JP3540915B2 - Organic thin film EL device - Google Patents
Organic thin film EL device Download PDFInfo
- Publication number
- JP3540915B2 JP3540915B2 JP15233597A JP15233597A JP3540915B2 JP 3540915 B2 JP3540915 B2 JP 3540915B2 JP 15233597 A JP15233597 A JP 15233597A JP 15233597 A JP15233597 A JP 15233597A JP 3540915 B2 JP3540915 B2 JP 3540915B2
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- substituted
- integer
- aromatic hydrocarbon
- unsubstituted
- Prior art date
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- 239000010409 thin film Substances 0.000 title claims description 48
- 229920005668 polycarbonate resin Polymers 0.000 claims description 45
- 239000004431 polycarbonate resin Substances 0.000 claims description 45
- 125000003118 aryl group Chemical group 0.000 claims description 44
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 239000010408 film Substances 0.000 claims description 19
- 238000002347 injection Methods 0.000 claims description 17
- 239000007924 injection Substances 0.000 claims description 17
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 239000010410 layer Substances 0.000 description 48
- -1 diol compound Chemical class 0.000 description 35
- 239000012044 organic layer Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- 239000000758 substrate Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 230000004075 alteration Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- XZCJVWCMJYNSQO-UHFFFAOYSA-N butyl pbd Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=CC(=CC=2)C=2C=CC=CC=2)O1 XZCJVWCMJYNSQO-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000001302 tertiary amino group Chemical group 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- 0 C*(***=*N(C)c1cc(N(C)C)ccc1)=O Chemical compound C*(***=*N(C)c1cc(N(C)C)ccc1)=O 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- KLCLIOISYBHYDZ-UHFFFAOYSA-N 1,4,4-triphenylbuta-1,3-dienylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)=CC=C(C=1C=CC=CC=1)C1=CC=CC=C1 KLCLIOISYBHYDZ-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- 125000005978 1-naphthyloxy group Chemical group 0.000 description 1
- GUPMCMZMDAGSPF-UHFFFAOYSA-N 1-phenylbuta-1,3-dienylbenzene Chemical compound C=1C=CC=CC=1[C](C=C[CH2])C1=CC=CC=C1 GUPMCMZMDAGSPF-UHFFFAOYSA-N 0.000 description 1
- NIDFGXDXQKPZMA-UHFFFAOYSA-N 14h-benz[4,5]isoquino[2,1-a]perimidin-14-one Chemical compound C1=CC(N2C(=O)C=3C4=C(C2=N2)C=CC=C4C=CC=3)=C3C2=CC=CC3=C1 NIDFGXDXQKPZMA-UHFFFAOYSA-N 0.000 description 1
- XFSAZBKSWGOXRH-UHFFFAOYSA-N 2-(2-carbonochloridoyloxyethoxy)ethyl carbonochloridate Chemical compound ClC(=O)OCCOCCOC(Cl)=O XFSAZBKSWGOXRH-UHFFFAOYSA-N 0.000 description 1
- MLMTTYBBAJMLCF-UHFFFAOYSA-N 2-(4-hydroxybenzoyl)oxyethyl 4-hydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCCOC(=O)C1=CC=C(O)C=C1 MLMTTYBBAJMLCF-UHFFFAOYSA-N 0.000 description 1
- YVEJKPOENFQMLJ-UHFFFAOYSA-N 2-[2-(4-hydroxybenzoyl)oxyethoxy]ethyl 4-hydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCCOCCOC(=O)C1=CC=C(O)C=C1 YVEJKPOENFQMLJ-UHFFFAOYSA-N 0.000 description 1
- UWDLNKOFUPMXCB-UHFFFAOYSA-N 2-[2-[2-(4-hydroxybenzoyl)oxyethoxy]ethoxy]ethyl 4-hydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCCOCCOCCOC(=O)C1=CC=C(O)C=C1 UWDLNKOFUPMXCB-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- HYFFNAVAMIJUIP-UHFFFAOYSA-N 2-ethylpropane-1,3-diol Chemical compound CCC(CO)CO HYFFNAVAMIJUIP-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005979 2-naphthyloxy group Chemical group 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 1
- BKTRENAPTCBBFA-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-phenylphenyl)propan-2-yl]-2-phenylphenol Chemical compound C=1C=C(O)C(C=2C=CC=CC=2)=CC=1C(C)(C)C(C=1)=CC=C(O)C=1C1=CC=CC=C1 BKTRENAPTCBBFA-UHFFFAOYSA-N 0.000 description 1
- IJWIRZQYWANBMP-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-propan-2-ylphenyl)propan-2-yl]-2-propan-2-ylphenol Chemical compound C1=C(O)C(C(C)C)=CC(C(C)(C)C=2C=C(C(O)=CC=2)C(C)C)=C1 IJWIRZQYWANBMP-UHFFFAOYSA-N 0.000 description 1
- SAKSLEUNBMYMPZ-UHFFFAOYSA-N 4-[[(4-hydroxyphenyl)-dimethylsilyl]oxy-dimethylsilyl]phenol Chemical compound C=1C=C(O)C=CC=1[Si](C)(C)O[Si](C)(C)C1=CC=C(O)C=C1 SAKSLEUNBMYMPZ-UHFFFAOYSA-N 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004217 4-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 1
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- 125000006189 4-phenyl benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- ZYASLTYCYTYKFC-UHFFFAOYSA-N 9-methylidenefluorene Chemical compound C1=CC=C2C(=C)C3=CC=CC=C3C2=C1 ZYASLTYCYTYKFC-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- VESMRDNBVZOIEN-UHFFFAOYSA-N 9h-carbazole-1,2-diamine Chemical compound C1=CC=C2C3=CC=C(N)C(N)=C3NC2=C1 VESMRDNBVZOIEN-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QNIZQZCRPYLJRI-UHFFFAOYSA-N OC=1C=C(C=CC1)N(C1=CC(=CC=C1)N(C1=CC=C(C=C1)C)C1=CC=C(C=C1)C)C1=CC(=CC=C1)O Chemical compound OC=1C=C(C=CC1)N(C1=CC(=CC=C1)N(C1=CC=C(C=C1)C)C1=CC=C(C=C1)C)C1=CC(=CC=C1)O QNIZQZCRPYLJRI-UHFFFAOYSA-N 0.000 description 1
- AJXWFYJRVIVSPV-UHFFFAOYSA-N Oc1ccc(cc1)C1(CCCC1)c1ccc(O)cc1.Oc1ccc(cc1)C1(CCCCC1)c1ccc(O)cc1 Chemical compound Oc1ccc(cc1)C1(CCCC1)c1ccc(O)cc1.Oc1ccc(cc1)C1(CCCCC1)c1ccc(O)cc1 AJXWFYJRVIVSPV-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005530 alkylenedioxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzoquinoline Natural products C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical compound OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
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- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 239000000990 laser dye Substances 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
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- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
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- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
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- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- NZFNXWQNBYZDAQ-UHFFFAOYSA-N thioridazine hydrochloride Chemical compound Cl.C12=CC(SC)=CC=C2SC2=CC=CC=C2N1CCC1CCCCN1C NZFNXWQNBYZDAQ-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
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- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は新規な有機薄膜ＥＬ素子に関するものである。さらに詳しく言えば、本発明は耐熱性、機械的強度、経時変化に優れたポリカーボネート樹脂からなる有機薄膜ＥＬ素子に関するものである。
【０００２】
【従来の技術】
近年、有機薄膜ＥＬ素子は自己発光型であるために視野角依存性に富み、視認性が高く、さらには薄膜型の完全固体素子であるために省スペース等の観点から注目され、実用化研究への展開が開始されている。しかしながらエネルギー変換効率、発光量子効率のさらなる向上や、経時での有機薄膜の安定性の付与など解決すべき問題が多数ある。
【０００３】
これまで有機薄膜ＥＬ素子は低分子を利用したものと高分子を利用したものが報告されている。低分子系においては種々の積層構造の採用により高効率化の実現が、またドーピング法をうまくコントロールすることにより耐久性の向上が報告されている。ただし、低分子集合体の場合、長時間における経時での膜状態の変化が生じることが報告されており膜の安定性に関して、本質的な問題点を抱えている。一方、高分子系材料においては、これまで主にＰＰＶ（ｐｏｌｙ−ｐ−ｐｈｅｎｙｌｅｎｅｖｉｎｙｌｅｎｅ）系列やｐｏｌｙ−ｔｈｉｏｐｈｅｎｅ等について精力的に検討が行われてきた。しかしながらこれらの材料系は純度を上げることが困難であることや、本質的に蛍光量子収率が低いことが挙げられ、高性能なＥＬ素子は得られていないが現状である。高分子材料の場合、本質的にガラス状態が安定であることを考慮した場合、高蛍光量子効率を付与することができれば、優れたＥＬ素子の構築が可能となる。
【０００４】
【発明が解決しようとする課題】
本発明は上記従来技術の現状に鑑みてなされたものであり、有機層を構成する成分として、特に電荷輸送性を有し耐熱性に優れる芳香族ポリカーボネート樹脂を含有した耐久性に優れる有機ＥＬ素子を提供することをその目的とする。
【０００５】
【課題を解決するための手段】
本発明者らは鋭意検討した結果、下記に示される特定の芳香族ポリカーボネート樹脂を含有する有機層を有するＥＬ素子が優れた発光特性を有することを見出し、本発明に至った。
【０００６】
すなわち、本発明は、
（１）互いに対向する陽極と陰極間に１層または複数層の有機化合物薄膜よりなる発光層を備えた有機薄膜ＥＬ素子において、少なくとも１層が下記一般式（Ｉ）に示される芳香族ポリカーボネート樹脂を含有する層であることを特徴とする有機薄膜ＥＬ素子、
【０００７】
【化２１】
〔式中、ｎは５〜５０００の整数、Ａｒ1及びＡｒ4は同一又は異なる芳香族炭化水素の２価基、Ａｒ2及びＡｒ3は同一又は異なる、置換もしくは無置換の芳香族炭化水素基、または置換もしくは無置換の複素環基を表わす。Ｘは脂肪族の２価基、環状脂肪族の２価基または、
【０００９】
【化２２】
（ここで、Ｒ1及びＲ2は各々独立して置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基またはハロゲン原子であり、ｌ及びｍは各々独立して０〜４の整数であり、Ｙは単結合、炭素原子数１〜１２の直鎖状、分岐状もしくは環状のアルキレン基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ2−、
【００１１】
【化２３】
から選ばれ、Ｚは脂肪族炭化水素の２価基を表わし、ａは０〜２０の整数、ｂは１〜２０００の整数、Ｒ3，Ｒ4は各々独立して置換又は無置換のアルキル基ないしは置換又は無置換の芳香族炭化水素基を表わす。）を表わす。〕
（２）互いに対向する陽極と陰極間に少なくとも１層以上のホール注入輸送層を有する複数層の有機化合物薄膜よりなる発光層を備えた有機薄膜ＥＬ素子において、少なくともホール注入輸送層の１層が前記一般式（Ｉ）に示される芳香族ポリカーボネート樹脂を含有する層であることを特徴とする有機薄膜ＥＬ素子、
（３）上記（１）項における発光層のうち少なくとも１層が、前記一般式（Ｉ）に示される芳香族ポリカーボネート樹脂と電子輸送性物質の混合膜とからなることを特徴とする有機薄膜ＥＬ素子、
（４）上記（１）項における発光層のうち少なくとも１層が、前記一般式（Ｉ）に示される芳香族ポリカーボネート樹脂と電子輸送性物質と発光性物質の混合膜からなることを特徴とする有機薄膜ＥＬ素子、
（５）互いに対向する陽極と陰極間に、複数層の有機化合物薄膜よりなる発光層を備えた有機薄膜ＥＬ素子において、発光層が前記一般式（Ｉ）に示される芳香族ポリカーボネート樹脂を含有する層と少なくとも１層以上のホール注入輸入層もしくは１層以上の電子注入輸送層もしくは少なくとも１層以上の両注入輸送層から構成されていることを特徴とする有機薄膜ＥＬ素子、
（６）芳香族ポリカーボネート樹脂が下記一般式（II）および（III）で表わされる繰り返し単位からなり、繰り返し単位の組成比が０＜ｋ／（ｋ＋ｊ）≦１である芳香族ポリカーボネート樹脂であることを特徴とする前記（１）〜（５）項記載の有機薄膜ＥＬ素子、
【００１３】
【化２４】
〔式中、ｋは５〜５０００の整数、ｊは０〜５０００の整数、Ａｒ1及びＡｒ4は同一又は異なる芳香族炭化水素の２価基、Ａｒ2及びＡｒ3は同一又は異なる置換もしくは無置換の芳香族炭化水素基、または置換もしくは無置換の複素環基を表わす。Ｘは脂肪族の２価基、環状脂肪族の２価基または、
【００１５】
【化２５】
（ここで、Ｒ1及びＲ2は各々独立して置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基またはハロゲン原子であり、ｌ及びｍは各々独立して０〜４の整数であり、Ｙは単結合、炭素原子数１〜１２の直鎖状、分岐状もしくは環状のアルキレン基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ2−、
【００１７】
【化２６】
から選ばれ、Ｚは脂肪族炭化水素の２価基を表わし、ａは０〜２０の整数、ｂは１〜２０００の整数、Ｒ3，Ｒ4は各々独立して置換又は無置換のアルキル基ないしは置換又は無置換の芳香族炭化水素基を表わす。）を表わす。〕
（７）芳香族ポリカーボネート樹脂が下記一般式（IV）に示される芳香族ポリカーボネート樹脂であることを特徴とする上記（１）〜（５）項記載の有機薄膜ＥＬ素子、
【００１９】
【化２７】
〔式中、ｎ，Ａｒ2，Ａｒ3，Ｘは前記と同義〕
（８）芳香族ポリカーボネート樹脂が下記一般式（Ｖ）および（III）で表わされる繰り返し単位からなり、繰り返し単位の組成比が０＜ｋ／（ｋ＋ｊ）≦１である芳香族ポリカーボネート樹脂であることを特徴とする上記（１）〜（５）項記載の有機薄膜ＥＬ素子である。
【００２１】
【化２８】
〔式中、ｋ，ｊ，Ａｒ2，Ａｒ3，Ｘは前記と同義〕
以下、本発明に用いる芳香族ポリカーボネート樹脂について説明する。
【００２３】
本発明の芳香族ポリカーボネート樹脂は、従来ポリカーボネート樹脂の製造法として公知のビスフェノールと炭酸誘導体との重合の同様の方法で製造できる。
すなわち、本発明の上記一般式（II）又は一般式（Ｖ）で表わされる繰り返し単位からなる芳香族ポリカーボネート樹脂は、下記一般式（VI）又は一般式（VII）で表わされる第３級アミノ基を有するジオール化合物と、ビスアリールカーボネートとのエステル交換法、ホスゲンとの溶液または界面重合によるホスゲン法、あるいはジオールから誘導されるビスクロロホーメートを用いるビスクロロホーメート法等により製造される。この際、下記一般式（VIII）で表わされるジオール化合物を併用することによって、上記一般式（Ｉ）又は一般式（IV）で表わされる繰り返し単位からなる芳香族ポリカーボネート樹脂、更に、上記一般式（II）で表わされる繰り返し単位と上記一般式（III）で表わされる繰り返し単位からなる芳香族ポリカーボネート樹脂あるいは上記一般式（Ｖ）で表わされる繰り返し単位と上記一般式（III）で表わされる繰り返し単位からなる芳香族ポリカーボネート樹脂を製造することができ、こうすることによって所望の特性を備えた芳香族ポリカーボネート樹脂が得られる。上記一般式（II）で表わされる繰り返し単位と上記一般式（III）で表わされる繰り返し単位との割合及び上記一般式（Ｖ）で表わされる第３級アミノ基を有する繰り返し単位と上記一般式（III）で表わされる繰り返し単位との割合は所望の特性により広い範囲から選択することができる。
【００２４】
【化２９】
ＨＯ−Ｘ−ＯＨ （VIII）
〔各式中のＡｒ1〜Ａｒ4，Ｘは前記と同義〕
一般式（VI）及び一般式（VII）で示される第３級アミノ基を有するジオール化合物の具体例を以下に示す。Ａｒ2，Ａｒ3が同一又は異なる置換もしくは無置換の芳香族炭化水素基である場合、及び置換もしくは無置換の複素環基である場合の具体例としては以下のものを挙げることができる。
【００２６】
（１）芳香族炭化水素基；フェニル基、縮合多環基としてナフチル基、ピレニル基、２−フルオレニル基、９，９−ジメチル−２−フルオレニル基、アズレニル基、アントリル基、トリフェニレニル基、クリセニル基、フルオレニリデンフェニル基、５Ｈ−ジベンゾ〔ａ，ｄ〕シクロヘプテニリデンフェニル基、非縮合多環基としてビフェニリル基、ターフェニリル基、または
【００２７】
【化３０】
ここで、Ｗは−Ｏ−，−Ｓ−，−ＳＯ−，−ＳＯ2−，−ＣＯ−及び以下の２価基を表わす。
【００２９】
【化３１】
で表わされる。Ｒ6は水素原子、置換又は無置換のアルキル基、置換又は無置換の芳香族炭化水素基を表わす。
（２）複素環基；チエニル基、ベンゾチエニル基、フリル基、ベンゾフラニル基、カルバゾリル基などが挙げられる。
また、Ａｒ1及びＡｒ4で示される芳香族炭化水素の２価基としては上記Ａｒ2及びＡｒ3で示した芳香族炭化水素基の２価基が挙げられる。
【００３１】
上述の芳香族炭化水素基及び複素環基は以下に示す基を置換基として有してもよい。又、これら置換基は上記一般式中のＲ5の具体例として表わされる。
（３）ハロゲン原子、トリフルオロメチル基、シアノ基、ニトロ基。
【００３２】
（４）アルキル基；好ましくはＣ1〜Ｃ12とりわけＣ1〜Ｃ8、さらに好ましくはＣ1〜Ｃ4の直鎖または分岐鎖のアルキル基であり、これらのアルキル基はさらにフッ素原子、水酸基、シアノ基、Ｃ1〜Ｃ4のアルコキシ基、フェニル基、又はハロゲン原子、Ｃ1〜Ｃ4のアルキル基もしくはＣ1〜Ｃ4のアルコキシ基で置換されたフェニル基を含有してもよい。具体的にはメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基、ｓ−ブチル基、ｎ−ブチル基、ｉ−ブチル基、トリフルオロメチル基、２−ヒドロキシエチル基、２−シアノエチル基、２−エトキシエチル基、２−メトキシエチル基、ベンジル基、４−クロロベンジル基、４−メチルベンジル基、４−メトキシベンジル基、４−フェニルベンジル基等が挙げられる。
【００３３】
（５）アルコキシ基（−ＯＲ7）；Ｒ7は上記（４）で定義したアルキル基を表わす。具体的にはメトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｔ−ブトキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｉ−ブトキシ基、２−ヒドロキシエトキシ基、２−シアノエトキシ基、ベンジルオキシ基、４−メチルベンジルオキシ基、トリフルオロメトキシ基等が挙げられる。
【００３４】
（６）アリールオキシ基；アリール基としてフェニル基、ナフチル基が挙げられる。これはＣ1〜Ｃ4のアルコキシ基、Ｃ1〜Ｃ4のアルキル基またはハロゲン原子を置換基として含有してもよい。具体的にはフェノキシ基、１−ナフチルオキシ基、２−ナフチルオキシ基、４−メチルフェノキシ基、４−メトキシフェノキシ基、４−クロロフェノキシ基、６−メチル−２−ナフチルオキシ基等が挙げられる。
【００３５】
（７）置換メルカプト基またはアリールメルカプト基；具体的にはメチルチオ基、エチルチオ基、フェニルチオ基、ｐ−メチルフェニルチオ基等が挙げられる。
（８）
【００３６】
【化３２】
式中、Ｒ8及びＲ9は各々独立に（４）で定義したアルキル基またはアリール基を表わし、アリール基としては例えばフェニル基、ビフェニリル基またはナフチル基が挙げられ、これらはＣ1〜Ｃ4のアルコキシ基、Ｃ1〜Ｃ4のアルキル基またはハロゲン原子を置換基として含有してもよい。またアリール基上の炭素原子と共同で環を形成してもよい。具体的にはジエチルアミノ基、Ｎ−メチル−Ｎ−フェニルアミノ基、Ｎ，Ｎ−ジフェニルアミノ基、Ｎ，Ｎ−ジ（ｐ−トリル）アミノ基、ジベンジルアミノ基、ピペリジノ基、モルホリノ基、ユロリジル基等が挙げられる。
【００３８】
（９）メチレンジオキシ基、またはメチレンジチオ基等のアルキレンジオキシ基またはアルキレンジチオ基等が挙げられる。
一般式（VIII）で示されるジオール化合物の具体例を以下に示す。
【００３９】
１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，８−オクタンジオール、１，１０−デカンジオール、２−メチル−１，３−プロパンジオール、２，２−ジメチル−１，３−プロパンジオール、２−エチル−１，３−プロパンジオール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ポリテトラメチレンエーテルグリコール等の脂肪族ジオールや１，４−シクロヘキサンジオール、１，３−シクロヘキサンジオール、シクロヘキサン−１，４−ジメタノール等の環状脂肪族ジオールが挙げられる。
【００４０】
又、芳香環を有するジオール化合物としては、４，４’−ジヒドロキシジフェニル、ビス（４−ヒドロキシフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、２，２−ビス（４−ヒドロキシフェニル）プロパン、２，２−ビス（３−メチル−４−ヒドロキシフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、１，１−ビス（４−ヒドロキシフェニル）シクロペンタン、２，２−ビス（３−フェニル−４−ヒドロキシフェニル）プロパン、２，２−ビス（３−イソプロピル−４−ヒドロキシフェニル）プロパン、２，２−ビス（４−ヒドロキシフェニル）ブタン、２，２−ビス（３，５−ジメチル−４−ヒドロキシフェニル）プロパン、２，２−ビス（３，５−ジブロモ−４−ヒドロキシフェニル）プロパン、４，４’−ジヒドロキシジフェニルスルホン、４，４’−ジヒドロキシジフェニルスルホキシド、４，４’−ジヒドロキシジフェニルスルフィド、３，３’−ジメチル−４，４’−ジヒドロキシジフェニルスルフィド、４，４’−ジヒドロキシジフェニルオキシド、２，２−ビス（４−ヒドロキシフェニル）ヘキサフルオロプロパン、９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（４−ヒドロキシフェニル）キサンテン、エチレングリコール−ビス（４−ヒドロキシベンゾエート）、ジエチレングリコール−ビス（４−ヒドロキシベンゾエート）、トリエチレングリコール−ビス（４−ヒドロキシベンゾエート）、１，３−ビス（４−ヒドロキシフェニル）−テトラメチルジシロキサン、フェノール変性シリコーンオイル等が挙げられる。
【００４１】
【発明の実施の形態】
以下、実施例により本発明を説明する。なお、下記実施例において部はすべて重量部である。
製造例
出発物質として、下記構造の第３級アミノ基を有する化合物を用いた。
【００４２】
【化３３】
乾燥ＴＨＦ５０ｍｌにＮ，Ｎ−ビス（３−ヒドロキシフェニル）−Ｎ’，Ｎ’−ビス（４−トリル）−ｍ−フェニレンジアミン３．１３ｇ（０．００６５ｍｏｌ）、トリエチルアミン１．７１ｇ（０．０１７ｍｏｌ）を溶解した。この溶液にジエチレングリコールビスクロロフォーメート１．６７ｇ（０．００７２ｍｏｌ）を乾燥ＴＨＦ１０ｍｌに溶かしたものを、水冷下、３０分かけて滴下した。滴下終了後、粘稠混合物をさらに１５分間撹拌し、０．１３ｇのフェノールを３ｍｌの乾燥ＴＨＦに溶かしたものを加えた。５分間撹拌の後、得られた粘稠混合物をメタノール中に沈殿させ、粗生成物を濾取した。このものにジクロロメタン溶解−メタノール沈殿の処理を２回施し、沈殿物を濾取、乾燥して下記構造式のポリカーボネート樹脂（化合物Ｎo.１）を得た。得られた目的物は３．３０ｇで収率は８０．５％であり、ガラス転移点は８２．６℃であった。
【００４４】
【化３４】
この物の分子量をゲルパーミエーションクロマトグラフィーにより測定したところ、ポリスチレン換算の分子量は以下のようであった。
数平均分子量 ２５４００
重量平均分子量 ４０２００
また、元素分析結果は以下のとおりであった。
【００４６】
【００４７】
本発明の有機薄膜ＥＬ素子における有機層のうち上記の芳香族ポリカーボネート樹脂を含有する層は、スピンコート法やキャスト法等の公知の方法によって薄膜化することができる。上記芳香族ポリカーボネート樹脂はジクロロメタンやテトラヒドロフラン等の有機溶媒に容易に溶解する。従って上記芳香族ポリカーボネート樹脂を溶解できる適当な溶媒により適当な濃度の溶液を作製し、これを用いて上記方法等により塗工し薄膜を作製できる。電子輸送性物質や発光性物質との混合膜を作製する場合は上記芳香族ポリカーボネート樹脂溶液にそれらを共に溶解させて塗工すれば作製できる。又、異種のポリマーを相溶しにくい性質を利用して一種のポリマー媒体中に他種のポリマー微小分散相を形成するような膜を作製することもできる。この場合樹脂種の組み合わせや混合比を変えた混合溶液を作製し、これを用いて同様な湿式成膜法で塗工すればよい。このような膜においては前記一般式（Ｉ）に示される芳香族ポリカーボネート樹脂をポリマー媒体として使用してもよいし、微小分散相として使用しても良い。これらの膜は通常２０μｍ以下と薄いので、塗工前に孔径０．４５μｍ以下、より好ましくは孔径０．１μｍ以下のフィルターで溶液を濾過して使用するのが好ましい。有機薄膜ＥＬ素子における有機層が複数の有機層からなり低分子化合物層を有する場合には湿式成膜法以外に真空蒸着法やスパッタ法等の乾式成膜法を利用することができる。
【００４８】
有機ＥＬ素子を構成する有機層は有機層単層もしくは複数層から構成されてもよい。有機層が単層から構成される場合、その層がポリカーボネート樹脂単独から構成されても良いし、場合によっては電子輸送性を有する低分子化合物の分散や高分子とのブレンドまたは他の電荷輸送性ポリマーとのブレンド、さらには蛍光量子効率の極めて高い蛍光分子を微量ドーピングすることも高効率化に有効である。電子輸送性物質としては電子を輸送する能力を持つ既存の材料を使用することができる。例えばフルオレノン、アントラキノジメタン、ジフェノキノン、チオピランジオキシド、ペリレンテトラカルボン酸、フルオレニリデンメタン、アントラキノジメタン、アントロン等とその誘導体やこれまで優れた電子輸送性を有することが報告されているオキサジアゾール誘導体やトリアゾール誘導体を利用することが可能である。蛍光量子効率の極めて高い蛍光分子としては溶液状態において強い蛍光を示すレーザー色素等やこれまで有機ＥＬ素子に発光材として使用されてきた既存の低分子蛍光性材料を利用することが可能である。例えばアントラセン、ナフタレン、フェナントレン、ピレン、テトラセン、コロネン、クリセン、フルオレセイン、ペリレン、フタロペリレン、ナフタロペリレン、ペリノン、フタロペリノン、ナフタロペリノン、ジフェニルブタジエン、テトラフェニルブタジエン、クマリン、オキサジアゾール、アルダジン、ビスベンゾキサゾリン、ビススチリル、ピラジン、シクロペンタジエン、キノリン金属錯体、アミノキノリン金属錯体、ベンゾキノリン金属錯体、イミン、ジフェニルエチレン、ビニルアントラセン、ジアミノカルバゾール、ピラン、チオピラン、ポリメタン、メロシアニン、イミダゾールキノレート化オキシノイド化合物、キナクリドン、ルブレン等およびそれらの誘導体がある。
【００４９】
さらに必要であれば有機層を複数層から構成することも可能である。ポリカーボネート樹脂含有層の上部にさらにスピンコート法や真空蒸着法により電子注入輸送層や発光層等を積層することが可能である。又、ポリカーボネート樹脂含有層を形成する前にホール注入輸送層を形成することも性能向上に有効な場合がある。ホール注入輸送層を構成する材料としては、これまで有機ＥＬ素子において機能することが報告されているフタロシアニン系化合物、ポルフィリン系化合物、オキサジアゾール、トリアゾール、トリフェニルアミン系化合物、ポリシラン等の既存材料を利用することが可能である。
【００５０】
このようにして形成された有機層の膜厚については特に制限はなく、通常５ｎｍから２０μｍの範囲で選ばれる。更に好ましくは５ｎｍから０．２μｍの範囲である。膜厚はピンホール等の膜欠陥の発生や発光波長での素子内での光干渉や膜厚増加による印加電圧の上昇等を加味して調整される。
【００５１】
本発明における有機薄膜ＥＬ素子の陽極としては４ｅＶ好ましくは４．８ｅＶより大きな仕事関数を持つ金属、合金、酸化金属等が利用される。このような電極材料の具体例としては金、白金、パラジウム、銀、タングステン、ニッケル、コバルト、ＩＴＯ、ＣｕＩ、ＳｎＯ2、ＺｎＯ等の透明電極の利用が挙げられる。特に好ましくはＩＴＯ基板が好適である。ＩＴＯ基板の場合表面の平滑なものが好ましく、また表面の汚れを良く洗浄して使用する。洗浄法としては既知の方法でよいがオゾン雰囲気下での紫外線照射や酸素雰囲気下でのプラズマ処理を行ったものが好適である。
【００５２】
一方、陰極としては仕事関数の４ｅＶより小さい金属、合金等が利用される。このような物質の具体例としてはナトリウム、カルシウム、マグネシウム、リチウム、アルミニウム、サマリウム及びこれらの合金等が利用できる。
有機薄膜ＥＬ素子を面発光素子として使用する場合は、これらの電極は少なくとも一方が素子の発光波長領域において十分透明であり、その反対側は発光波長領域において十分反射率が大きいことが望まれる。端面発光の場合には透明である必要はない。透明電極としては先に述べたＩＴＯが好ましく、その基板も透明なガラス板やプラスチック板が使用される。
【００５３】
得られた有機薄膜ＥＬ素子の環境の温湿度、雰囲気に対する安定性向上のために素子の表面に保護層を設けたり、シリコンオイル等を封入して素子全体を保護することが有効である。
このようにして得られた本発明の有機薄膜ＥＬ素子に陽極にプラスを陰極にマイナスを接続し、電圧を印加するとＥＬ発光が観測できる。
【００５４】
有機薄膜ＥＬ素子では通電によりジュール熱が発生し、その熱により有機層の再結晶化、凝集の進行等や低分子材料の拡散が生じ、これらはいずれも素子の耐久性を低下させる。本発明の有機薄膜ＥＬ素子では有機層に融点温度の高くアモルファス状態の安定な芳香族ポリカーボネート樹脂を使用するため、結晶化や凝集による素子劣化や拡散による素子劣化を抑制することができ良好な耐久性を有する素子を得ることができる。
【００５５】
【実施例】
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらの実施例によってなんら限定されるものではない。
実施例１
２ｍｍのストライプ状にエッチングを行ったＩＴＯ基板を煮沸アルコールにより洗浄し、さらに表面を酸素プラズマにより表面処理した。化合物Ｎo.１の芳香族ポリカーボネート樹脂の１．０ｗｔ％ジクロロメタン溶液を作製し、孔径０．１μｍのメンブランフィルターで濾過した。この溶液を使用してＩＴＯ基板上にスピンコート法により１００ｎｍの膜厚で有機発光層を形成した。十分乾燥を行った後に、蒸着装置内部に基板をセットし、１０-4Ｐａの真空度にてマスクを介しＭｇＡｇ合金層を２００ｎｍ形成した。発光面のサイズは２ｍｍ×２ｍｍであった。
【００５６】
このようにして作成したＥＬ素子にＩＴＯを陽極に、ＭｇＡｇを陰極に接続したところ、加圧電圧１０Ｖにて青色発光が観測された。又、この有機層は結晶化等の変質は起こさなかった。
【００５７】
実施例２
実施例１と同様にＥＬ素子の作成を行った。ただし、この場合さらにジクロロメタン溶液内に電子輸送性物質として２−（４−Ｂｉｐｈｅｎｙｌｙｌ）−５−（４−ｔ−ｂｕｔｙｌｐｈｅｎｙｌ）−１，３，４−ｏｘａｄｉａｚｏｌｅ（ＰＢＤ）を固形分の３０ｗｔ％になるように化合物Ｎo.１の芳香族ポリカーボネート樹脂とともに溶解させ、単層の有機発光層を形成した。このようにして作成したＥＬ素子にＩＴＯを陽極に、ＭｇＡｇを陰極に接続したところ、印加電圧１０Ｖにて青色発光が観測された。又、この有機層は結晶化等の変質は起こさなかった。
【００５８】
【化３５】
実施例３
実施例１と同様にＥＬ素子の作成を行った。ただし、ジクロロメタン溶液内に２−（４−Ｂｉｐｈｅｎｙｌｙｌ）−５−（４−ｔ−ｂｕｔｙｌｐｈｅｎｙｌ）−１，３，４−ｏｘａｄｉａｚｏｌｅ（ＰＢＤ）を固形分の３０ｗｔ％と発光材としてペリレン誘導体（Ｂ）を固形分の３ｗｔ％を化合物Ｎo.１の芳香族ポリカーボネート樹脂とともに溶解させ、単層の有機発光層を形成した。このようにして作成したＥＬ素子にＩＴＯを陽極に、ＭｇＡｇを陰極に接続したところ、印加電圧１０Ｖにてオレンジ色の発光が観測された。又、この有機層は結晶化等の変質は起こさなかった。
【００６０】
【化３６】
実施例４
ＩＴＯ基板上にホール注入輸送層として、実施例１と同様に処理したＩＴＯ基板上に実施例１と同じジクロロメタン溶液を用いてｄｉｐｐｉｎｇ法により実施例１と同様な膜を５０ｎｍ形成した。十分乾燥を行った後に、蒸着装置内部に基板をセットし、１０-4Ｐａの真空度にて下記構造（Ｃ）の分子堆積膜を５０ｎｍ形成し、２層型の発光層を形成した。さらにマスクを介しＭｇＡｇ合金層を２００ｎｍ形成した。発光面のサイズは２ｍｍ×２ｍｍであった。
このようにして作成したＥＬ素子にＩＴＯを陽極に、ＭｇＡｇを陰極に接続したところ、印加電圧１０Ｖにて緑色の発光が観測された。又、この有機層は結晶化等の変質は起こさなかった。
【００６２】
【化３７】
実施例５
２ｍｍのストライプ状にエッチングを行ったＩＴＯ基板を煮沸アルコールにより洗浄し、さらに表面を酸素プラズマにより表面処理した。この上にホール注入輸送層として銅フタロシアニンを１０ｎｍの膜厚で真空蒸着により作製した。この上に実施例１で使用した化合物Ｎo.１の芳香族ポリカーボネート樹脂溶液を用いて９０ｎｍの膜厚でスピンコート法により有機発光層を形成した。十分乾燥を行った後に、蒸着装置内部に基板をセットし、１０-4Ｐａの真空度にてマスクを介しＭｇＡｇ合金層を２００ｎｍ形成した。発光面のサイズは２ｍｍ×２ｍｍであった。
このようにして作成したＥＬ素子にＩＴＯを陽極に、ＭｇＡｇを陰極に接続したところ、印加電圧１０Ｖにて青色発光が観測された。又、この有機層は結晶化等の変質は起こさなかった。
【００６４】
実施例６
実施例５と同様にしてＩＴＯ基板上にホール注入輸送層としての銅フタロシアニン層と化合物Ｎo.１の芳香族ポリカーボネート層を作製した。この上に実施例４と同じように真空蒸着法により構造（Ｃ）の分子堆積膜を５０ｎｍ形成し、３層型の発光層を形成した。さらにマスクを介しＭｇＡｇ合金層を２００ｎｍ形成した。発光面のサイズは２ｍｍ×２ｍｍであった。このようにして作成したＥＬ素子にＩＴＯを陽極に、ＭｇＡｇを陰極に接続したところ、印加電圧１０Ｖにて緑色の発光が観測された。又、この有機層は結晶化等の変質は起こさなかった。
実施例７
実施例５と同様にしてＩＴＯ基板上に銅フタロシアニン層を作製した。この上に実施例３で用いた化合物Ｎo.１の芳香族ポリカーボネート樹脂とＰＢＤとペリレン誘導体（Ｂ）の混合溶液を用いてスピンコート法で有機発光層を作製した。さらに下記構造（Ｃ）のオキサジアゾール化合物を真空蒸着法で３０ｎｍの電子注入輸送層を作製した。さらにマスクを介しＭｇＡｇ合金層を２００ｎｍ形成した。発光面のサイズは２ｍｍ×２ｍｍであった。このようにして作成したＥＬ素子にＩＴＯを陽極に、ＭｇＡｇを陰極に接続したところ、印加電圧１０Ｖにてオレンジ色の発光が観測された。又、この有機層は結晶化等の変質は起こさなかった。
【００６５】
【化３８】
【発明の効果】
以上説明したように、本発明により有機薄膜層に特定の芳香族ポリカーボネート樹脂を用いることにより結晶化等の変質を起すことがないなど耐久性に優れた有機薄膜ＥＬ素子を得ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel organic thin film EL device. More specifically, the present invention relates to an organic thin film EL device made of a polycarbonate resin having excellent heat resistance, mechanical strength, and aging.
[0002]
[Prior art]
In recent years, organic thin-film EL devices are self-luminous, have a high viewing angle dependency, have high visibility, and are thin-film, completely solid-state devices. Deployment to has been started. However, there are many problems to be solved, such as further improvement of energy conversion efficiency and emission quantum efficiency, and provision of stability of the organic thin film over time.
[0003]
Heretofore, organic thin film EL devices using low molecules and those using polymers have been reported. It has been reported that in a low-molecular-weight system, high efficiency can be realized by adopting various laminated structures, and that durability can be improved by properly controlling the doping method. However, it has been reported that in the case of a low-molecular assembly, a change in the film state occurs over time for a long time, and there is an essential problem with respect to the stability of the film. On the other hand, in the case of high molecular materials, the PPV (poly-p-phenylenevinylene) series, poly-thiophene, and the like have been vigorously studied. However, it is difficult to increase the purity of these material systems, and the fluorescence quantum yield is essentially low. Therefore, a high-performance EL device has not been obtained, but is present. In the case of a polymer material, considering that the glass state is essentially stable, if high fluorescence quantum efficiency can be imparted, an excellent EL device can be constructed.
[0004]
[Problems to be solved by the invention]
The present invention has been made in view of the above-mentioned state of the art, and has excellent durability including an aromatic polycarbonate resin having a charge transporting property and excellent heat resistance as a component constituting an organic layer. The purpose is to provide.
[0005]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that an EL element having an organic layer containing a specific aromatic polycarbonate resin shown below has excellent light-emitting characteristics, and have reached the present invention.
[0006]
That is, the present invention
(1) In an organic thin-film EL device having a light-emitting layer composed of one or more organic compound thin films between an anode and a cathode facing each other, at least one layer is an aromatic polycarbonate resin represented by the following general formula (I) An organic thin film EL element, which is a layer containing
[0007]
Embedded image
Wherein n is an integer of 5-5000, Ar 1 And Ar Four Is a divalent group of the same or different aromatic hydrocarbons, Ar Two And Ar Three Represents the same or different, substituted or unsubstituted aromatic hydrocarbon group, or substituted or unsubstituted heterocyclic group. X is an aliphatic divalent group, a cycloaliphatic divalent group, or
[0009]
Embedded image
(Where R 1 And R Two Are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group or a halogen atom, l and m are each independently an integer of 0 to 4, Y is a single bond, A linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-, -SO Two −,
[0011]
Embedded image
Z is a divalent group of an aliphatic hydrocarbon, a is an integer of 0 to 20, b is an integer of 1 to 2000, R Three , R Four Each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ). ]
(2) In an organic thin-film EL device provided with a light-emitting layer composed of a plurality of organic compound thin films having at least one or more hole injection / transport layers between an anode and a cathode facing each other, at least one of the hole injection / transport layers is An organic thin-film EL device comprising a layer containing the aromatic polycarbonate resin represented by the general formula (I),
(3) An organic thin film EL, wherein at least one of the light emitting layers in the above item (1) comprises a mixed film of the aromatic polycarbonate resin represented by the general formula (I) and an electron transporting substance. element,
(4) At least one of the light emitting layers in the above item (1) comprises a mixed film of the aromatic polycarbonate resin represented by the general formula (I), the electron transporting substance and the light emitting substance. Organic thin film EL element,
(5) In an organic thin-film EL device having a light-emitting layer composed of a plurality of organic compound thin films between an anode and a cathode facing each other, the light-emitting layer contains the aromatic polycarbonate resin represented by the general formula (I). An organic thin-film EL device comprising a layer and at least one or more hole injection / import layers, at least one electron injection / transport layer, or at least one or more double injection / transport layers.
(6) The aromatic polycarbonate resin is composed of repeating units represented by the following general formulas (II) and (III), and the composition ratio of the repeating units is 0 <k / (k + j) ≦ 1. The organic thin film EL device according to any one of (1) to (5),
[0013]
Embedded image
[In the formula, k is an integer of 5-5000, j is an integer of 0-5000, Ar 1 And Ar Four Is a divalent group of the same or different aromatic hydrocarbons, Ar Two And Ar Three Represents the same or different substituted or unsubstituted aromatic hydrocarbon group, or substituted or unsubstituted heterocyclic group. X is an aliphatic divalent group, a cycloaliphatic divalent group, or
[0015]
Embedded image
(Where R 1 And R Two Are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group or a halogen atom, l and m are each independently an integer of 0 to 4, Y is a single bond, A linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-, -SO Two −,
[0017]
Embedded image
Z is a divalent group of an aliphatic hydrocarbon, a is an integer of 0 to 20, b is an integer of 1 to 2000, R Three , R Four Each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ). ]
(7) The organic thin film EL device according to any one of (1) to (5), wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin represented by the following general formula (IV).
[0019]
Embedded image
[Wherein, n, Ar Two , Ar Three , X is as defined above)
(8) The aromatic polycarbonate resin is composed of repeating units represented by the following general formulas (V) and (III), and the composition ratio of the repeating units is 0 <k / (k + j) ≦ 1. The organic thin film EL device according to any one of the above (1) to (5), wherein
[0021]
Embedded image
[Where k, j, Ar Two , Ar Three , X is as defined above)
Hereinafter, the aromatic polycarbonate resin used in the present invention will be described.
[0023]
The aromatic polycarbonate resin of the present invention can be produced by the same method as polymerization of bisphenol and a carbonic acid derivative, which is conventionally known as a method for producing a polycarbonate resin.
That is, the aromatic polycarbonate resin comprising a repeating unit represented by the above general formula (II) or (V) of the present invention has a tertiary amino group represented by the following general formula (VI) or (VII): Is produced by a transesterification method between a diol compound having the formula (1) and a bisaryl carbonate, a phosgene method by solution or interfacial polymerization with phosgene, or a bischloroformate method using a bischloroformate derived from a diol. At this time, by using a diol compound represented by the following general formula (VIII) in combination, an aromatic polycarbonate resin comprising a repeating unit represented by the above general formula (I) or (IV), An aromatic polycarbonate resin comprising a repeating unit represented by II) and a repeating unit represented by the above general formula (III) or a repeating unit represented by the above general formula (V) and a repeating unit represented by the above general formula (III) Thus, an aromatic polycarbonate resin having desired characteristics can be obtained. The ratio of the repeating unit represented by the general formula (II) to the repeating unit represented by the general formula (III) and the repeating unit having a tertiary amino group represented by the general formula (V) and the general formula ( The ratio with the repeating unit represented by III) can be selected from a wide range depending on desired characteristics.
[0024]
Embedded image
HO-X-OH (VIII)
[Ar in each formula 1 ~ Ar Four , X is as defined above)
Specific examples of the diol compounds having a tertiary amino group represented by the general formulas (VI) and (VII) are shown below. Ar Two , Ar Three Are the same or different, substituted or unsubstituted aromatic hydrocarbon groups, and substituted or unsubstituted heterocyclic groups, and specific examples thereof include the following.
[0026]
(1) Aromatic hydrocarbon group: phenyl group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group as a condensed polycyclic group A fluorenylidenephenyl group, a 5H-dibenzo [a, d] cycloheptenylidenephenyl group, a biphenylyl group, a terphenylyl group as a non-fused polycyclic group, or
[0027]
Embedded image
Here, W is -O-, -S-, -SO-, -SO Two -, -CO- and the following divalent groups are represented.
[0029]
Embedded image
Is represented by R 6 Represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group.
(2) Heterocyclic group: thienyl group, benzothienyl group, furyl group, benzofuranyl group, carbazolyl group and the like.
Also, Ar 1 And Ar Four As the divalent group of the aromatic hydrocarbon represented by Two And Ar Three And divalent aromatic hydrocarbon groups.
[0031]
The above-mentioned aromatic hydrocarbon group and heterocyclic group may have the following groups as substituents. These substituents are represented by R in the above general formula. Five Is shown as a specific example.
(3) a halogen atom, a trifluoromethyl group, a cyano group, or a nitro group.
[0032]
(4) an alkyl group; preferably C 1 ~ C 12 Especially C 1 ~ C 8 And more preferably C 1 ~ C Four Is a straight-chain or branched-chain alkyl group. These alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, 1 ~ C Four An alkoxy group, a phenyl group, or a halogen atom, C 1 ~ C Four Alkyl group or C 1 ~ C Four May contain a phenyl group substituted with an alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl, trifluoromethyl, 2-hydroxyethyl , 2-cyanoethyl, 2-ethoxyethyl, 2-methoxyethyl, benzyl, 4-chlorobenzyl, 4-methylbenzyl, 4-methoxybenzyl, 4-phenylbenzyl and the like.
[0033]
(5) alkoxy group (-OR 7 ); R 7 Represents an alkyl group defined in the above (4). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyanoethoxy Group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
[0034]
(6) aryloxy group; examples of the aryl group include a phenyl group and a naphthyl group. This is C 1 ~ C Four An alkoxy group of C 1 ~ C Four May be contained as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, and a 6-methyl-2-naphthyloxy group. .
[0035]
(7) Substituted mercapto group or arylmercapto group; specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(8)
[0036]
Embedded image
Where R 8 And R 9 Each independently represents an alkyl group or an aryl group defined in (4), and examples of the aryl group include a phenyl group, a biphenylyl group and a naphthyl group; 1 ~ C Four An alkoxy group of C 1 ~ C Four May be contained as a substituent. Also, a ring may be formed together with the carbon atom on the aryl group. Specifically, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (p-tolyl) amino group, dibenzylamino group, piperidino group, morpholino group, eurololidyl And the like.
[0038]
(9) An alkylenedioxy group or an alkylenedithio group such as a methylenedioxy group or a methylenedithio group.
Specific examples of the diol compound represented by the general formula (VIII) are shown below.
[0039]
1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1,3- Aliphatic diols such as propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol, and polytetramethylene ether glycol; And cycloaliphatic diols such as cyclohexanediol, 1,3-cyclohexanediol and cyclohexane-1,4-dimethanol.
[0040]
Examples of the diol compound having an aromatic ring include 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxy Phenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane 1,1-bis (4-hydroxyphenyl) cyclopentane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, , 2-bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) p Lopan, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 3, 3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl oxide, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene , 9,9-bis (4-hydroxyphenyl) xanthene, ethylene glycol-bis (4-hydroxybenzoate), diethylene glycol-bis (4-hydroxybenzoate), triethylene glycol-bis (4-hydroxybenzoate), 1,3 -Bis (4-hydroxy Phenyl) - tetramethyldisiloxane, phenol-modified silicone oils.
[0041]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described with reference to examples. In the following examples, all parts are parts by weight.
Manufacturing example
As a starting material, a compound having a tertiary amino group having the following structure was used.
[0042]
Embedded image
N, N-bis (3-hydroxyphenyl) -N ', N'-bis (4-tolyl) -m-phenylenediamine 3.13 g (0.0065 mol), triethylamine 1.71 g (0.017 mol) in 50 ml of dry THF. Was dissolved. A solution of 1.67 g (0.0072 mol) of diethylene glycol bischloroformate dissolved in 10 ml of dry THF was added dropwise to this solution over 30 minutes while cooling with water. After completion of the dropwise addition, the viscous mixture was further stirred for 15 minutes, and a solution prepared by dissolving 0.13 g of phenol in 3 ml of dry THF was added. After stirring for 5 minutes, the resulting viscous mixture was precipitated in methanol, and the crude product was collected by filtration. This was treated twice with dichloromethane-methanol precipitation, and the precipitate was collected by filtration and dried to obtain a polycarbonate resin having the following structural formula (Compound No. 1). The obtained target product was 3.30 g, the yield was 80.5%, and the glass transition point was 82.6 ° C.
[0044]
Embedded image
When the molecular weight of this product was measured by gel permeation chromatography, the molecular weight in terms of polystyrene was as follows.
Number average molecular weight 25400
Weight average molecular weight 40200
The results of elemental analysis were as follows.
[0046]
[0047]
The layer containing the aromatic polycarbonate resin among the organic layers in the organic thin film EL device of the present invention can be thinned by a known method such as a spin coating method or a casting method. The aromatic polycarbonate resin is easily dissolved in an organic solvent such as dichloromethane and tetrahydrofuran. Accordingly, a thin film can be prepared by preparing a solution having an appropriate concentration using an appropriate solvent capable of dissolving the aromatic polycarbonate resin, and applying the solution by the above method or the like. When a mixed film with an electron transporting substance or a luminescent substance is prepared, they can be prepared by dissolving them together in the above aromatic polycarbonate resin solution and coating. Further, it is also possible to produce a film that forms another kind of polymer micro-dispersed phase in one kind of polymer medium by utilizing the property that different kinds of polymers are hardly compatible with each other. In this case, a mixed solution in which the combination of the resin types and the mixing ratio are changed is prepared, and the solution may be applied by a similar wet film forming method. In such a film, the aromatic polycarbonate resin represented by the general formula (I) may be used as a polymer medium or as a finely dispersed phase. Since these films are usually as thin as 20 μm or less, it is preferable to use the solution before filtration by filtering the solution with a filter having a pore size of 0.45 μm or less, more preferably 0.1 μm or less. When the organic layer in the organic thin film EL element is composed of a plurality of organic layers and has a low molecular compound layer, a dry film forming method such as a vacuum evaporation method and a sputtering method can be used in addition to the wet film forming method.
[0048]
The organic layer constituting the organic EL element may be composed of a single organic layer or a plurality of layers. When the organic layer is composed of a single layer, the layer may be composed of a polycarbonate resin alone, or in some cases, a dispersion of a low molecular compound having an electron transport property, a blend with a polymer, or other charge transport properties. It is also effective to increase the efficiency by blending with a polymer and doping a trace amount of a fluorescent molecule having extremely high fluorescence quantum efficiency. As the electron transporting substance, an existing material capable of transporting electrons can be used. For example, fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, etc. It is possible to use oxadiazole derivatives or triazole derivatives. As the fluorescent molecules having extremely high fluorescence quantum efficiency, it is possible to use a laser dye or the like which shows strong fluorescence in a solution state or an existing low molecular fluorescent material which has been used as a light emitting material in an organic EL device. For example, anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl , Pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethane, merocyanine, imidazole quinolated oxinoid compounds, quinacridone, rubrene, etc. And their derivatives.
[0049]
Furthermore, if necessary, the organic layer can be composed of a plurality of layers. An electron injection transport layer, a light emitting layer, and the like can be further laminated on the polycarbonate resin-containing layer by a spin coating method or a vacuum evaporation method. Forming a hole injection / transport layer before forming a polycarbonate resin-containing layer may also be effective in improving performance in some cases. As materials constituting the hole injection transport layer, existing materials such as phthalocyanine-based compounds, porphyrin-based compounds, oxadiazole, triazole, triphenylamine-based compounds, and polysilane, which have been reported to function in organic EL devices, have been used. It is possible to use.
[0050]
The thickness of the organic layer thus formed is not particularly limited, and is usually selected from the range of 5 nm to 20 μm. More preferably, it is in the range of 5 nm to 0.2 μm. The film thickness is adjusted in consideration of the occurrence of film defects such as pinholes, light interference in the device at the emission wavelength, an increase in applied voltage due to an increase in film thickness, and the like.
[0051]
As the anode of the organic thin film EL element in the present invention, a metal, an alloy, a metal oxide, or the like having a work function of 4 eV, preferably greater than 4.8 eV is used. Specific examples of such an electrode material include gold, platinum, palladium, silver, tungsten, nickel, cobalt, ITO, CuI, and SnO. Two , ZnO or the like. Particularly preferably, an ITO substrate is suitable. In the case of an ITO substrate, a substrate having a smooth surface is preferable, and a dirt on the surface is thoroughly washed before use. As a cleaning method, a known method may be used, but a method in which ultraviolet irradiation in an ozone atmosphere or plasma treatment in an oxygen atmosphere is performed is preferable.
[0052]
On the other hand, a metal, alloy, or the like having a work function smaller than 4 eV is used as the cathode. Specific examples of such a substance include sodium, calcium, magnesium, lithium, aluminum, samarium, and alloys thereof.
When an organic thin-film EL element is used as a surface-emitting element, it is desired that at least one of these electrodes is sufficiently transparent in the emission wavelength region of the element, and that the other side has a sufficiently large reflectance in the emission wavelength region. In the case of edge emission, it is not necessary to be transparent. The above-mentioned ITO is preferable as the transparent electrode, and a transparent glass plate or a plastic plate is also used for the substrate.
[0053]
It is effective to provide a protective layer on the surface of the organic thin-film EL device and improve the stability of the obtained organic thin-film EL device against the atmosphere and to protect the entire device by enclosing silicon oil or the like.
When a positive electrode is connected to the positive electrode and a negative electrode is connected to the cathode of the thus obtained organic thin film EL device of the present invention, and a voltage is applied, EL emission can be observed.
[0054]
In an organic thin film EL device, Joule heat is generated by energization, and the heat causes recrystallization of the organic layer, progress of aggregation, and diffusion of a low molecular material, all of which reduce the durability of the device. In the organic thin film EL device of the present invention, a stable amorphous polycarbonate resin having a high melting point and an amorphous state is used for the organic layer, so that device deterioration due to crystallization or aggregation and device deterioration due to diffusion can be suppressed, and good durability can be achieved. An element having the property can be obtained.
[0055]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1
The ITO substrate etched into a 2 mm stripe was washed with boiling alcohol, and the surface was further treated with oxygen plasma. A 1.0 wt% dichloromethane solution of the aromatic polycarbonate resin of Compound No. 1 was prepared and filtered with a membrane filter having a pore size of 0.1 μm. Using this solution, an organic light emitting layer having a thickness of 100 nm was formed on an ITO substrate by spin coating. After performing sufficient drying, the substrate is set inside the evaporation apparatus, and -Four An MgAg alloy layer was formed to a thickness of 200 nm via a mask at a degree of vacuum of Pa. The size of the light emitting surface was 2 mm × 2 mm.
[0056]
When ITO was connected to the anode and MgAg was connected to the cathode of the EL device thus produced, blue light emission was observed at a pressure of 10 V. This organic layer did not undergo any alteration such as crystallization.
[0057]
Example 2
An EL element was prepared in the same manner as in Example 1. However, in this case, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD) as an electron transporting substance in the dichloromethane solution becomes 30 wt% of the solid content. As described above, the compound was dissolved together with the aromatic polycarbonate resin of Compound No. 1 to form a single organic light emitting layer. When ITO was connected to the anode and MgAg was connected to the cathode of the EL device thus produced, blue light emission was observed at an applied voltage of 10 V. This organic layer did not undergo any alteration such as crystallization.
[0058]
Embedded image
Example 3
An EL element was prepared in the same manner as in Example 1. However, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD) is contained in a dichloromethane solution at 30 wt% of solid content and a perylene derivative (B) as a luminescent material. 3 wt% of the solid content was dissolved together with the aromatic polycarbonate resin of Compound No. 1 to form a single organic light emitting layer. When ITO was connected to the anode and MgAg was connected to the cathode for the EL device thus produced, orange light emission was observed at an applied voltage of 10 V. This organic layer did not undergo any alteration such as crystallization.
[0060]
Embedded image
Example 4
As a hole injection / transport layer on an ITO substrate, a film similar to that of Example 1 was formed to a thickness of 50 nm on the ITO substrate treated in the same manner as in Example 1 using the same dichloromethane solution as in Example 1 by the dipping method. After performing sufficient drying, the substrate is set inside the evaporation apparatus, and -Four A molecular deposition film having the following structure (C) was formed to a thickness of 50 nm at a degree of vacuum of Pa to form a two-layer light emitting layer. Further, a 200 nm-thick MgAg alloy layer was formed via a mask. The size of the light emitting surface was 2 mm × 2 mm.
When ITO was connected to the anode and MgAg was connected to the cathode of the EL device thus produced, green light emission was observed at an applied voltage of 10 V. This organic layer did not undergo any alteration such as crystallization.
[0062]
Embedded image
Example 5
The ITO substrate etched into a 2 mm stripe was washed with boiling alcohol, and the surface was further treated with oxygen plasma. A copper phthalocyanine having a thickness of 10 nm was formed thereon as a hole injection transport layer by vacuum evaporation. An organic light-emitting layer was formed thereon by a spin coating method with a thickness of 90 nm using the aromatic polycarbonate resin solution of the compound No. 1 used in Example 1. After performing sufficient drying, the substrate is set inside the evaporation apparatus, and -Four An MgAg alloy layer was formed to a thickness of 200 nm via a mask at a degree of vacuum of Pa. The size of the light emitting surface was 2 mm × 2 mm.
When ITO was connected to the anode and MgAg was connected to the cathode of the EL device thus produced, blue light emission was observed at an applied voltage of 10 V. This organic layer did not undergo any alteration such as crystallization.
[0064]
Example 6
In the same manner as in Example 5, a copper phthalocyanine layer as a hole injection / transport layer and an aromatic polycarbonate layer of Compound No. 1 were formed on an ITO substrate. A 50 nm-thick molecular deposited film having the structure (C) was formed thereon by a vacuum evaporation method in the same manner as in Example 4 to form a three-layer light emitting layer. Further, a 200 nm-thick MgAg alloy layer was formed via a mask. The size of the light emitting surface was 2 mm × 2 mm. When ITO was connected to the anode and MgAg was connected to the cathode for the EL device thus produced, green light emission was observed at an applied voltage of 10 V. This organic layer did not undergo any alteration such as crystallization.
Example 7
A copper phthalocyanine layer was formed on an ITO substrate in the same manner as in Example 5. An organic light emitting layer was formed thereon by spin coating using a mixed solution of the aromatic polycarbonate resin of Compound No. 1 used in Example 3 and PBD and a perylene derivative (B). Further, an oxadiazole compound having the following structure (C) was formed into a 30-nm electron injection / transport layer by a vacuum evaporation method. Further, a 200 nm-thick MgAg alloy layer was formed via a mask. The size of the light emitting surface was 2 mm × 2 mm. When ITO was connected to the anode and MgAg was connected to the cathode for the EL device thus produced, orange light emission was observed at an applied voltage of 10 V. This organic layer did not undergo any alteration such as crystallization.
[0065]
Embedded image
【The invention's effect】
As described above, by using the specific aromatic polycarbonate resin for the organic thin film layer according to the present invention, it is possible to obtain an organic thin film EL element having excellent durability such as not causing deterioration such as crystallization.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15233597A JP3540915B2 (en) | 1997-06-10 | 1997-06-10 | Organic thin film EL device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15233597A JP3540915B2 (en) | 1997-06-10 | 1997-06-10 | Organic thin film EL device |
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| JP3540915B2 true JP3540915B2 (en) | 2004-07-07 |
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| JP2009176762A (en) * | 2007-01-11 | 2009-08-06 | Fujikura Ltd | Organic electroluminescent element and optical interconnect module |
| JP6035706B2 (en) | 2010-04-09 | 2016-11-30 | 三菱化学株式会社 | Manufacturing method of composition for organic electric field element, composition for organic electric field element, manufacturing method of organic electroluminescent element, organic electroluminescent element, organic EL display device and organic EL lighting |
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