氟苯基)硼酸鹽等。 As the above-mentioned aromatic sulfide salt, for example, bis(4-(diphenylaunyl)phenyl) sulfide bishexafluorophosphate, bis(4-(diphenylaunyl)phenyl) sulfide bis Hexafluoroantimonate, bis(4-(diphenylarunyl)phenyl) sulfide bistetrafluoroborate, bis(4-(diphenylarunyl)phenyl) sulfide tetrakis(pentafluorophenyl) )Borate, diphenyl-4-(phenylthio)phenyl sulfonium hexafluorophosphate, diphenyl-4-(phenylthio) phenyl sulfonium hexafluoroantimonate, diphenyl-4-( Phenylsulfanyl) phenyl sulfonium tetrafluoroborate, diphenyl-4-(phenylsulfanyl) phenyl sulfonium tetrakis (pentafluorophenyl) borate, triphenyl sulfonium hexafluorophosphate, triphenyl sulfonium hexafluoride Fluorantimonate, triphenyl Alumium tetrafluoroborate, triphenyl alumium tetrakis (pentafluorophenyl) borate, bis (4-(bis(4-(2-hydroxyethoxy)) phenyl arunnyl) phenyl) sulfide bishexa Fluorophosphate, bis(4-(bis(4-(2-hydroxyethoxy))phenylaunyl)phenyl)sulfide bishexafluoroantimonate, bis(4-(bis(4-(2 -Hydroxyethoxy)) phenylarunyl)phenyl) sulfide bistetrafluoroborate, bis(4-(bis(4-(2-hydroxyethoxy))phenylarunyl)phenyl)sulfur Ether tetrakis (pentafluorophenyl) borate and the like.
作為上述芳香族錪鹽，例如可列舉：二苯基錪六氟磷酸鹽、二苯基錪六氟銻酸鹽、二苯基錪四氟硼酸鹽、二苯基錪四(五氟苯基)硼酸鹽、雙(十二烷基苯基)錪六氟磷酸鹽、雙(十二烷基苯基)錪六氟銻酸鹽、雙(十二烷基苯基)錪四氟硼酸鹽、雙(十二烷基苯基)錪四(五氟苯基)硼酸鹽、4-甲基苯基-4-(1-甲基乙基)苯基錪六氟磷酸鹽、4-甲基苯基-4-(1-甲基乙基)苯基錪六氟銻酸鹽、4-甲基苯基-4-(1-甲基乙基)苯基錪四氟硼酸鹽、4-甲基苯基-4-(1-甲基乙基)苯基錪四(五氟苯基)硼酸鹽等。 As the above-mentioned aromatic iodonium salt, for example, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium tetrafluoroborate, diphenyl iodonium tetrakis (pentafluorophenyl) Borate, bis(dodecylphenyl) hexafluorophosphate, bis(dodecylphenyl) hexafluoroantimonate, bis(dodecylphenyl) tetrafluoroborate, double (Dodecylphenyl) tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4-(1-methylethyl)phenyl hexafluorophosphate, 4-methylphenyl -4-(1-Methylethyl)phenylphosphonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenylphosphonium tetrafluoroborate, 4-methylbenzene 4-(1-methylethyl)phenylphosphonium tetrakis(pentafluorophenyl)borate and the like.
作為上述芳香族重氮鎓鹽，例如可列舉：苯基重氮鎓六氟磷酸鹽、苯基重氮鎓六氟銻酸鹽、苯基重氮鎓四氟硼酸鹽、苯基重氮鎓四(五氟苯基)硼酸鹽等。 Examples of the above-mentioned aromatic diazonium salts include: phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrafluoroborate. (Pentafluorophenyl) borate and the like.
作為上述芳香族銨鹽，例如可列舉：1-苄基-2-氰基吡啶鎓六氟磷酸鹽、1-苄基-2-氰基吡啶鎓六氟銻酸鹽、1-苄基-2-氰基吡啶鎓四氟硼酸鹽、1-苄基-2-氰基吡啶鎓四(五氟苯基)硼酸鹽、1-(萘基甲基)-2-氰基吡啶鎓六氟磷酸鹽、1-(萘基甲基)-2-氰基吡啶鎓六氟銻酸鹽、1-(萘基甲基)-2-氰基吡啶鎓四氟硼酸鹽、1-(萘基甲基)-2-氰基吡啶鎓四(五氟苯基)硼酸鹽等。 As the above-mentioned aromatic ammonium salt, for example, 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2 -Cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetra(pentafluorophenyl) borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate , 1-(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl)-2-cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate and the like.
作為上述(2,4-環戊二烯-1-基)((1-甲基乙基)苯)-鐵鹽，例如可列舉：(2,4-環戊二烯-1-基)((1-甲基乙基)苯)-鐵(II)六氟磷酸鹽、(2,4-環戊二烯 -1-基)((1-甲基乙基)苯)-鐵(II)六氟銻酸鹽、(2,4-環戊二烯-1-基)((1-甲基乙基)苯)-鐵(II)四氟硼酸鹽、(2,4-環戊二烯-1-基)((1-甲基乙基)苯)-鐵(II)四(五氟苯基)硼酸鹽等。 As the above-mentioned (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-iron salt, for example, (2,4-cyclopentadien-1-yl)( (1-methylethyl)benzene)-iron(II) hexafluorophosphate, (2,4-cyclopentadiene) -1-yl)((1-methylethyl)benzene)-iron(II)hexafluoroantimonate, (2,4-cyclopentadien-1-yl)((1-methylethyl) Benzene)-iron(II) tetrafluoroborate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-iron(II) tetrakis(pentafluorophenyl)boronic acid Salt etc.
作為上述非離子性光酸產生型之光陽離子聚合起始劑，例如可列舉：硝基苄酯、磺酸衍生物、磷酸酯、苯酚磺酸酯、重氮萘醌、N-羥基醯亞胺磺酸酯等。 Examples of the aforementioned nonionic photo-acid-generating photocationic polymerization initiator include: nitrobenzyl ester, sulfonic acid derivatives, phosphoric acid ester, phenol sulfonate, diazonaphthoquinone, and N-hydroxyimide Sulfonate etc.
作為上述光陽離子聚合起始劑中之市售者，例如可列舉：DTS-200(Midori Kagaku公司製造)、UVI6990、UVI6974(均為Union Carbide公司製造)、SP-150、SP-170(均為ADEKA公司製造)、FC-508、FC-512(均為3M公司製造)、Irgacure290(BASF公司製造)、PI2074(Rhodia公司製造)等。 Examples of commercially available photo-cationic polymerization initiators include: DTS-200 (manufactured by Midori Kagaku), UVI6990, UVI6974 (all manufactured by Union Carbide), SP-150, SP-170 (all are ADEKA Corporation), FC-508, FC-512 (all manufactured by 3M Corporation), Irgacure290 (manufactured by BASF Corporation), PI2074 (manufactured by Rhodia Corporation), and the like.
作為上述熱陽離子聚合起始劑，可列舉陰離子部分由BF4-、PF6-、SbF6 -、或(BX4)-(其中，X表示經至少2個以上之氟或三氟甲基取代之苯基)所構成之鋶鹽、鏻鹽、四級銨鹽、重氮鎓鹽、或錪鹽等。 As the thermal cationic polymerization initiator, the anionic moiety include BF 4-, PF 6-, SbF 6 -, or (BX 4) - (wherein, X is substituted with at least two of fluoro or trifluoromethyl The phenyl) constituted by sulfonium salt, phosphonium salt, quaternary ammonium salt, diazonium salt, or enonium salt.
作為上述鋶鹽，可列舉：三苯基鋶四氟化硼、三苯基鋶六氟化銻、三苯基鋶六氟化砷、三(4-甲氧基苯基)鋶六氟化砷、二苯基(4-苯基噻吩基)鋶六氟化砷等。 Examples of the above-mentioned sulfonium salt include: triphenylsulfonium boron tetrafluoride, triphenylsulfonium antimony hexafluoride, triphenylsulfonium arsenic hexafluoride, and tris(4-methoxyphenyl)sulfonium arsenic hexafluoride , Diphenyl (4-phenylthienyl) arsenic hexafluoride and so on.
作為上述鏻鹽，可列舉乙基三苯基鏻六氟化銻、四丁基鏻六氟化銻等。 As said phosphonium salt, ethyl triphenyl phosphonium antimony hexafluoride, tetrabutyl phosphonium antimony hexafluoride, etc. are mentioned.
作為上述四級銨鹽，例如可列舉：二甲基苯基(4-甲氧基苄基)銨六氟磷酸鹽、二甲基苯基(4-甲氧基苄基)銨六氟銻酸鹽、二甲基苯基(4-甲氧基苄基)銨四(五氟苯基)硼酸鹽、二甲基苯基(4-甲基苄基)銨六氟磷酸鹽、二甲基苯基(4-甲基苄基)銨六氟銻酸鹽、二甲基苯基(4-甲基苄基)銨六氟 四(五氟苯基)硼酸鹽、甲基苯基二苄基銨、甲基苯基二苄基銨六氟銻酸鹽六氟磷酸鹽、甲基苯基二苄基銨四(五氟苯基)硼酸鹽、苯基三苄基銨四(五氟苯基)硼酸鹽、二甲基苯基(3,4-二甲基苄基)銨四(五氟苯基)硼酸鹽、N,N-二甲基-N-苄基苯銨六氟化銻、N,N-二乙基-N-苄基苯銨四氟化硼、N,N-二甲基-N-苄基吡啶鎓六氟化銻、N,N-二乙基-N-苄基吡啶鎓三氟甲磺酸鹽等。 As the quaternary ammonium salt, for example, dimethylphenyl(4-methoxybenzyl)ammonium hexafluorophosphate, dimethylphenyl(4-methoxybenzyl)ammonium hexafluoroantimonate Salt, dimethylphenyl(4-methoxybenzyl)ammonium tetra(pentafluorophenyl)borate, dimethylphenyl(4-methylbenzyl)ammonium hexafluorophosphate, dimethylbenzene Benzyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethyl phenyl (4-methylbenzyl) ammonium hexafluoro Tetrakis(pentafluorophenyl)borate, methylphenyldibenzylammonium, methylphenyldibenzylammonium hexafluoroantimonate hexafluorophosphate, methylphenyldibenzylammonium tetra(pentafluorobenzene) Base) borate, phenyl tribenzyl ammonium tetra (pentafluorophenyl) borate, dimethyl phenyl (3,4-dimethylbenzyl) ammonium tetra (pentafluorophenyl) borate, N, N-dimethyl-N-benzylanilinium antimony hexafluoride, N,N-diethyl-N-benzylanilinium boron tetrafluoride, N,N-dimethyl-N-benzylpyridinium Antimony hexafluoride, N,N-diethyl-N-benzylpyridinium trifluoromethanesulfonate, etc.
作為上述熱陽離子聚合起始劑中之市售者，例如可列舉：San-Aid SI-60、Sam-Aid SI-80、San-Aid SI-B3、San-Aid SI-B3A、San-Aid SI-B4(均為三新化學工業公司製造)、CXC-1612、CXC-1821(均為King Industries公司製造)等。 As the commercially available one among the above thermal cationic polymerization initiators, for example, San-Aid SI-60, Sam-Aid SI-80, San-Aid SI-B3, San-Aid SI-B3A, San-Aid SI -B4 (all manufactured by Sanxin Chemical Industry Co., Ltd.), CXC-1612, CXC-1821 (all manufactured by King Industries), etc.
其中，上述陽離子聚合起始劑就所獲得之有機EL顯示元件用密封劑成為可進一步抑制釋氣之產生者而言，較佳為含有四級銨鹽。 Among them, the above-mentioned cationic polymerization initiator preferably contains a quaternary ammonium salt in terms of the obtained sealing agent for an organic EL display element that can further suppress the generation of outgassing.
關於上述陽離子聚合起始劑之含量，相對於上述陽離子聚合性化合物100重量份，較佳之下限為0.05重量份，較佳之上限為10重量份。藉由上述陽離子聚合起始劑之含量為該範圍，所獲得之有機EL顯示元件用密封劑成為硬化性、保存穩定性、及硬化物之耐濕性更優異者。上述陽離子聚合起始劑之含量之更佳之下限為0.1重量份，更佳之上限為5重量份。 Regarding the content of the cationic polymerization initiator, the lower limit is preferably 0.05 parts by weight, and the upper limit is preferably 10 parts by weight relative to 100 parts by weight of the cationic polymerizable compound. When the content of the cationic polymerization initiator is within this range, the obtained sealing agent for an organic EL display element is more excellent in curability, storage stability, and moisture resistance of the cured product. The lower limit of the content of the cationic polymerization initiator is more preferably 0.1 parts by weight, and the upper limit is more preferably 5 parts by weight.
本發明之有機EL顯示元件用密封劑於不阻礙本發明之目的之範圍內，除可含有上述陽離子聚合性化合物及上述陽離子聚合起始劑以外，亦可含有其他成分。 The sealing agent for organic EL display elements of the present invention may contain other components in addition to the above-mentioned cationically polymerizable compound and the above-mentioned cation polymerization initiator within the range that does not hinder the purpose of the present invention.
本發明之有機EL顯示元件用密封劑中，為了提高本發明之有機EL顯示元件用密封劑與基板等之接著性，作為上述其他成分，可含有矽烷偶合劑，但就抑制釋氣之產生之觀點而言，較佳為不含矽烷偶合劑。 In the sealing agent for organic EL display elements of the present invention, in order to improve the adhesion between the sealing agent for organic EL display elements of the present invention and the substrate, etc., a silane coupling agent may be contained as the above-mentioned other components, but the generation of outgassing is suppressed From a viewpoint, it is preferable not to contain a silane coupling agent.
作為上述矽烷偶合劑，例如可列舉：3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-異氰酸酯基丙基三甲氧基矽烷等。該等矽烷偶合劑可單獨使用，亦可併用兩種以上。 As said silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanate propyl Trimethoxysilane, etc. These silane coupling agents may be used alone, or two or more of them may be used in combination.
於含有上述矽烷偶合劑之情形時，關於上述矽烷偶合劑之含量，相對於上述陽離子聚合性化合物100重量份，較佳之上限為0.5重量份。藉由上述矽烷偶合劑之含量為0.5重量份以下，能夠抑制釋氣之產生或剩餘之矽烷偶合劑之滲出，且發揮出更高之接著性提昇效果。上述矽烷偶合劑之含量之更佳之上限為0.1重量份。 When the silane coupling agent is contained, the content of the silane coupling agent is preferably 0.5 parts by weight relative to 100 parts by weight of the cationically polymerizable compound. When the content of the above-mentioned silane coupling agent is 0.5 parts by weight or less, the generation of outgassing or the exudation of the remaining silane coupling agent can be suppressed, and a higher adhesion improvement effect can be exerted. The more preferable upper limit of the content of the silane coupling agent is 0.1 parts by weight.
本發明之有機EL顯示元件用密封劑就提高保存穩定性之觀點而言，可含有穩定劑作為上述其他成分。 From the viewpoint of improving storage stability, the sealing agent for organic EL display elements of the present invention may contain a stabilizer as the above-mentioned other components.
作為上述穩定劑，例如可列舉苄胺等胺系化合物等。 As said stabilizer, amine compounds, such as benzylamine, etc. are mentioned, for example.
本發明之有機EL顯示元件用密封劑可含有熱硬化劑作為上述其他成分。 The sealing agent for organic EL display elements of the present invention may contain a thermosetting agent as the above-mentioned other components.
作為上述熱硬化劑，例如可列舉：醯肼化合物、咪唑衍生物、酸酐、雙氰胺、胍衍生物、改質脂肪族聚胺、各種胺與環氧樹脂之加成產物等。 Examples of the thermosetting agent include hydrazine compounds, imidazole derivatives, acid anhydrides, dicyandiamide, guanidine derivatives, modified aliphatic polyamines, and addition products of various amines and epoxy resins.
作為上述醯肼化合物，例如可列舉1,3-雙(肼基羰乙基-5-異丙基乙內醯脲)等。 As said hydrazine compound, 1, 3-bis (hydrazinocarbonylethyl-5-isopropyl hydantoin) etc. are mentioned, for example.
作為上述咪唑衍生物，例如可列舉：1-氰基乙基-2-苯基咪唑、N-(2-(2-甲基-1-咪唑基)乙基)脲、2,4-二胺基-6-(2'-甲基咪唑基-(1'))-乙基-對稱三
該等熱硬化劑可單獨使用，亦可併用兩種以上。 These thermosetting agents may be used alone, or two or more of them may be used in combination.
本發明之有機EL顯示元件用密封劑可含有表面改質劑作為上述其他成分。藉由含有上述表面改質劑，能夠提高本發明之有機EL顯示元件用密封劑之塗膜之平坦性。 The sealing agent for organic EL display elements of the present invention may contain a surface modifier as the above-mentioned other components. By containing the said surface modifier, the flatness of the coating film of the sealing agent for organic electroluminescent display elements of this invention can be improved.
作為上述表面改質劑，例如可列舉界面活性劑或調平劑等。 As said surface modifier, surfactant, a leveling agent, etc. are mentioned, for example.
作為上述表面改質劑，例如可列舉：聚矽氧系、丙烯酸系、氟系等者。 Examples of the above-mentioned surface modifier include silicone-based, acrylic-based, fluorine-based, and the like.
作為上述表面改質劑中之市售者，例如可列舉：BYK-302、BYK-331(均為BYK-Chemie Japan公司製造)、UVX-272(楠本化成公司製造)、Surflon S-611(AGC Seimi Chemical公司製造)等。 Examples of commercially available ones among the above-mentioned surface modifiers include BYK-302, BYK-331 (all are manufactured by BYK-Chemie Japan), UVX-272 (manufactured by Kusumoto Chemical Co., Ltd.), Surflon S-611 (AGC Seimi Chemical Corporation) and so on.
本發明之有機EL顯示元件用密封劑中，作為上述其他成分，為了提高元件電極之耐久性，可含有與於有機EL顯示元件用密封劑中產生之酸進行反應之化合物或離子交換樹脂。 The sealing agent for an organic EL display element of the present invention may contain a compound or ion exchange resin that reacts with the acid generated in the sealing agent for an organic EL display element as the above-mentioned other components in order to improve the durability of the element electrode.
作為與上述所產生之酸進行反應之化合物，可列舉與酸進行中和之物質，例如，鹼金屬之碳酸鹽或碳酸氫鹽、或鹼土金屬之碳酸鹽或碳酸氫鹽等。具體而言，例如可使用碳酸鈣、碳酸氫鈣、碳酸鈉、碳酸氫鈉等。 As the compound that reacts with the acid generated above, a substance that neutralizes with an acid can be mentioned, for example, carbonate or bicarbonate of alkali metal, or carbonate or bicarbonate of alkaline earth metal. Specifically, for example, calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, etc. can be used.
作為上述離子交換樹脂，可使用陽離子交換型、陰離子交換型、兩離子交換型之任一種，尤其適宜為可吸附氯化物離子之陽離子交換型或兩離子交換型。 As the above-mentioned ion exchange resin, any of a cation exchange type, an anion exchange type, and a two-ion exchange type can be used, and a cation exchange type or a two-ion exchange type capable of adsorbing chloride ions is particularly suitable.
又，本發明之有機EL顯示元件用密封劑中，作為上述其他 成分，視需要可含有硬化延遲劑、補強劑、軟化劑、塑化劑、黏度調整劑、紫外線吸收劑、抗氧化劑等公知之各種添加劑。 In addition, in the sealing agent for organic EL display elements of the present invention, as the above-mentioned other The ingredients may contain various known additives such as hardening retarders, reinforcing agents, softeners, plasticizers, viscosity modifiers, ultraviolet absorbers, and antioxidants, if necessary.
作為製造本發明之有機EL顯示元件用密封劑之方法，例如可列舉如下方法等：使用勻相分散機、均質攪拌機、萬能攪拌機、行星式混合機、捏合機、3輥研磨機等混合機，將陽離子聚合性化合物、陽離子聚合起始劑、及視需要添加之其他成分混合。 As a method of manufacturing the sealant for an organic EL display element of the present invention, for example, the following methods are used: using a mixer such as a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill, etc. The cationic polymerizable compound, the cationic polymerization initiator, and other components added as necessary are mixed.
關於本發明之有機EL顯示元件用密封劑，於25℃使用E型黏度計測定之黏度之較佳之下限為5mPa‧s，較佳之上限為500mPa‧s。藉由上述黏度為該範圍，本發明之有機EL顯示元件用密封劑成為塗佈性更優異者。上述黏度之更佳之下限為10mPa‧s，更佳之上限為100mPa‧s。 Regarding the sealant for organic EL display elements of the present invention, the lower limit of the viscosity measured with an E-type viscometer at 25° C. is preferably 5 mPa·s, and the preferable upper limit is 500 mPa·s. When the viscosity is in this range, the sealing agent for an organic EL display element of the present invention is more excellent in coatability. The lower limit of the above viscosity is more preferably 10mPa‧s, and the more preferable upper limit is 100mPa‧s.
再者，上述黏度為例如可藉由使用VISCOMETER TV-22(東機產業公司製造)作為E型黏度計，利用CP1之錐板，自各黏度範圍中之最佳之扭矩數中適當選擇1~100rpm之轉數而進行測定。 Furthermore, the above-mentioned viscosity can be, for example, by using VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) as an E-type viscometer, using the cone plate of CP1, and appropriately selecting 1~100rpm from the best torque in each viscosity range. The number of revolutions is measured.
本發明之有機EL顯示元件用密封劑可尤其適宜地用作被覆具有有機發光材料層之積層體而進行密封之面內密封劑。 The sealant for an organic EL display element of the present invention can be particularly suitably used as an in-plane sealant for covering and sealing a laminate having an organic light-emitting material layer.
根據本發明，可提供一種對於可撓性基板等之接著性亦優異、且能夠抑制由元件之劣化所引起之顯示不良的有機電激發光顯示元件用密封劑。 According to the present invention, it is possible to provide a sealant for an organic electroluminescent display element that is excellent in adhesiveness to flexible substrates and the like, and can suppress display defects caused by the deterioration of the element.
以下，列舉實施例更詳細地說明本發明，但本發明並不僅限於該等實施例。 Hereinafter, the present invention will be explained in more detail with examples, but the present invention is not limited to these examples.
(實施例1) (Example 1)
使用攪拌混合機(Thinky公司製造，「AR-250」)，將作為本發明之水解性陽離子聚合性化合物之上述式(1)表示之化合物(Daicel公司製造，「Celloxide 2021P」)100重量份、與作為熱陽離子聚合起始劑之二甲基苯基(4-甲氧基苄基)銨四(五氟苯基)硼酸鹽(King Industries公司製造，「CXC-1821」)0.5重量份以攪拌速度3000rpm均勻地攪拌混合，而製作有機EL顯示元件用密封劑。 Using a stirring mixer (manufactured by Thinky, "AR-250"), 100 parts by weight of the compound represented by the above formula (1) (manufactured by Daicel, "Celloxide 2021P") as the hydrolyzable cationically polymerizable compound of the present invention, And 0.5 parts by weight of dimethylphenyl(4-methoxybenzyl)ammonium tetrakis(pentafluorophenyl) borate (manufactured by King Industries, "CXC-1821") as a thermal cationic polymerization initiator. Stir and mix uniformly at a speed of 3000 rpm to produce a sealing agent for an organic EL display element.
將所獲得之有機EL顯示元件用密封劑稱量300mg並封入至小瓶中，於100℃加熱30分鐘而使之硬化。進而，將該小瓶於85℃之恆溫烘箱中加熱100小時，將小瓶中之氣化成分設為釋氣產生量，並使用氣相層析質譜分析計(日本電子公司製造，「JMS-Q1050」)進行測定。將結果示於表1。 The obtained sealant for organic EL display elements was weighed 300 mg, sealed in a vial, and heated at 100° C. for 30 minutes to harden it. Furthermore, the vial was heated in a constant temperature oven at 85°C for 100 hours, the vaporization component in the vial was set as the amount of outgassing generation, and a gas chromatography mass spectrometer (manufactured by JEOL Co., Ltd., "JMS-Q1050" was used. ) Perform the measurement. The results are shown in Table 1.
(實施例2~6、比較例1~3) (Examples 2 to 6, Comparative Examples 1 to 3)
依據表1中所記載之摻合比，將表1中所記載之各材料以與實施例1同樣之方式攪拌混合，而製作實施例2~6、比較例1~3之有機EL顯示元件用密封劑。 According to the blending ratio described in Table 1, the materials described in Table 1 were stirred and mixed in the same manner as in Example 1 to produce organic EL display elements of Examples 2 to 6 and Comparative Examples 1 to 3 Sealants.
對所獲得之各有機EL顯示元件用密封劑，以與實施例1同樣之方式測定釋氣產生量。將結果示於表1。再者，針對實施例2中所獲得之密封劑，代替於100℃進行加熱30分鐘，於照射紫外線1500mJ/cm2後，於80℃加熱 30分鐘而使之硬化。 With respect to each of the obtained sealing agents for organic EL display elements, the amount of outgas generation was measured in the same manner as in Example 1. The results are shown in Table 1. Furthermore, for the sealant obtained in Example 2, instead of heating at 100°C for 30 minutes, after irradiating ultraviolet rays at 1500 mJ/cm 2 , it was cured by heating at 80°C for 30 minutes.
<評價> <evaluation>
針對實施例及比較例中所獲得之各有機EL顯示元件用密封劑進行以下之評價。將結果示於表1。 The following evaluation was performed about each sealing agent for organic electroluminescent display elements obtained in an Example and a comparative example. The results are shown in Table 1.
(1)黏度 (1) Viscosity
針對實施例及比較例中所獲得之各有機EL顯示元件用密封劑，使用E型黏度計(東機產業公司製造，「VISCOMETER TV-22」)，測定25℃之黏度。 For each organic EL display device sealant obtained in Examples and Comparative Examples, an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., "VISCOMETER TV-22") was used to measure the viscosity at 25°C.
(2)對於可撓性基板之接著性 (2) Adhesion to flexible substrates
取極微量之實施例及比較例中所獲得之各有機EL顯示元件用密封劑置於20mm×50mm之聚碳酸酯板(Takiron公司製造)之中央部，使相同大小之聚碳酸酯板重疊於其上而將密封劑壓散開。於該狀態下使密封劑硬化(實施例1、3~6、及比較例1~3中所獲得之各密封劑係於100℃加熱30分鐘而使之硬化，實施例2中所獲得之密封劑係於照射紫外線1500mJ/cm2後，於80℃加熱30分鐘而使之硬化)，而獲得接著試片。使用EZgraph(島津製作所公司製造)對所獲得之接著試片之接著強度進行測定。此時，將接著強度為1.0kgf/cm2以上者評價為「○」，將接著強度為0.5kgf/cm2以上且未達1.0kgf/cm2者評價為「△」，將接著強度未達0.5kgf/cm2者評價為「×」，而評價對於可撓性基板之接著性。 A very small amount of each organic EL display device sealant obtained in the Examples and Comparative Examples was placed on the center of a 20mm×50mm polycarbonate plate (manufactured by Takiron Corporation), and the polycarbonate plates of the same size were overlapped On top of it, the sealant will be dispersed. In this state, the sealant was hardened (each of the sealants obtained in Examples 1, 3 to 6, and Comparative Examples 1 to 3 was heated at 100°C for 30 minutes to harden, and the seal obtained in Example 2 The agent system was irradiated with ultraviolet rays of 1500 mJ/cm 2 and then heated at 80° C. for 30 minutes to harden) to obtain an adhesive test piece. The adhesive strength of the obtained adhesive test piece was measured using EZgraph (manufactured by Shimadzu Corporation). In this case, the bonding strength of 1.0kgf / cm 2 or more were evaluated as "○", and then the strength of 0.5kgf / cm 2 or more and less than 1.0kgf / cm 2 were evaluated as "△", less than the adhesion strength The value of 0.5 kgf/cm 2 was evaluated as "×", and the adhesiveness to the flexible substrate was evaluated.
(3)硬化性 (3) Hardening
針對實施例及比較例中所獲得之各有機EL顯示元件用密封劑，使用DSC裝置(Agilent Technologies公司製造，「UMA600」)對進行硬化(實施例1、3~6、及比較例1~3中所獲得之各密封劑係於100℃加熱30分鐘而 使之硬化，實施例2中所獲得之密封劑係於照射紫外線1500mJ/cm2後，於80℃加熱30分鐘而使之硬化)時之硬化前後之發熱量進行測定，並根據下述式導出環氧基之反應率。 The sealants for organic EL display elements obtained in the Examples and Comparative Examples were cured using a DSC device (manufactured by Agilent Technologies, "UMA600") (Examples 1, 3 to 6, and Comparative Examples 1 to 3) The sealants obtained in Example 2 were cured by heating them at 100°C for 30 minutes, and the sealants obtained in Example 2 were cured by heating them at 80°C for 30 minutes after being irradiated with ultraviolet rays of 1500mJ/cm 2) The calorific value before and after curing was measured, and the reaction rate of epoxy group was derived according to the following formula.
環氧基之反應率(%)=100×(硬化前之發熱量-硬化後之發熱量)/硬化前之發熱量 Epoxy reaction rate (%)=100×(heat value before curing-heat value after curing)/heat value before curing
將環氧基之反應率為90%以上之情形評價為「○」，將為70%以上且未達90%之情形評價為「△」，將未達70%之情形評價為「×」，而對硬化性進行評價。 The case where the reaction rate of the epoxy group is 90% or more is evaluated as "○", the case where the reaction rate of epoxy group is more than 70% and less than 90% is evaluated as "△", and the case where the reaction rate is less than 70% is evaluated as "×", And the hardenability is evaluated.
(4)有機EL顯示元件之顯示性能 (4) Display performance of organic EL display element
(配置有具有有機發光材料層之積層體的基板之製作) (Production of a substrate equipped with a laminate with organic light-emitting material layers)
將於玻璃基板(長度30mm、寬度30mm、厚度0.7mm)上使ITO電極以1000Å之厚度進行成膜而成者設為基板。對上述基板利用丙酮、鹼性水溶液、離子交換水、異丙醇分別進行15分鐘超音波洗淨後，利用煮沸之異丙醇進行10分鐘洗淨，進而，利用UV-Ozone Cleaner(Nippon Laser Electronics公司製造，「NL-UV253」)進行事前處理。 A glass substrate (length 30mm, width 30mm, thickness 0.7mm) was formed by forming an ITO electrode with a thickness of 1000Å as a substrate. After ultrasonic cleaning of the above-mentioned substrate with acetone, alkaline aqueous solution, ion-exchange water, and isopropanol for 15 minutes, the substrate was cleaned with boiling isopropanol for 10 minutes, and then UV-Ozone Cleaner (Nippon Laser Electronics Manufactured by the company, "NL-UV253") for pre-processing.
其次，將該基板固定於真空蒸鍍裝置之基板夾，向素燒之坩堝中添加N,N'-二(1-萘基)-N,N'-二苯基聯苯胺(α-NPD)200mg，向另一不同之素燒坩堝中添加三(8-羥基喹啉)鋁(Alq3)200mg，並將真空腔室內減壓至1×10-4Pa。其後，對添加有α-NPD之坩堝進行加熱，將α-NPD以蒸鍍速度15Å/s堆積於基板，使膜厚600Å之電洞輸送層成膜。繼而，對添加有Alq3之坩堝進行加熱，以15Å/s之蒸鍍速度使膜厚600Å之有機發光材料層成膜。其後，將形成有電洞輸送層及有機發光材料層之基板轉移至另一真空蒸鍍 裝置，並向該真空蒸鍍裝置內之鎢製電阻加熱舟皿中添加氟化鋰200mg，向另一鎢製舟皿中添加鋁線1.0g。其後，將真空蒸鍍裝置之蒸鍍器內減壓至2×10-4Pa，使氟化鋰以0.2Å/s之蒸鍍速度進行5Å成膜後，使鋁以20Å/s之速度進行1000Å成膜。利用氮氣使蒸鍍器內恢復至常壓，並取出配置有具有有機發光材料層之積層體之基板。 Next, fix the substrate to the substrate holder of the vacuum evaporation device, and add N,N'-bis(1-naphthyl)-N,N'-diphenylbenzidine (α-NPD) to the crucible of unburnt 200 mg, add 200 mg of tris(8-hydroxyquinoline) aluminum (Alq 3 ) to another different unburnt crucible, and reduce the pressure in the vacuum chamber to 1×10 -4 Pa. After that, the crucible added with α-NPD was heated, and α-NPD was deposited on the substrate at a deposition rate of 15 Å/s to form a 600 Å hole transport layer. Then, the crucible added with Alq 3 was heated, and an organic light-emitting material layer with a film thickness of 600 Å was formed at a vapor deposition rate of 15 Å/s. After that, the substrate on which the hole transport layer and the organic light-emitting material layer were formed was transferred to another vacuum evaporation device, and 200 mg of lithium fluoride was added to the tungsten resistance heating boat in the vacuum evaporation device. Add 1.0g of aluminum wire to a tungsten boat. After that, the pressure in the vaporizer of the vacuum vapor deposition device was reduced to 2×10 -4 Pa, lithium fluoride was deposited at a vapor deposition rate of 0.2 Å/s for 5 Å, and then aluminum was formed at a rate of 20 Å/s. Perform 1000Å film formation. The inside of the evaporator is returned to normal pressure with nitrogen, and the substrate on which the laminate with the organic luminescent material layer is arranged is taken out.
(利用無機材料膜A進行之被覆) (Coating with inorganic material film A)
以覆蓋配置有所獲得之積層體之基板之該積層體整體之方式設置具有開口部之光罩，並藉由電漿CVD法形成無機材料膜A。 A photomask having an opening is provided so as to cover the entire substrate on which the obtained laminate is arranged, and an inorganic material film A is formed by a plasma CVD method.
電漿CVD法係於如下條件下進行：使用SiH4氣體及氮氣作為原料氣體，將SiH4氣體之流量設為10sccm，將氮氣之流量設為200sccm，將RF功率設為10W(頻率2.45GHz)，將腔室內溫度設為100℃，將腔室內壓力設為0.9Torr。 The plasma CVD method is performed under the following conditions: SiH 4 gas and nitrogen are used as raw materials, the flow rate of SiH 4 gas is set to 10 sccm, the flow rate of nitrogen is set to 200 sccm, and the RF power is set to 10W (frequency 2.45GHz) , The temperature in the chamber is set to 100°C, and the pressure in the chamber is set to 0.9 Torr.
所形成之無機材料膜A之厚度為約1μm。 The thickness of the formed inorganic material film A was about 1 μm.
(樹脂保護膜之形成) (Formation of resin protective film)
使用噴墨噴出裝置(Microjet公司製造，「NanoPrinter 300」)，將實施例及比較例中所獲得之各有機EL顯示元件用密封劑藉由噴墨方式以80pL之噴出量塗佈於玻璃基板上。於塗佈時進行調整以使膜厚成為20μm以下。繼而，使有機EL顯示元件用密封劑硬化(實施例1、3~6、及比較例1~3中所獲得之各密封劑係於100℃加熱30分鐘而使之硬化，實施例2中所獲得之密封劑係於照射紫外線1500mJ/cm2後，於80℃加熱30分鐘而使之硬化)，而形成樹脂保護膜。 Using an inkjet ejection device (manufactured by Microjet, "NanoPrinter 300"), each of the organic EL display device sealants obtained in the examples and comparative examples were coated on the glass substrate with an ejection amount of 80 pL by an inkjet method . During coating, adjustment is made so that the film thickness becomes 20 μm or less. Then, the sealant for organic EL display elements was hardened (each of the sealants obtained in Examples 1, 3 to 6, and Comparative Examples 1 to 3 was heated at 100°C for 30 minutes to harden, as described in Example 2 The obtained sealant was irradiated with ultraviolet rays of 1500 mJ/cm 2 and then heated at 80° C. for 30 minutes to harden it to form a resin protective film.
(利用無機材料膜B進行之被覆) (Coating with inorganic material film B)
於形成樹脂保護膜後，以覆蓋該樹脂保護膜之整體之方式設置具有開口部之光罩，並藉由電漿CVD法形成無機材料膜B，而獲得有機EL顯示元件。 After the resin protective film is formed, a photomask with 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 to obtain an organic EL display element.
電漿CVD法係於如下條件下進行：使用SiH4氣體及氮氣作為原料氣體，將SiH4氣體之流量設為10sccm，將氮氣之流量設為200sccm，將RF功率設為10W(頻率2.45GHz)，將腔室內溫度設為100℃，將腔室內壓力設為0.9Torr。 The plasma CVD method is performed under the following conditions: SiH 4 gas and nitrogen are used as raw materials, the flow rate of SiH 4 gas is set to 10 sccm, the flow rate of nitrogen is set to 200 sccm, and the RF power is set to 10W (frequency 2.45GHz) , The temperature in the chamber is set to 100°C, and the pressure in the chamber is set to 0.9 Torr.
所形成之無機材料膜B之厚度為約1μm。 The thickness of the formed inorganic material film B was about 1 μm.
(有機EL顯示元件之發光狀態) (Light-emitting state of organic EL display element)
將所獲得之有機EL顯示元件於溫度85℃、濕度85%之條件下暴露100小時後，施加10V之電壓，藉由目測觀察元件之發光狀態(有無發光及暗點)。將無暗點或周邊淬熄而均勻地發光之情形評價為「○」，將確認到暗點或周邊淬熄之情形評價為「△」，將非發光部明顯擴大之情形評價為「×」。 After the obtained organic EL display device was exposed to the conditions of temperature 85° C. and humidity 85% for 100 hours, a voltage of 10V was applied, and the light-emitting state of the device (the presence or absence of light-emitting and dark spots) was visually observed. The case where there is no dark spot or peripheral quenching and uniform light emission is evaluated as "○", the case where dark spots or peripheral quenching is confirmed is evaluated as "△", and the non-luminous area is significantly enlarged as "×" .
[產業上之可利用性] [Industrial availability]
根據本發明，可提供一種對於可撓性基板等之接著性亦優異、且能夠抑制由元件之劣化所引起之顯示不良的有機電激發光顯示元件用密封劑。 According to the present invention, it is possible to provide a sealant for an organic electroluminescent display element that is excellent in adhesiveness to flexible substrates and the like, and can suppress display defects caused by the deterioration of the element.
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|---|---|---|---|
| TW105135637A TWI726934B (en) | 2015-11-19 | 2016-11-03 | Sealant for organic electroluminescent display element |
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| JP (2) | JP6530767B2 (en) |
| KR (1) | KR20180084633A (en) |
| CN (2) | CN107852790B (en) |
| TW (1) | TWI726934B (en) |
| WO (1) | WO2017086144A1 (en) |
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| KR20200016195A (en) * | 2017-06-02 | 2020-02-14 | 세키스이가가쿠 고교가부시키가이샤 | Encapsulant for Organic EL Display Element |
| TWI688142B (en) * | 2017-09-01 | 2020-03-11 | 南韓商Ｌｇ化學股份有限公司 | Organic electronic device and method for preparing the same |
| KR102448613B1 (en) * | 2020-11-23 | 2022-09-28 | 솔루스첨단소재 주식회사 | Resin composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201428026A (en) * | 2012-11-28 | 2014-07-16 | Nippon Kayaku Kk | Resin composition and cured product thereof (2) |
| TW201542669A (en) * | 2014-02-27 | 2015-11-16 | Sekisui Chemical Co Ltd | Curable resin composition for sealing organic electroluminescent display element, curable resin sheet for sealing organic electroluminescent display element, and organic electroluminescent display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5427858A (en) * | 1990-11-30 | 1995-06-27 | Idemitsu Kosan Company Limited | Organic electroluminescence device with a fluorine polymer layer |
| 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 |
| CN1558921A (en) * | 2001-08-03 | 2004-12-29 | Dsm | Curable compositions for display devices |
| KR100799146B1 (en) * | 2003-08-21 | 2008-01-29 | 아사히 가세이 케미칼즈 가부시키가이샤 | Photosensitive composition and cured product 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 |
| CN102010686B (en) * | 2010-09-30 | 2013-04-17 | 烟台德邦科技有限公司 | Double-solidification system fast-flowing underfill and preparation method thereof |
| 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 |
| WO2014175129A1 (en) * | 2013-04-26 | 2014-10-30 | 三洋化成工業株式会社 | Adhesive agent for low-polarity resin, and molded article produced using 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 |
| KR20220098297A (en) * | 2014-05-20 | 2022-07-11 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for organic electroluminescence display element |
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2016
- 2016-11-01 WO PCT/JP2016/082407 patent/WO2017086144A1/en active Application Filing
- 2016-11-01 CN CN201680045108.XA patent/CN107852790B/en active Active
- 2016-11-01 JP JP2016567694A patent/JP6530767B2/en active Active
- 2016-11-01 CN CN201911373443.4A patent/CN111031623A/en active Pending
- 2016-11-01 KR KR1020177036421A patent/KR20180084633A/en active IP Right Grant
- 2016-11-03 TW TW105135637A patent/TWI726934B/en active
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201428026A (en) * | 2012-11-28 | 2014-07-16 | Nippon Kayaku Kk | Resin composition and cured product thereof (2) |
| TW201542669A (en) * | 2014-02-27 | 2015-11-16 | Sekisui Chemical Co Ltd | Curable resin composition for sealing organic electroluminescent display element, curable resin sheet for sealing organic electroluminescent display element, and organic electroluminescent display element |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107852790B (en) | 2020-05-12 |
| KR20180084633A (en) | 2018-07-25 |
| JP6530767B2 (en) | 2019-06-12 |
| JPWO2017086144A1 (en) | 2018-06-07 |
| CN107852790A (en) | 2018-03-27 |
| WO2017086144A1 (en) | 2017-05-26 |
| JP2019147963A (en) | 2019-09-05 |
| TW201730269A (en) | 2017-09-01 |
| CN111031623A (en) | 2020-04-17 |
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