JPH11199567A - 1,2,3-triazole compound, its production and organic electroluminescent element - Google Patents
1,2,3-triazole compound, its production and organic electroluminescent elementInfo
- Publication number
- JPH11199567A JPH11199567A JP10006126A JP612698A JPH11199567A JP H11199567 A JPH11199567 A JP H11199567A JP 10006126 A JP10006126 A JP 10006126A JP 612698 A JP612698 A JP 612698A JP H11199567 A JPH11199567 A JP H11199567A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- group
- layer
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 1,2,3-triazole compound Chemical class 0.000 title claims abstract description 80
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000000732 arylene group Chemical group 0.000 claims abstract description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 238000002347 injection Methods 0.000 claims description 49
- 239000007924 injection Substances 0.000 claims description 49
- 230000004888 barrier function Effects 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000005394 methallyl group Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims 4
- SYOANZBNGDEJFH-UHFFFAOYSA-N 2,5-dihydro-1h-triazole Chemical class C1NNN=C1 SYOANZBNGDEJFH-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 238000004020 luminiscence type Methods 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 abstract 1
- KHKSGZWXFYAHHW-UHFFFAOYSA-N 2-[4-[4-(4,5-diphenyltriazol-2-yl)-3-methylphenyl]-2-methylphenyl]-4,5-diphenyltriazole Chemical group CC1=CC(C=2C=C(C)C(=CC=2)N2N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)=CC=C1N(N=1)N=C(C=2C=CC=CC=2)C=1C1=CC=CC=C1 KHKSGZWXFYAHHW-UHFFFAOYSA-N 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
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- 235000019441 ethanol Nutrition 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000872 buffer Substances 0.000 description 6
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- 229910052751 metal Inorganic materials 0.000 description 6
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- 239000005695 Ammonium acetate Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 229940043376 ammonium acetate Drugs 0.000 description 5
- 235000019257 ammonium acetate Nutrition 0.000 description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
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- 238000004544 sputter deposition Methods 0.000 description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
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- 238000001914 filtration Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 150000007857 hydrazones Chemical class 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- YNRGDPQTVDWXPB-UHFFFAOYSA-N 3-(1,2,4-triazol-3-ylidene)-1,2,4-triazole Chemical class N1=NC=NC1=C1N=NC=N1 YNRGDPQTVDWXPB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 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
- 238000001953 recrystallisation Methods 0.000 description 2
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- 238000004528 spin coating Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- MPDDTAJMJCESGV-CTUHWIOQSA-M (3r,5r)-7-[2-(4-fluorophenyl)-5-[methyl-[(1r)-1-phenylethyl]carbamoyl]-4-propan-2-ylpyrazol-3-yl]-3,5-dihydroxyheptanoate Chemical compound C1([C@@H](C)N(C)C(=O)C2=NN(C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C2C(C)C)C=2C=CC(F)=CC=2)=CC=CC=C1 MPDDTAJMJCESGV-CTUHWIOQSA-M 0.000 description 1
- UWRZIZXBOLBCON-VOTSOKGWSA-N (e)-2-phenylethenamine Chemical class N\C=C\C1=CC=CC=C1 UWRZIZXBOLBCON-VOTSOKGWSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-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
- KQZLRWGGWXJPOS-NLFPWZOASA-N 1-[(1R)-1-(2,4-dichlorophenyl)ethyl]-6-[(4S,5R)-4-[(2S)-2-(hydroxymethyl)pyrrolidin-1-yl]-5-methylcyclohexen-1-yl]pyrazolo[3,4-b]pyrazine-3-carbonitrile Chemical compound ClC1=C(C=CC(=C1)Cl)[C@@H](C)N1N=C(C=2C1=NC(=CN=2)C1=CC[C@@H]([C@@H](C1)C)N1[C@@H](CCC1)CO)C#N KQZLRWGGWXJPOS-NLFPWZOASA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
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- TVTJUIAKQFIXCE-HUKYDQBMSA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynyl-1H-purine-6,8-dione Chemical compound NC=1NC(C=2N(C(N(C=2N=1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C)=O TVTJUIAKQFIXCE-HUKYDQBMSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
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- 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
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- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 1
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- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
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- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 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
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- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- OENLEHTYJXMVBG-UHFFFAOYSA-N pyridine;hydrate Chemical compound [OH-].C1=CC=[NH+]C=C1 OENLEHTYJXMVBG-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- 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
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、１，２，３−トリ
アゾール化合物、その製造方法及び有機電界発光素子に
関し、より詳細には、新規な構造を有するビス又はトリ
ス−１，２，３−トリアゾール化合物、その製造方法及
びこの新規化合物を使用した、駆動電圧が小さく、発光
効率が良好な有機電界発光素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a 1,2,3-triazole compound, a method for producing the same, and an organic electroluminescent device, and more particularly, to a bis or tris-1,2,3- having a novel structure. The present invention relates to a triazole compound, a method for producing the same, and an organic electroluminescent device using the novel compound, having a low driving voltage and good luminous efficiency.
【０００２】[0002]
【従来の技術】近年、有機電界発光素子（以下ＥＬ素子
と略す）は、自己発光性のため視界認識性が高く、かつ
完全固体素子であるため耐衝撃性に優れる等の特徴を有
していることから、各種表示、バックライト用ランプ等
に適用することが注目されている。2. Description of the Related Art In recent years, organic electroluminescent devices (hereinafter abbreviated as EL devices) have characteristics such as high self-luminous properties, high visibility recognition, and excellent solid-state impact resistance. Therefore, application to various displays, backlight lamps, and the like has attracted attention.
【０００３】このＥＬ素子には、発光層に無機化合物を
用いる無機ＥＬ素子と有機化合物を用いてなる有機ＥＬ
素子とがある。これらＥＬ素子のなかでも、有機ＥＬ素
子は、印加電圧を低くして、かつフルカラーに対応する
ことを目的として、その実用化の研究が積極的になされ
ている。This EL element includes an inorganic EL element using an inorganic compound for a light emitting layer and an organic EL element using an organic compound.
There is an element. Among these EL devices, organic EL devices have been actively studied for practical use for the purpose of lowering the applied voltage and supporting full color.
【０００４】有機ＥＬ素子は、陽極／発光層／陰極を基
本構成とし、これに陽極より注入された正孔を、効率よ
く発光層に伝達する機能を有する正孔注入輸送層や、陰
極より注入された電子を、効率よく発光層に伝達する機
能を有する電子注入輸送層を、適宜設けたものがよく知
られている。An organic EL device has a basic structure of an anode / light-emitting layer / cathode, and a hole injection / transport layer having a function of efficiently transmitting holes injected from the anode to the light-emitting layer, and an injection from the cathode. It is well known that an electron injecting and transporting layer having a function of efficiently transmitting the transferred electrons to the light emitting layer is appropriately provided.
【０００５】このような構成の有機ＥＬ素子の中で、特
に優れた性能を有しているものとして、陽極／正孔注入
輸送層／発光層／陰極の構成を有する素子が種々提案さ
れている（米国特許第4,539,507 号、同第4,769,292
号、特開昭59−194393号公報、同昭63−295695号公報
等）。例えば、上記構成の有機ＥＬ素子においては、正
孔注入輸送層に薄膜形成性に優れた材料を用いることに
より、正孔注入輸送層と発光層との合計膜厚を１５０ｎ
ｍ以下にすることを可能にし、その結果、２０Ｖ以下の
駆動電圧で高輝度の発光を得ることに成功している。[0005] Among the organic EL devices having such a structure, various devices having a structure of anode / hole injection / transport layer / light emitting layer / cathode have been proposed as having particularly excellent performance. (U.S. Pat.Nos. 4,539,507 and 4,769,292
JP-A-59-194393, JP-A-63-295695, etc.). For example, in the organic EL device having the above structure, by using a material having excellent thin film forming properties for the hole injecting and transporting layer, the total thickness of the hole injecting and transporting layer and the light emitting layer can be reduced to 150 n.
m, and as a result, high-luminance light emission has been successfully obtained with a drive voltage of 20 V or less.
【０００６】また、正孔注入輸送層に、電子を輸送せず
電子に対して障壁として作用するトリフェニルアミン系
の正孔注入輸送化合物を用いて、正孔注入輸送層と発光
層との界面に存在する電子の障壁により、発光層内のこ
の界面に電子を蓄積し、さらに、発光層の材料としてア
ルミニウム（III）錯体を用いることによって、１０Ｖ
以下の低い印加電圧で、１０００ｃｄ／ｍの高輝度の緑
色発色を、発光効率１．５ルーメン／Ｖという高い値で
実現している。An interface between the hole injecting and transporting layer and the light emitting layer is formed by using a triphenylamine-based hole injecting and transporting compound which does not transport electrons and acts as a barrier against electrons. By accumulating electrons at this interface in the light emitting layer due to the electron barrier existing in the light emitting layer, and further using an aluminum (III) complex as a material for the light emitting layer, 10 V
With the following low applied voltage, a green color with high luminance of 1000 cd / m is realized at a high value of luminous efficiency 1.5 lumen / V.
【０００７】ところで、上記有機ＥＬ素子は、電子と正
孔との再結合を発光機構としているため、発光ダイオー
ドなみの低電圧駆動（２〜６Ｖ）が可能なはずである。
しかし、現状では駆動電圧は８Ｖ以上である。これは陽
極と正孔注入輸送層との界面に存在する正孔注入に対す
るエネルギー障壁又は発光層と陰極との界面に存在する
電子注入に対するエネルギー障壁によるものである。さ
らに、一般的な発光の量子効率は、４０％程度が上限で
あるといわれているが、有機ＥＬ素子においては、まだ
３％程度である。[0007] Since the organic EL element has a light-emitting mechanism that recombines electrons and holes, it should be possible to drive at a low voltage (2 to 6 V) as much as a light-emitting diode.
However, at present, the driving voltage is 8 V or more. This is due to the energy barrier against hole injection existing at the interface between the anode and the hole injection transport layer or the energy barrier against electron injection existing at the interface between the light emitting layer and the cathode. Furthermore, it is said that the upper limit of the general quantum efficiency of light emission is about 40%, but it is still about 3% in an organic EL device.
【０００８】このように、陽極／正孔注入輸送層／発光
層／陰極の構成を有する有機ＥＬ素子においては、他の
構成の有機ＥＬ素子に比べて、性能は優れているが、駆
動電圧及び発光効率については必ずしも十分に、満足し
うるものではない。さらに、有機ＥＬ素子は、無機ＥＬ
素子に比べてその構成材料の劣化特性が良くなく、この
ため長時間の使用に耐えられないとの問題点が未だ解決
されていない。As described above, the performance of the organic EL device having the structure of anode / hole injection / transport layer / light emitting layer / cathode is superior to that of the organic EL devices of other structures, but the drive voltage and The luminous efficiency is not always satisfactory. Further, the organic EL element is an inorganic EL element.
The problem that the deterioration characteristics of the constituent material is not as good as that of the element and the problem that the element cannot withstand long-time use has not been solved yet.
【０００９】本発明は、上記課題に鑑みなされたもので
あり、良好な発光効率、高輝度発光、低駆動電圧での発
光、水又は酸素等の物質による化学的及び光、熱等の物
理的劣化の小さい有機ＥＬ素子を提供することを目的と
している。The present invention has been made in view of the above problems, and has good luminous efficiency, high-luminance luminescence, luminescence at a low driving voltage, and chemicals such as water or oxygen and physical phenomena such as light and heat. An object is to provide an organic EL element with small deterioration.
【００１０】[0010]
【課題を解決するための手段】本発明者は、上記に述べ
た優れた特徴を有するＥＬ素子を開発すべく鋭意研究を
重ねた結果、陽極／発光層／陰極の基本構成に、少なく
とも輸送層中の正孔注入輸送層化合物として上記のビス
又はトリス−トリアゾール化合物を用いた場合に、各界
面に存在する電荷注入のエネルギー障壁が緩和され、よ
り低い駆動電圧が可能となるとともに、高い発光効率と
長時間安定な有機ＥＬ素子が得られることを見い出し、
本発明を完成するに至った。The inventor of the present invention has conducted intensive studies to develop an EL device having the above-mentioned excellent characteristics. As a result, the basic structure of the anode / light-emitting layer / cathode has at least a transport layer. When the above-mentioned bis or tris-triazole compound is used as the hole injection transport layer compound in the inside, the energy barrier of the charge injection existing at each interface is relaxed, and a lower driving voltage becomes possible, and high luminous efficiency is obtained. And a long-term stable organic EL element can be obtained.
The present invention has been completed.
【００１１】すなわち本発明によれば、式（Ｉ）That is, according to the present invention, the formula (I)
【００１２】[0012]
【化１０】 Embedded image
【００１３】〔式中、Ａｒ及びＡｒ’は、同一又は異な
って、炭素数６〜１２の置換又は非置換のアリーレン基
であり；Ｘは酸素原子、硫黄原子、−（ＣＨ2 ）n −、
−Ｎ（Ｒ3 ）−又は−ＣＨ（Ｒ4 ）−であり（ここで、
ｎは０〜２の整数であり、Ｒ3は水素原子、炭素数１〜
８のアルキル基、置換又は非置換のフェニル基、メタリ
ル基、アリル基であり、Ｒ4 は水素原子、炭素数１〜８
のアルキル基、置換又は非置換のフェニル基である）；
Ｒ1及びＲ2は、同一又は異なって、水素原子、炭素数１
〜４のアルキル基、置換又は非置換のアリール基であ
る〕で示される１，２，３−トリアゾール化合物が提供
される。Wherein Ar and Ar ′ are the same or different and are a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; X is an oxygen atom, a sulfur atom, — (CH 2 ) n —,
—N (R 3 ) — or —CH (R 4 ) — (where,
n is an integer of 0 to 2; R 3 is a hydrogen atom;
An alkyl group, a substituted or unsubstituted phenyl group, a methallyl group, and an allyl group, wherein R 4 is a hydrogen atom,
An alkyl group or a substituted or unsubstituted phenyl group);
R 1 and R 2 are the same or different and each represent a hydrogen atom,
To 4, an alkyl group or a substituted or unsubstituted aryl group].
【００１４】また、本発明によれば、式（IV）Further, according to the present invention, the formula (IV)
【００１５】[0015]
【化１１】 Embedded image
【００１６】（式中、Ｒ1及びＲ2は式（Ｉ）と同義であ
る）で示されるエタンジオン化合物と、式（Ｖ） Ｈ2ＮＨＮ−Ａｒ−Ｘ−Ａｒ’−ＮＨＮＨ2 ……（Ｖ） （式中、Ａｒ、Ａｒ’及びＸは式（Ｉ）と同義である）
で示されるヒドラジン化合物、又は式（VIII)(Wherein R 1 and R 2 have the same meanings as in formula (I)) and a compound represented by formula (V) H 2 NHN—Ar—X—Ar′—NHNH 2 (V (Wherein, Ar, Ar ′ and X have the same meanings as in formula (I))
Or a hydrazine compound represented by the formula (VIII):
【００１７】[0017]
【化１２】 Embedded image
【００１８】で示されるトリス−（４−ヒドラジノフェ
ニル）アミン化合物とを反応させることにより、上記式
（Ｉ）の１，２，３−トリアゾール化合物を製造する
１，２，３−トリアゾール化合物の製造方法が提供され
る。By reacting with a tris- (4-hydrazinophenyl) amine compound represented by the formula (1), a 1,2,3-triazole compound of the above formula (I) is produced. A manufacturing method is provided.
【００１９】さらに、本発明によれば、陽極、正孔注入
輸送層、発光層及び陰極がこの順で積層された有機電界
発光素子であって、前記正孔注入輸送層が、式（Ｉ）の
１，２，３−トリアゾール化合物を含有する有機電界発
光素子が提供される。Further, according to the present invention, there is provided an organic electroluminescent device in which an anode, a hole injecting and transporting layer, a light emitting layer and a cathode are laminated in this order, wherein the hole injecting and transporting layer has the formula (I) The organic electroluminescent device containing the 1,2,3-triazole compound of the above is provided.
【００２０】[0020]
【発明の実施の態様】本発明のアゾール化合物は、新規
なビス又はトリス−アゾール化合物である。しかし、そ
の反面、合成方法については、一般に良く知られた方法
を適用することができる。DETAILED DESCRIPTION OF THE INVENTION The azole compound of the present invention is a novel bis or tris-azole compound. However, on the other hand, a generally well-known method can be applied to the combining method.
【００２１】本発明の式（Ｉ）の１，２，３−トリアゾ
ール化合物は、以下の構造The 1,2,3-triazole compound of the formula (I) of the present invention has the following structure:
【００２２】[0022]
【化１３】 Embedded image
【００２３】〔式中、Ａｒ及びＡｒ’は、同一又は異な
って、炭素数６〜１２の置換又は非置換のアリーレン基
であり；Ｘは酸素原子、硫黄原子、−（ＣＨ2 ）n −、
−Ｎ（Ｒ3 ）−又は−ＣＨ（Ｒ4 ）−であり（ここで、
ｎは０〜２の整数であり、Ｒ3は水素原子、炭素数１〜
８のアルキル基、置換又は非置換のフェニル基、メタリ
ル基、アリル基であり、Ｒ4 は水素原子、炭素数１〜８
のアルキル基、置換又は非置換のフェニル基である）；
Ｒ1及びＲ2は、同一又は異なって、水素原子、炭素数１
〜４のアルキル基、置換又は非置換のアリール基であ
る〕を有する。Wherein Ar and Ar ′ are the same or different and are a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; X is an oxygen atom, a sulfur atom, — (CH 2 ) n —,
—N (R 3 ) — or —CH (R 4 ) — (where,
n is an integer of 0 to 2; R 3 is a hydrogen atom;
An alkyl group, a substituted or unsubstituted phenyl group, a methallyl group, and an allyl group, wherein R 4 is a hydrogen atom,
An alkyl group or a substituted or unsubstituted phenyl group);
R 1 and R 2 are the same or different and each represent a hydrogen atom,
To 4 alkyl groups or substituted or unsubstituted aryl groups].
【００２４】ここで、Ａｒ及びＡｒ’における「炭素数
６〜１２のアリーレン基」としては、例えば、フェニレ
ン、トリレン、ナフチレン基等が挙げられる。また、こ
の「アリーレン基の置換基」としては、ハロゲン原子、
メチル基、ジメチル基、メトキシ基、エトキシ基、トリ
フロロメチル基等が挙げられる。なお、Ａｒ及びＡｒ’
は同一の置換基であてもよいし、異なる置換基であって
もよい。Here, the "arylene group having 6 to 12 carbon atoms" in Ar and Ar 'includes, for example, phenylene, tolylene, naphthylene and the like. The “substituent of the arylene group” includes a halogen atom,
Examples include a methyl group, a dimethyl group, a methoxy group, an ethoxy group, and a trifluoromethyl group. Note that Ar and Ar ′
May be the same substituent or different substituents.
【００２５】Ｒ1 及びＲ2 における「炭素数１〜４のア
ルキル基」としては、メチル、エチル、プロピル、ｎ−
ブチル、ｔ−ブチル基等が挙げられる。「アリール基」
としては、炭素数６〜１４のアリール基が挙げられ、具
体的にはフェニル基、ナフチル基、アントリル基、フェ
ナントリル基等が挙げられる。なお、Ｒ1 及びＲ2 は同
一の置換基であてもよいし、異なる置換基であってもよ
い。アリール基における置換基としては、メチル基、エ
チル基等の低級アルキル基、メトキシ基、エトキシ基等
の低級アルコキシ基、トリフロロメチル基、塩素等のハ
ロゲン原子等が挙げられる。なお、これら置換基は２個
以上置換されていてもよく、この場合置換基は同一であ
ってもよいし、異なってもよい。As the "alkyl group having 1 to 4 carbon atoms" for R 1 and R 2 , methyl, ethyl, propyl, n-
Butyl, t-butyl group and the like. "Aryl group"
Examples thereof include aryl groups having 6 to 14 carbon atoms, and specific examples include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Note that R 1 and R 2 may be the same substituent or different substituents. Examples of the substituent in the aryl group include a lower alkyl group such as a methyl group and an ethyl group, a lower alkoxy group such as a methoxy group and an ethoxy group, a trifluoromethyl group, and a halogen atom such as chlorine. In addition, two or more of these substituents may be substituted, and in this case, the substituents may be the same or different.
【００２６】Ｒ3 における「炭素数１〜８のアルキル
基」としては、メチル、エチル、プロピル、ｎ−ブチ
ル、ｔ−ブチル、ペンチル、ｎ−ヘプチル等が挙げられ
る。「置換フェニル基」における置換基としては、例え
ば、メチル基、エチル基等の低級アルキル基、メトキシ
基、エトキシ基等の低級アルコキシ基、トリフロロメチ
ル基、塩素等のハロゲン原子、The "alkyl group having 1 to 8 carbon atoms" for R 3 includes methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, n-heptyl and the like. Examples of the substituent in the `` substituted phenyl group '' include a lower alkyl group such as a methyl group and an ethyl group, a lower alkoxy group such as a methoxy group and an ethoxy group, a trifluoromethyl group, a halogen atom such as chlorine,
【００２７】[0027]
【化１４】 Embedded image
【００２８】等が挙げられる。And the like.
【００２９】Ｒ4 における「炭素数１〜８のアルキル
基」、「置換フェニル基」はＲ3 におけるのと同義であ
る。The "alkyl group having 1 to 8 carbon atoms" in R 4, "substituted phenyl group" is the same as in the R 3.
【００３０】上記化合物（Ｉ）のなかでも、式（II）Among the above compounds (I), those represented by the formula (II)
【００３１】[0031]
【化１５】 Embedded image
【００３２】（ここで、Ｒ6 は水素原子、ハロゲン原
子、炭素数１〜４のアルキル基、炭素数１〜４のアルコ
キシ基、トリフロロメチル基） 又は式（III)(Where R 6 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a trifluoromethyl group) or a compound of the formula (III)
【００３３】[0033]
【化１６】 Embedded image
【００３４】又は式（VI）Or the formula (VI)
【００３５】[0035]
【化１７】 Embedded image
【００３６】、ことに、式（VII)In particular, the formula (VII)
【００３７】[0037]
【化１８】 Embedded image
【００３８】の化合物が好ましい。The compound of the formula (1) is preferred.
【００３９】Ｒ6 における「炭素数１〜４のアルキル
基」としては、メチル、エチル、プロピル、ｎ−ブチ
ル、ｔ−ブチルが挙げられる。また、「炭素数１〜４の
アルコキシ基」としては、メトキシ、エトキシ、プロポ
キシ、ｎ−ブトキシ、ｔ−ブトキシが挙げられる。な
お、Ｒ6 はそれぞれ同一でもよいし、異なっていてもよ
い。The "alkyl group having 1 to 4 carbon atoms" for R 6 includes methyl, ethyl, propyl, n-butyl and t-butyl. Examples of the "alkoxy group having 1 to 4 carbon atoms" include methoxy, ethoxy, propoxy, n-butoxy and t-butoxy. Note that R 6 may be the same or different.
【００４０】化合物（Ｉ）〜（III)及び（VI）〜（VII)
の化合物の具体例を、以下に示す。Compounds (I) to (III) and (VI) to (VII)
Specific examples of the compound are shown below.
【００４１】[0041]
【表１】 [Table 1]
【００４２】[0042]
【表２】 [Table 2]
【００４３】[0043]
【表３】 [Table 3]
【００４４】上記化合物のうち、特に化合物３７〜４２
及び４５は、有機電界発光素子の正孔輸送材料として優
れた化合物であるため好ましい。Of the above compounds, particularly compounds 37 to 42
And 45 are preferable because they are excellent compounds as hole transporting materials for organic electroluminescent devices.
【００４５】[0045]
【表４】 （いずれのトリアゾール基もトリフェニルアミンのパラ
位に置換）[Table 4] (All triazole groups are substituted at the para position of triphenylamine)
【００４６】[0046]
【化１９】 Embedded image
【００４７】次に、本発明のトリアゾール化合物の合成
方法について説明する。Next, a method for synthesizing the triazole compound of the present invention will be described.
【００４８】本発明のトリアゾール化合物のうち、例え
ばビス体の合成方法は以下の方法が挙げられる。Among the triazole compounds of the present invention, for example, a method for synthesizing a bis-form is as follows.
【００４９】[0049]
【化２０】 Embedded image
【００５０】まず、式（IV）のエタンジオン化合物と、
式（Ｖ）のヒドラジン化合物とを、適当な溶媒（例えば
イソプロピルアルコール、エタノール等のアルコール
類、ベンゼン、酢酸エチル等）中、任意に触媒（酸触媒
又は塩素触媒）の存在下で、２：１〜４：１程度のモル
比で反応させることによりヒドラゾン化合物（IX）を得
る。ここで、式（IV）のエタンジオン化合物は、アルド
リッチ ケミカル社より試薬として容易に入手すること
ができる。First, an ethanedione compound of the formula (IV):
The hydrazine compound of the formula (V) is mixed with an appropriate solvent (for example, alcohols such as isopropyl alcohol and ethanol, benzene, ethyl acetate and the like) in the presence of a catalyst (acid catalyst or chlorine catalyst) in a ratio of 2: 1. The hydrazone compound (IX) is obtained by reacting at a molar ratio of about 4: 1. Here, the ethanedione compound of the formula (IV) can be easily obtained as a reagent from Aldrich Chemical Company.
【００５１】次いで、ヒドラゾン化合物（IX）を、好ま
しくは４級アンモニウム塩の存在下で、酸化して閉環さ
せ、式（Ｉ）の化合物を得ることができる。ここで、４
級アンモニウム塩としては、シュウ酸アンモニウム塩、
酢酸アンモニウム塩、炭酸アンモニウム塩等を使用する
ことができる。酸化は、例えば、クロム酸、重クロム酸
カリ、過酸化水素、酢酸鉛（４価）、フェリシアン化カ
リウム、塩化鉄、硫酸銅（II）等の酸化剤を用いること
により行うことができる。Next, the hydrazone compound (IX) is oxidized and ring-closed, preferably in the presence of a quaternary ammonium salt, to give a compound of the formula (I). Where 4
As the quaternary ammonium salt, ammonium oxalate,
Ammonium acetate, ammonium carbonate and the like can be used. The oxidation can be performed by using an oxidizing agent such as, for example, chromic acid, potassium dichromate, hydrogen peroxide, lead acetate (tetravalent), potassium ferricyanide, iron chloride, and copper (II) sulfate.
【００５２】なお、酸化して閉環させる際には、上記４
級アンモニウム塩の存在化で、ピリジン−水混合物中で
硫酸銅（II）を用いて行うことが好ましい。この酸化し
て閉環する際の反応温度は、７０〜１４０℃程度が好ま
しい。上記ビス−トリアゾール化合物の合成方法は、特
開昭６０−２２２４６８号公報及びJ. Hetero Cyclic C
hem. p1275 (1975) に記載の合成方法に準じて行うこと
ができる。When the ring is closed by oxidation, the above 4
In the presence of a quaternary ammonium salt, it is preferably carried out using copper (II) sulfate in a pyridine-water mixture. The reaction temperature at the time of ring closure by oxidation is preferably about 70 to 140 ° C. The method for synthesizing the above bis-triazole compound is disclosed in JP-A-60-222468 and J. Hetero Cyclic C.
hem. p1275 (1975).
【００５３】また、本発明のトリアゾール化合物のう
ち、例えばトリス体の合成方法は以下の方法が挙げられ
る。Further, among the triazole compounds of the present invention, for example, a method for synthesizing a tris form includes the following methods.
【００５４】[0054]
【化２１】 Embedded image
【００５５】まず、式（IV）のエタンジオン化合物と、
式（VIII) のトリス−（４−ヒドラジノフェニル）アミ
ン化合物とを反応させることにより、トリスヒドラゾン
化合物（Ｘ）を得る。ここで、式（IV）のエタンジオン
化合物は、上述したように、容易に入手できる。式（VI
II) のトリス−（４−ヒドラジノフェニル）アミン化合
物は、特開昭５７−２０５７４２号公報又は特開昭５７
−２０５７４３号公報等に記載の合成方法に従って、ト
リス−（アミノフェニル）アミンを合成し、この化合物
を公知の方法（例えば、Organic Synthesis (2nd ed.,
1941) vol.1, p442）に準じてヒドラジノ体に変換する
ことにより得ることができる。なお、式（VIII) のトリ
ス−（４−ヒドラジノフェニル）アミン化合物は、空気
中で酸化を受け易いため、塩酸塩、硝酸塩等の塩の形態
で使用することが好ましい。式（IV）のエタンジオン化
合物と式（VIII) のトリス−（４−ヒドラジノフェニ
ル）アミン化合物との反応は、適当な溶媒（例えばイソ
プロピルアルコール、エタノール等のアルコール類、氷
酢酸、ベンゼン、ジメチルホルムアミド等）中で、任意
に触媒（例えば、酢酸ソーダ、酢酸カリウム、炭酸ソー
ダ、リン酸カリ等の脱塩酸触媒）の存在下で反応させる
ことが好ましい。この際の反応温度は、５０〜１５０℃
程度が好ましい。First, an ethanedione compound of the formula (IV):
The tris- (4-hydrazinophenyl) amine compound of the formula (VIII) is reacted to obtain a trishydrazone compound (X). Here, the ethanedione compound of formula (IV) is readily available, as described above. Expression (VI
The tris- (4-hydrazinophenyl) amine compound (II) is disclosed in JP-A-57-205742 or JP-A-57-205742.
According to the synthesis method described in JP-A-205743 and the like, tris- (aminophenyl) amine is synthesized, and this compound is synthesized by a known method (for example, Organic Synthesis (2nd ed.,
1941) vol.1, p442), and can be obtained by converting to a hydrazino form. Note that the tris- (4-hydrazinophenyl) amine compound of the formula (VIII) is easily oxidized in the air, and thus is preferably used in the form of a salt such as a hydrochloride or a nitrate. The reaction between the ethanedione compound of the formula (IV) and the tris- (4-hydrazinophenyl) amine compound of the formula (VIII) can be carried out in a suitable solvent (for example, alcohols such as isopropyl alcohol and ethanol, glacial acetic acid, benzene, dimethylformamide). , Etc.) in the presence of a catalyst (for example, a catalyst for removing hydrochloric acid such as sodium acetate, potassium acetate, sodium carbonate, potassium phosphate, etc.). The reaction temperature at this time is 50 to 150 ° C.
The degree is preferred.
【００５６】次いで、ヒドラゾン化合物（Ｘ）を、好ま
しくは４級アンモニウム塩の存在下で、酸化して閉環さ
せ、式（VI）の化合物を得ることができる。ここで、４
級アンモニウム塩は上述したものと同様のものを使用す
ることができる。また酸化は、上述した酸化剤を用いる
ことにより行うことができる。なお、４級アンモニウム
塩は、理論量の５倍程度以上の過剰量を用いることが、
反応の進行をさせやすいため、好ましい。Next, the hydrazone compound (X) is oxidized and ring-closed, preferably in the presence of a quaternary ammonium salt, to give a compound of the formula (VI). Where 4
As the quaternary ammonium salt, the same one as described above can be used. The oxidation can be performed by using the above-mentioned oxidizing agent. The quaternary ammonium salt may be used in excess of about 5 times the theoretical amount.
This is preferable because the reaction can easily proceed.
【００５７】酸化して閉環させる際には、上記４級アン
モニウム塩の存在化で、酸化反応に影響を与えない溶媒
中で行うことが好ましい。化合物（Ｘ）は溶解性が悪い
ため、この溶媒としては、ジメチルスルホキシドに少量
（２０容量％程度）の氷酢酸を加えたものを使用するこ
とが好ましい。この酸化して閉環する際の反応温度は、
上記と同様に７０〜１４０℃程度が好ましい。The ring closure by oxidation is preferably carried out in a solvent which does not affect the oxidation reaction in the presence of the quaternary ammonium salt. Since the compound (X) has poor solubility, it is preferable to use a solvent obtained by adding a small amount (about 20% by volume) of glacial acetic acid to dimethyl sulfoxide. The reaction temperature for this oxidative ring closure is:
As above, the temperature is preferably about 70 to 140 ° C.
【００５８】本発明の有機ＥＬ素子は、主として、基板
上に陽極、正孔注入輸送層、発光層及び陰極がこの順で
積層されて構成される。なお、これら基板−陽極、陽極
−正孔注入輸送層、正孔注入輸送層−発光層、発光層−
陰極の間に、任意に、電子注入層、電荷障壁層、バッフ
ァ層等の中間層を設けてもよい。なかでも、発光層−陰
極の間に電子注入層が、発光層に面して電荷障壁層が形
成されていることが好ましい。The organic EL device of the present invention is mainly constituted by laminating an anode, a hole injection / transport layer, a light emitting layer and a cathode on a substrate in this order. In addition, these substrate-anode, anode-hole injection transport layer, hole injection transport layer-light emitting layer, light emitting layer-
Optionally, an intermediate layer such as an electron injection layer, a charge blocking layer, and a buffer layer may be provided between the cathodes. In particular, it is preferable that an electron injection layer is formed between the light emitting layer and the cathode, and a charge barrier layer is formed facing the light emitting layer.
【００５９】発光層に面した電荷障壁層としては、正孔
障壁層、電子障壁層の２つのタイプが挙げられるが、電
子障壁層の方が効率的であるため好ましい。発光層に面
して形成されているとは、電子障壁層の場合には発光層
と正孔注入輸送層との間、好ましくは発光層の陽極側表
面に接するように設けることが好ましい。また、正孔障
壁層の場合には、発光層と陰極との間、好ましくは発光
層の陰極側表面に接するように設けることが好ましい。
具体的には、 （１）陽極／正孔注入輸送層／発光層／陰極 （２）陽極／正孔注入輸送層／発光層／電子注入輸送層
／陰極 （３）陽極／正孔注入輸送層／電子障壁層／発光層／陰
極 （４）陽極／正孔注入輸送層／電子障壁層／発光層／電
子注入輸送層／陰極 （５）陽極／正孔注入輸送層／電子障壁層／発光層／正
孔障壁層／電子注入輸送層／陰極等が挙げられる。As the charge barrier layer facing the light emitting layer, there are two types, a hole barrier layer and an electron barrier layer, and the electron barrier layer is preferable because it is more efficient. The expression “formed so as to face the light emitting layer” means that in the case of an electron barrier layer, it is preferably provided between the light emitting layer and the hole injection / transport layer, preferably in contact with the anode side surface of the light emitting layer. In the case of a hole blocking layer, it is preferably provided between the light emitting layer and the cathode, preferably in contact with the cathode side surface of the light emitting layer.
Specifically, (1) anode / hole injection / transport layer / light emitting layer / cathode (2) anode / hole injection / transport layer / light emitting layer / electron injection / transport layer / cathode (3) anode / hole injection / transport layer / Electron barrier layer / light emitting layer / cathode (4) anode / hole injection / transport layer / electron barrier layer / light emitting layer / electron injection / transport layer / cathode (5) anode / hole injection / transport layer / electron barrier layer / light emitting layer / Hole barrier layer / electron injection / transport layer / cathode.
【００６０】上記有機ＥＬ素子は、基板に支持されてい
ることが好ましい。基板としては、通常有機ＥＬ素子に
用いられているものであれば特に限定されるものではな
く、例えば、ガラス、透明プラスチック、石英からなる
もの等が挙げられる。また、これらの基板上に所望の絶
縁層や、素子、回路等及び所望の絶縁層等が形成されて
いてもよい。ただし、層構成が多層になると、有機ＥＬ
素子の作製の制御が困難となるなどの問題も増大するた
め、できるだめ簡単な素子構造となるようにすることが
好ましい。The organic EL device is preferably supported on a substrate. The substrate is not particularly limited as long as it is generally used for an organic EL device, and examples thereof include a substrate made of glass, transparent plastic, and quartz. Further, a desired insulating layer, an element, a circuit, and the like, a desired insulating layer, and the like may be formed over these substrates. However, when the layer configuration is multi-layered, the organic EL
Since problems such as difficulty in controlling the production of the element also increase, it is preferable to make the element structure as simple as possible.
【００６１】本発明における陽極としては、仕事関数の
大きい（４ｅＶ以上）金属、合金、導電性化合物、透明
導電性化合物及びこれらの混合物を電極物質とするもの
等が挙げられる。なかでも、陽極側から発光を取り出す
ことが一般的であるため、透明導電性化合物が好まし
い。陽極は、上記金属等を蒸着やスパッタリングなどの
方法により薄膜状に形成することができる。Examples of the anode in the present invention include metals, alloys, conductive compounds, transparent conductive compounds, and mixtures thereof having a large work function (4 eV or more) as an electrode material. Above all, it is common to take out light emission from the anode side, and thus a transparent conductive compound is preferable. The anode can be formed in a thin film shape by the above-mentioned metal or the like by a method such as vapor deposition or sputtering.
【００６２】上記陽極によって発光を取り出す場合に
は、透過率を大きくすることが必要であるため、シール
抵抗が数１０2 程度以下が好ましい。また、陽極の膜厚
は、使用する電極物質によって異なるが、例えば１０〜
３００ｎｍ程度が好ましい。[0062] When light is emitted by said anode, since it is necessary to increase the transmittance, seal resistance is preferably not more than several 10 2. The thickness of the anode varies depending on the electrode material used.
About 300 nm is preferable.
【００６３】本発明における正孔注入輸送層は、陽極か
ら注入された正孔を、後述する発光層まで伝達する機能
を有している。この正孔注入輸送層には、上記の式
（Ｉ）で示される化合物が含有されている。これら化合
物は、正孔の移動度が１０-6ｃｍ2／Ｖ・Ｓ以上と良好
な移動効率を有しているため好ましい。The hole injection / transport layer according to the present invention has a function of transmitting holes injected from the anode to the light emitting layer described later. The hole injection transport layer contains the compound represented by the above formula (I). These compounds are preferable because they have a good hole mobility of 10 −6 cm 2 / V · S or more, which is good.
【００６４】上記の式（Ｉ）で示される化合物は、優れ
た熱安定性、高い移動効率、低い駆動電圧、非晶性の保
持等からも、正孔注入輸送層の主要材料として最適であ
る。The compound represented by the above formula (I) is most suitable as a main material of the hole injecting / transporting layer because of its excellent thermal stability, high transfer efficiency, low driving voltage, and non-crystalline retention. .
【００６５】なお、上記式（Ｉ）で示される化合物は、
任意に他の輸送材料と併用させることによって、さらに
低い駆動電圧及び高い発光効率で高輝度の発光を有する
有機ＥＬ素子を得ることができる場合がある。このよう
な輸送材料としては、従来から有機光半導体の正孔輸送
化合物として知られているもの、従来から有機ＥＬ素子
の正孔注入輸送化合物としてしられているもの等の中か
ら選択して使用することができる。例えば、トリアゾー
ル化合物（米国特許第３，１１２，１９７号）、ピラゾ
リン化合物（米国特許第３，１８０，７２９号）、アリ
ールアミン化合物（米国特許第３，５６７，４５０号、
同３，１８０，７０３号）、ポリフィリン化合物（特開
昭６３−２９５６９５号）、スチリルアミン化合物（米
国特許第４，１２７，４１２号、特開昭５４−５８４４
５号、特開昭５４−１４９６３４号）等が挙げられる。The compound represented by the above formula (I)
By optionally using it in combination with another transporting material, an organic EL element having higher luminance and lower driving voltage and higher luminous efficiency may be obtained in some cases. Such a transport material is selected from those conventionally known as a hole transport compound of an organic optical semiconductor and those conventionally used as a hole injection compound of an organic EL device. can do. For example, triazole compounds (US Pat. No. 3,112,197), pyrazoline compounds (US Pat. No. 3,180,729), arylamine compounds (US Pat. No. 3,567,450,
3,180,703), porphyrin compounds (JP-A-63-29569), styrylamine compounds (U.S. Pat. No. 4,127,412, JP-A-54-5844).
No. 5, JP-A-54-149634).
【００６６】本発明における発光層は、固体状態で発光
性を有する有機化合物からなり、少なくとも（１）電界
印加時に、陽極又は正孔注入層より正孔を注入すること
ができる注入性能、（２）注入した電荷（電子又は正
孔）を電界の力で移動させる輸送機能又は（３）電子と
正孔との再結合の場を提供し、これを発光につなげる発
光機能のいずれか１つ、好ましくはすべての機能を有し
ているものである。発光層の膜厚は、５ｎｍ〜１５００
ｎｍ程度の薄膜状のものが好ましい。なお、発光層は、
正孔の注入されやすさと、電子の注入されやすさとに違
いあっても良いし、電子と正孔の移動度で表される輸送
機能に大小があってもよいが、少なくともどちらか一方
の電荷を移動させることができることが好ましい。The light emitting layer in the present invention is composed of an organic compound having a light emitting property in a solid state, and has at least (1) an injection performance capable of injecting holes from an anode or a hole injection layer when an electric field is applied; ) One of the following: a transport function for transferring injected charges (electrons or holes) by the force of an electric field; or (3) a light-emitting function for providing a field of recombination of electrons and holes and connecting the same to light emission; Preferably, it has all functions. The thickness of the light emitting layer is 5 nm to 1500
A thin film having a thickness of about nm is preferable. The light emitting layer is
There may be a difference between the ease with which holes are injected and the ease with which electrons are injected, and the transport function represented by the mobility of electrons and holes may be large or small, but at least one of the charges Can be moved.
【００６７】上記（１）の注入機能において、適当な陽
極材料を選べば比較的正孔を注入しやすいことから、発
光層のイオン化エネルギーは６．０ｅＶ程度以下である
ことが好ましく、一方、適当な陰極材料を選べば比較的
電子を注入しやすいことから、電子親和力は２．５ｅＶ
程度以下であることが好ましい。また、上記（３）の発
光機能については、固体状態での蛍光性が強いことが望
ましい。In the injection function of the above (1), the ionization energy of the light-emitting layer is preferably about 6.0 eV or less, since it is relatively easy to inject holes if an appropriate anode material is selected. If a suitable cathode material is selected, electrons are relatively easy to inject, so the electron affinity is 2.5 eV
It is preferable that it is not more than about. As for the light emitting function of the above (3), it is desirable that the fluorescent property in the solid state is strong.
【００６８】上記発光層を構成する有機化合物は、特に
限定されるものではなく、公知の化合物の中から、任意
のものを選択して用いることができる。例えば、多環縮
合芳香族化合物；ベンゾチアゾール、ベンゾイミダゾー
ル、ベンゾオキサゾール等の蛍光増白剤；金属キレート
化オキシド化合物；スチリル化合物等が挙げられる。The organic compound constituting the light emitting layer is not particularly limited, and any one of known compounds can be used. For example, polycyclic fused aromatic compounds; fluorescent brighteners such as benzothiazole, benzimidazole and benzoxazole; metal chelated oxide compounds; styryl compounds.
【００６９】多環縮合化合物としては、例えば、アント
ラセン、ナフタレン、フェナスレン、ピレン、ペリレン
骨格を含む縮合環発光化合物、８個の縮合環を含む他の
縮合環発光材料等を挙げることができる。Examples of the polycyclic condensed compound include a condensed ring light emitting compound having an anthracene, naphthalene, phenathrene, pyrene and perylene skeleton, and other condensed ring light emitting materials containing eight condensed rings.
【００７０】蛍光増白剤としては、例えば、特開昭５９
−１９４３９３号に記載のものを挙げることができる。As the fluorescent whitening agent, for example, JP-A-59
No. 194393.
【００７１】金属キレート化オキシド化合物としては、
例えば、特開昭６３−２９５６９５号に記載のものを挙
げることができる。The metal chelated oxide compounds include:
For example, those described in JP-A-63-295695 can be mentioned.
【００７２】スチリル化合物としては、例えば、特開昭
６２−３１２３５６号又は昭６３−８０２５７号等に記
載されているものを挙げることができる。Examples of the styryl compound include those described in, for example, JP-A-62-31356 and JP-A-63-80257.
【００７３】また、上記発光層は、任意に２層以上の積
層構造をとってもよい。例えば、米国特許４，７６９，
２９２号に記載されているように、ホスト物質と蛍光物
質との積層構造でもよい。この場合のホスト物質は薄膜
状の層であって、発光層の機能のうち、注入輸送機能及
び発光機能の一部を受け持ち、蛍光物質は、ホスト物質
の層中に微量（数％）存在させ、電子と正孔の結合に応
じて発光するという発光機能の一部を担う。The light emitting layer may optionally have a laminated structure of two or more layers. For example, U.S. Pat.
As described in No. 292, a laminated structure of a host substance and a fluorescent substance may be used. In this case, the host material is a thin film-like layer, which is responsible for part of the functions of the light emitting layer, such as the injection / transport function and the light emitting function. The fluorescent material is present in the host material layer in a small amount (several%). Plays a part of a light emitting function of emitting light in accordance with the combination of electrons and holes.
【００７４】また、発光層に用いる有機化合物は薄膜形
成性を有しいない化合物であってもよく、例えば、１，
１，４，４−テトラフェニル−１，３−ブタジエン等も
用いることができる。The organic compound used for the light emitting layer may be a compound having no thin film forming property.
1,4,4-tetraphenyl-1,3-butadiene and the like can also be used.
【００７５】これらの有機発光材料の薄膜化の方法は、
例えば、スピンコート法、キャスト法、ＬＢ法、蒸着法
等が挙げられるが、なかでも、均質な膜が得られやす
く、かつピンホールが生成しにくい方法である蒸着法が
好ましい。蒸着法を用いる場合、その蒸着条件は、使用
する有機材料の昇華温度、目的とする薄膜の状態、結晶
性、結晶の配向などにより異なるが、一般にボード加熱
温度５０〜５００℃、真空度１０-6〜１０-3Ｐａ、蒸着
速度０．０１〜５０ｎｍ／秒、基板温度−５０〜＋３０
０℃、膜厚５ｎｍ〜５００ｎｍの範囲で適宜選択するこ
とができる。The method for thinning these organic light emitting materials is as follows.
For example, a spin coating method, a casting method, an LB method, an evaporation method and the like can be mentioned, and among them, an evaporation method is preferred, in which a uniform film is easily obtained and a pinhole is hardly generated. When using the vapor deposition method, the vapor deposition conditions vary depending on the sublimation temperature of the organic material to be used, the state of the target thin film, crystallinity, crystal orientation, etc., but generally, the board heating temperature is 50 to 500 ° C., and the degree of vacuum is 10 −. 6 to 10 -3 Pa, deposition rate 0.01 to 50 nm / sec, substrate temperature -50 to +30
It can be appropriately selected within a range of 0 ° C. and a film thickness of 5 nm to 500 nm.
【００７６】本発明における陰極としては、仕事関数の
小さい（４ｅＶ程度以下）金属、合金、導電性化合物、
透明導電性化合物及びこれらの混合物を電極物質とする
もの等が挙げられる。なお、一般的には、陽極、陰極の
いずれかが透明又は半透明であることが発光を取り出す
効率が良いため好ましい。陰極は、上記金属等を蒸着や
スパッタリングなどの方法により薄膜状に形成すること
ができる。なお、陰極のシール抵抗、膜厚等は陽極と同
様とすることができる。As the cathode in the present invention, metals, alloys, conductive compounds, and the like having a small work function (about 4 eV or less) are used.
Examples thereof include those using a transparent conductive compound and a mixture thereof as an electrode material. In general, it is preferable that one of the anode and the cathode is transparent or translucent because the efficiency of extracting light emission is high. The cathode can be formed from the above-mentioned metal or the like into a thin film by a method such as vapor deposition or sputtering. Note that the cathode seal resistance, film thickness, and the like can be the same as those of the anode.
【００７７】本発明において、任意に設けることができ
る電子注入輸送層は、電子伝達化合物からなるものであ
って、陰極より注入された電子を発光層に伝達する機能
を有している。上記電子伝達化合物は、特に限定される
ものではなく、公知の化合物の中から適宜選択して用い
ることができる。このような化合物としては、例えば、
ニトロ置換フロレノン化合物、チオピラジンオキシド化
合物、ジフェニルキノン化合物、アントラキノジメタン
化合物（特開昭５７−１４９２５９号又は同５８−５５
４５０号）、アントロン化合物（特開昭６１−２２５１
５１号、同６１−２３３７５０号）等を挙げることがで
きる。In the present invention, the optional electron injecting and transporting layer is made of an electron transporting compound, and has a function of transmitting electrons injected from the cathode to the light emitting layer. The electron transfer compound is not particularly limited, and may be appropriately selected from known compounds. Such compounds include, for example,
Nitro-substituted fluorenone compounds, thiopyrazine oxide compounds, diphenylquinone compounds, anthraquinodimethane compounds (JP-A-57-149259 or 58-55)
No. 450), anthrone compound (JP-A-61-2251)
No. 51, No. 61-233750).
【００７８】本発明において、任意に設けることができ
る電荷障壁層のうち、電子障壁層は、発光層より陽極側
に出ていこうとする電子を発光層内に留める役割を有し
ており、発光層の電子移動度より低い電子移動度をもつ
層であるか又は発光層の電子親和力より小さい電子親和
力をもつ層であることが好ましい。In the present invention, among the charge barrier layers that can be provided arbitrarily, the electron barrier layer has a role of retaining electrons which are going to the anode side from the light emitting layer in the light emitting layer. Preferably, the layer has an electron mobility lower than the electron mobility of the layer or a layer having an electron affinity lower than the electron affinity of the light emitting layer.
【００７９】このような電子障壁層は、トリフェニルア
ミン系化合物（特開昭５９−１９４３９３号又は同６３
−２９５６９５号）、無機アモルファス化合物（特開平
３−７７２９９号）が好ましい。Such an electron barrier layer is made of a triphenylamine compound (JP-A-59-194393 or 63).
-295695) and inorganic amorphous compounds (JP-A-3-77299).
【００８０】正孔障壁層は、発光層より陰極側に出てい
こうとする正孔を、発光層内に留める役割を有してお
り、発光層の正孔移動度より低い正孔移動度をもつ層で
あるか又は発光層のイオン化エネルギーより小さいエネ
ルギーをもつ層であることが好ましい。このような正孔
障壁層は、無機アモルファス化合物（特開平３−７７２
９９号）が好ましい。上記電荷障壁層は、１〜２００ｎ
ｍ、好ましくは５０ｎｍ以下の膜厚を有することが好ま
しい。The hole barrier layer has a role of keeping holes that are going to the cathode side of the light emitting layer in the light emitting layer, and has a hole mobility lower than the hole mobility of the light emitting layer. It is preferable that the light-emitting layer has a lower energy than the light-emitting layer. Such a hole blocking layer is made of an inorganic amorphous compound (JP-A-3-772).
No. 99) is preferred. The charge barrier layer has a thickness of 1 to 200 n.
m, preferably 50 nm or less.
【００８１】本発明においては、さらに任意にバッファ
層を設けてもよい。バッファ層は、剥離現象の防止、さ
らには正孔又は電子の注入効率の向上を目的とする層で
ある。これらバッファ層は、各種フタロシアニン顔料、
各種有機金属化合物（例えばトリアルコキシアルミニウ
ム、ステアリン酸亜鉛、トリアセチルアセトンアルミニ
ウム、ジアセチルアセトンマグネシウム等）、カーボン
ブラック等が挙げられる。バッファ層の設ける位置は、
特に限定されるものではないが、剥離現象が起こりやす
い上記（１）の場合には、陽極−正孔注入輸送層の間、
発光層−陰極の間、上記（２）〜（５）の場合には、陽
極−正孔注入輸送層の間、電子注入輸送層−陰極の間に
設けることが効果的である。バッファ層の膜厚は、どの
位置に設けるかにより異なるが、例えば、１０〜５００
ｎｍ程度が好ましい。In the present invention, an optional buffer layer may be further provided. The buffer layer is a layer for the purpose of preventing the separation phenomenon and improving the injection efficiency of holes or electrons. These buffer layers are composed of various phthalocyanine pigments,
Various organic metal compounds (for example, trialkoxyaluminum, zinc stearate, aluminum triacetylacetone, magnesium diacetylacetone), carbon black, and the like. The position of the buffer layer is
Although not particularly limited, in the case of the above (1) where the peeling phenomenon is likely to occur, the distance between the anode and the hole injection / transport layer is
It is effective to provide between the light emitting layer and the cathode, and in the above cases (2) to (5), between the anode and the hole injection and transport layer and between the electron injection and transport layer and the cathode. The thickness of the buffer layer varies depending on where it is provided.
About nm is preferable.
【００８２】次に、本発明の有機ＥＬ素子の好適な製造
方法について説明する。上記（１）陽極／正孔注入輸送
層／発光層／陰極の構成を有する有機ＥＬ素子は、以下
のように作製することができる。Next, a preferred method for manufacturing the organic EL device of the present invention will be described. The organic EL device having the configuration of (1) anode / hole injection / transport layer / light emitting layer / cathode can be manufactured as follows.
【００８３】まず、適当な基板上に、所望の陽極材料か
らなる薄膜を５００ｎｍ以下、好ましくは１０〜３００
ｎｍの範囲になるように、蒸着やスパッタリングなどの
方法より形成し、陽極を形成する。次いで、本発明のト
リアゾール化合物を、蒸着やスピンコートなどの方法に
より陽極上に薄膜状に形成することにより、正孔注入輸
送層を形成する。この際の膜厚は、発光を基板側より取
り出す場合には透明率を高めるために、５〜２００ｎｍ
程度が好ましい。続いて、このトリアゾール化合物から
なる正孔注入輸送層の上に、有機発光材料を、蒸着法に
より、５〜１５００ｎｍの範囲の膜厚で積層して発光層
を形成する。その後、この発光層の上に、陰極用物質か
らなる薄膜を、蒸着やスパッタリングなどの方法によ
り、５００ｎｍ以下、好ましくは１０〜３００ｎｍの範
囲の膜厚で積層し、陰極を形成する。First, a thin film made of a desired anode material is formed on an appropriate substrate in a thickness of 500 nm or less, preferably 10 to 300 nm.
An anode is formed by a method such as evaporation or sputtering so that the thickness is in the range of nm. Next, the hole injection transport layer is formed by forming the triazole compound of the present invention in a thin film on the anode by a method such as vapor deposition or spin coating. The thickness at this time is 5 to 200 nm in order to increase the transparency when light is extracted from the substrate side.
The degree is preferred. Subsequently, an organic light-emitting material is laminated on the hole injection / transport layer made of the triazole compound by a vapor deposition method so as to have a thickness in the range of 5 to 1500 nm to form a light-emitting layer. Thereafter, a thin film made of a cathode material is laminated on the light emitting layer by a method such as vapor deposition or sputtering to a thickness of 500 nm or less, preferably 10 to 300 nm, to form a cathode.
【００８４】なお、上記方法は、陰極側から逆の工程で
行ってもよい。上記（２）陽極／正孔注入輸送層／発光
層／電子注入輸送層／陰極の構成を有する有機ＥＬ素子
は、発光層上に、蒸着やスパッタリング法により有機系
化合物を又はプラズマＣＶＤ法によりＮ型ａ−ＳｉＣを
薄膜状に成膜して、膜厚１００ｎｍ程度以下の電子注入
輸送層を形成し、その後に陰極を形成する以外は、上記
（１）と同様に作製することができる。Note that the above method may be performed in reverse steps from the cathode side. The organic EL device having the constitution of (2) anode / hole injection / transport layer / light-emitting layer / electron injection / transport layer / cathode has a structure in which an organic compound is formed on the light-emitting layer by vapor deposition or sputtering or N 2 by plasma CVD. It can be manufactured in the same manner as in the above (1) except that the mold a-SiC is formed into a thin film, an electron injection / transport layer having a thickness of about 100 nm or less is formed, and then a cathode is formed.
【００８５】上記（３）〜（５）の構成を有する有機Ｅ
Ｌ素子についても、上記（１）及び（２）に準じて作製
することができる。Organic E having the above-mentioned constitutions (3) to (5)
The L element can also be manufactured according to the above (1) and (2).
【００８６】このようにして得られた本発明の有機ＥＬ
素子に、直流電圧を印加する場合には、陽極を＋、陰極
を−の極性として駆動電圧１〜３０Ｖ程度の電圧を印可
すると、発光が透明又は半透明の電極側より観察でき
る。なお、逆の極性で電圧を印加しても発光は生じな
い。また、交流電圧を印加する場合には、陽極が＋、陰
極が−の状態になったときに発光する。なお、印加する
交流電圧の波形は任意でよい。The organic EL of the present invention thus obtained
When a DC voltage is applied to the device, when a voltage of about 1 to 30 V is applied with a positive polarity of the anode and a negative polarity of the cathode, light emission can be observed from the transparent or translucent electrode side. Note that no light emission occurs even when a voltage is applied with the opposite polarity. When an AC voltage is applied, light is emitted when the anode is in the positive state and the cathode is in the negative state. The waveform of the applied AC voltage may be arbitrary.
【００８７】[0087]
【実施例】以下の本発明の１，２，３−トリアゾール化
合物、その製造方法及び有機電界発光素子の実施例を説
明する。EXAMPLES Examples of the following 1,2,3-triazole compound of the present invention, a method for producing the same, and an organic electroluminescent device will be described.
【００８８】合成例１：（例示化合物２７の合成） （ａ）３，３’−ジメチル−４，４’−ジヒドラジノ−
ビフェニル １２ｇとベンジル３０ｇをイソプロピルア
ルコール２００ｍｌに溶解し、これに微量の酢酸を加え
て油浴中で４時間加熱還流を行なう。冷後、沈澱した黄
色結晶を吸引口過し、メタノールで洗浄した。えられた
結晶の収量は、１８．５ｇであった。Synthesis Example 1 (Synthesis of Exemplified Compound 27) (a) 3,3′-Dimethyl-4,4′-dihydrazino-
12 g of biphenyl and 30 g of benzyl are dissolved in 200 ml of isopropyl alcohol, a trace amount of acetic acid is added thereto, and the mixture is heated under reflux in an oil bath for 4 hours. After cooling, the precipitated yellow crystals were passed through a suction port and washed with methanol. The yield of the obtained crystals was 18.5 g.
【００８９】（ｂ）上記（ａ）で得られたヒドラゾン１
８．５ｇ、塩化銅（II）１７．８ｇ及び酢酸アンモニウ
ム４０ｇの混合物を、ジメチルホルムアミド２００ｍｌ
中に加え、浴温１１０℃（内温９５〜１０５℃）中、約
１５時間加熱撹拌を行なう。(B) Hydrazone 1 obtained in (a) above
A mixture of 8.5 g, 17.8 g of copper (II) chloride and 40 g of ammonium acetate was added to 200 ml of dimethylformamide.
The mixture is heated and stirred at a bath temperature of 110 ° C. (inner temperature of 95 to 105 ° C.) for about 15 hours.
【００９０】室温まで冷却した後、反応溶液を大量（約
１リットル）の水中に注入し、析出した固形物を濾取し
た。次いで水洗を行ないアルコールを用いて熱洗浄を行
ない、黄橙色の粉末１７．６ｇを得る。最後に、この粉
末を昇華精製し、濃黄色の微粉末３．６ｇを得る。得ら
れた微粉末の融点は２８８．５℃〜２９１．０℃、ＭＳ
（ｍ／ｚ）：６２０であった。After cooling to room temperature, the reaction solution was poured into a large amount (about 1 liter) of water, and the precipitated solid was collected by filtration. Next, the resultant is washed with water and then washed with heat using alcohol to obtain 17.6 g of yellow-orange powder. Finally, the powder is purified by sublimation to obtain 3.6 g of a dark yellow fine powder. The melting point of the obtained fine powder was 288.5 ° C. to 291.0 ° C., MS
(M / z): 620.
【００９１】上記（ｂ）の合成において、酢酸アンモニ
ウム化合物の代わりに以下の表に示す各種アンモニウム
塩及びモノエチルアミンの塩酸塩を用いて同様の合成を
行なった。得られた粉末の量、外観及び反応生成物の割
合を表５に示す。In the synthesis of the above (b), similar synthesis was carried out by using various ammonium salts and monoethylamine hydrochloride shown in the following table instead of the ammonium acetate compound. Table 5 shows the amount, appearance and reaction product ratio of the obtained powder.
【００９２】[0092]
【表５】 [Table 5]
【００９３】上記表から、アンモニウム塩化合物が本発
明の化合物の閉環剤として有効であることが判明した。
なお、アンモニア水を用いた反応方法も検討したが、ア
ンモニアガスの分離が起こり、あまり有効な合成方法と
はいえなかった。From the above table, it was found that ammonium salt compounds are effective as ring-closing agents for the compounds of the present invention.
In addition, although a reaction method using aqueous ammonia was also studied, separation of ammonia gas occurred, and it was not a very effective synthesis method.
【００９４】合成例２：（例示化合物３１の合成） （ａ）ジ−（Ｐ−ヒドラジノフェニル−メチルアミン１
２．０ｇとベンジル３０ｇをエタノール１５０ｍｌに溶
解し、これに微量のＰ−トルエンスルホン酸を加え、油
浴中で４時間加熱還流を行なう。室温まで放冷した後、
沈澱した黄白色結晶を吸引口過し、メタノールで洗浄を
行ない、次いで減圧乾燥した。収量は１６．３ｇであっ
た。Synthesis Example 2: (Synthesis of Exemplified Compound 31) (a) Di- (P-hydrazinophenyl-methylamine 1)
2.0 g and 30 g of benzyl are dissolved in 150 ml of ethanol, a small amount of P-toluenesulfonic acid is added thereto, and the mixture is heated and refluxed for 4 hours in an oil bath. After cooling to room temperature,
The precipitated yellow-white crystals were passed through a suction port, washed with methanol, and then dried under reduced pressure. The yield was 16.3 g.
【００９５】（ｂ）上記（ａ）で得られたヒドラゾン１
６．３ｇ、塩化銅１５．６ｇ及び酢酸アンモニウム３５
ｇの混合物を、ジメチルホルムアミド１５０ｍｌ中に加
え、浴温中で約２０時間加熱撹拌を行なう。室温まで冷
却した後、反応液を大量の水中に注入し、析出した固形
物を濾取した。次いで水洗を行ない、アルコールを用い
て数回熱洗浄を行ない、黄橙色の粉末１２．８ｇを得
た。(B) Hydrazone 1 obtained in (a) above
6.3 g, copper chloride 15.6 g and ammonium acetate 35
g of the mixture is added to 150 ml of dimethylformamide, and the mixture is heated and stirred at a bath temperature for about 20 hours. After cooling to room temperature, the reaction solution was poured into a large amount of water, and the precipitated solid was collected by filtration. Next, the product was washed with water and heated several times with alcohol to obtain 12.8 g of yellow-orange powder.
【００９６】このようにして得た粉末を昇華精製し、薄
黄色の微粉末２．８ｇを得る。 融点２５４．５℃〜２５７℃ ＭＳ（ｍ／ｚ）：６２１The powder thus obtained is purified by sublimation to obtain 2.8 g of a pale yellow fine powder. 254.5 ° C-257 ° C MS (m / z): 621
【００９７】なお、本発明の他のビス−１，２，３−ト
リアゾール化合物についても上記と同様の合成方法によ
り合成できる。また、これらのトリアゾール化合物は、
融点がかなり高い傾向にあり、特に例示化合物のうち、
一般式（II）及び一般式（III）で示される化合物は、
すべて融点が２００℃を越えていた。さらに、精製につ
いては洗浄、昇華が好適であり、適当な再結晶溶剤は見
当たらない場合が多かった。The other bis-1,2,3-triazole compounds of the present invention can be synthesized by the same synthesis method as described above. Also, these triazole compounds,
Melting point tends to be quite high, especially among the exemplified compounds,
The compounds represented by the general formulas (II) and (III)
All had melting points above 200 ° C. Further, for purification, washing and sublimation were preferred, and in many cases, no suitable recrystallization solvent was found.
【００９８】合成例３：（例示化合物５０の合成） （ａ）４，４′，４″−トリ−ヒドラジノフェニルアミ
ン三塩酸塩４．４ｇとベンジル９．５ｇをｎ−ブチルア
ルコール１００ｍｌ中、酢酸カリウム３．３ｇを加えて
加熱還流した。反応収量後、析出いた黄橙色粉末を濾取
し、充分熱水洗し、次いで減圧乾燥した。得られた粉末
の収量は、８．１ｇであった。Synthesis Example 3 (Synthesis of Exemplified Compound 50) (a) 4.4 g of 4,4 ′, 4 ″ -tri-hydrazinophenylamine trihydrochloride and 9.5 g of benzyl were dissolved in 100 ml of n-butyl alcohol. After addition of 3.3 g of potassium acetate, the mixture was heated and refluxed, and after the yield of the reaction, the precipitated yellow-orange powder was collected by filtration, sufficiently washed with hot water, and dried under reduced pressure, and the yield of the obtained powder was 8.1 g. .
【００９９】（ｂ）上記（ａ）で得られたヒドラゾン
８．１ｇ、塩化銅（II）８．７ｇ及び酢酸アンモニウム
２５ｇの混合物を、ジメチルスルホオキサイド１２０ｍ
ｌ中に加え、油浴（浴温１２０℃）中、約２０時間加熱
撹拌を行なう。反応終了後、反応液を大量（約１リット
ル）の水中に注入し、析出した固形物を濾取した。次い
で熱水及びアセトンで数回洗浄を繰り返し、若干赤みが
かった橙色粉末３．６ｇを得る。得られた粉末を昇華精
製し、黄橙色の微粉末１．２ｇを得る。 融点：２９６℃〜２９７．５℃ この化合物のＩＲ（ＫＢｒ法）から３１８０ｃｍ-1のヒ
ドラゾンの吸収は消失していた。(B) A mixture of 8.1 g of the hydrazone obtained in the above (a), 8.7 g of copper (II) chloride and 25 g of ammonium acetate was mixed with 120 m of dimethyl sulfoxide.
The mixture is heated and stirred in an oil bath (bath temperature 120 ° C.) for about 20 hours. After the completion of the reaction, the reaction solution was poured into a large amount (about 1 liter) of water, and the precipitated solid was collected by filtration. Subsequently, washing with hot water and acetone is repeated several times to obtain 3.6 g of a slightly reddish orange powder. The obtained powder is purified by sublimation to obtain 1.2 g of yellow-orange fine powder. Melting point: 296 ° C. to 297.5 ° C. From the IR (KBr method) of this compound, the absorption of hydrazone at 3180 cm −1 has disappeared.
【０１００】また、ケールダール法で窒素の含有度を測
定した結果、１５．２％であり、計算値である１５．５
％に近い値を示した。Further, as a result of measuring the nitrogen content by the Kehldahl method, it was 15.2%, which was a calculated value of 15.5.
%.
【０１０１】なお、本発明の他のトリス−１，２，３−
トリアゾール化合物についても上記と同様の合成方法に
より合成できる。また、これらのトリアゾール化合物の
精製については熱洗浄、昇華が好適であり、適当な再結
晶溶剤は見当たらない場合が多かった。The other Tris-1,2,3-
The triazole compound can be synthesized by the same synthesis method as described above. For the purification of these triazole compounds, thermal washing and sublimation are suitable, and an appropriate recrystallization solvent has not been found in many cases.
【０１０２】実施例１〜４ ガラス基板（２５ｍｍ×７５ｍｍ×厚さ１．１ｍｍのサ
イズ、ＨＯＹＡ社製）上に、透明電極として用いるＩＴ
Ｏを膜厚１００ｎｍで蒸着して透明支持基板とし、これ
をイソプロピルアルコール中、超音波洗浄し、さらにア
セトンに浸漬し洗浄した。得られた透明支持基板を、乾
燥Ｎ2ガスで乾燥した。次いで、透明支持基板上に、表
６に示す本発明のビス−トリアゾール化合物４種からな
る膜厚２００ｎｍの正孔注入輸送層を真空蒸着法で形成
し、この層上にトリス（８−キノリノール）アルミニウ
ム（III）を膜厚３００ｎｍで連続して蒸着して発光層
を形成した。なお、この際の蒸着は、１０-5Ｐａ前後の
真空度で行った。Examples 1-4 An IT used as a transparent electrode on a glass substrate (25 mm × 75 mm × 1.1 mm thick, manufactured by HOYA)
O was deposited to a thickness of 100 nm to form a transparent support substrate, which was subjected to ultrasonic cleaning in isopropyl alcohol and further immersed in acetone for cleaning. The obtained transparent support substrate was dried with dry N 2 gas. Next, a 200 nm-thick hole injection / transport layer composed of the four bis-triazole compounds of the present invention shown in Table 6 was formed on the transparent support substrate by a vacuum evaporation method, and tris (8-quinolinol) was formed on this layer. Aluminum (III) was continuously deposited to a thickness of 300 nm to form a light emitting layer. In this case, the vapor deposition was performed at a degree of vacuum of about 10 −5 Pa.
【０１０３】その後、マグネシウム入りのボートに通電
し、真空速度５〜６ｎｍ／秒でマグネシウムを蒸着し
た。この際、同時に電子ビームにより銅を加熱し、０．
１〜０．３μｍ／秒で銅を蒸着することにより、マグネ
シウムに銅を混合した電極を形成した。Thereafter, electricity was supplied to the boat containing magnesium, and magnesium was deposited at a vacuum rate of 5 to 6 nm / sec. At this time, copper is simultaneously heated by an electron beam,
By depositing copper at 1 to 0.3 μm / sec, an electrode in which copper was mixed with magnesium was formed.
【０１０４】このようにして作製した４種類の有機ＥＬ
素子をＩＴＯ電極を正極、マグネシウムと銅の混合物よ
りなる電極を負極とし、表６の印加電圧を各々印加した
結果、緑色の発光を得た。この際の発光輝度を表６に示
す。The four types of organic EL thus produced
The device was used as a positive electrode with an ITO electrode and a negative electrode with an electrode made of a mixture of magnesium and copper. As a result of applying the applied voltages shown in Table 6, green light was emitted. Table 6 shows the emission luminance at this time.
【０１０５】また、これら４種類の有機ＥＬ素子に使用
した各ビス−トリアゾール化合物の正孔輸送度及びガラ
ス転移点について、代表的な正孔注入輸送化合物である
ＴＰＤ（Appl.Phys.dett,51 (1987) p913 及び特開昭５
９−１９４３９３号）を参照として測定した。その結果
を表６に示すThe hole transporting degree and the glass transition point of each of the bis-triazole compounds used in these four types of organic EL devices were determined with respect to TPD (Appl. Phys. Dett, 51) which is a typical hole injecting and transporting compound. (1987) p913 and JP-A-5
No. 9-194393). Table 6 shows the results.
【０１０６】[0106]
【表６】 [Table 6]
【０１０７】実施例１〜４で用いたビス−トリアゾール
化合物は、高いガラス転移点（いいかえると熱安定性の
優位性）及び高い輸送度（いいかえると発光輝度優位
性）を有する正孔注入輸送化合物であることがわかっ
た。The bis-triazole compounds used in Examples 1-4 have a high glass transition point (in other words, superior thermal stability) and a high degree of transport (in other words, superior emission brightness). It turned out to be.
【０１０８】実施例５〜８ 実施例１〜４と同様の透明支持基板を、エチルアルコー
ル、次いでアセトンで超音波洗浄した。得られた透明支
持基板を、乾燥Ｎ2ガスで乾燥した。次いで、透明支持
基板を真空蒸着装置の基板ホルダーに固定し、モリブデ
ン性抵抗加熱用ボートに第１表の昇華精製を行ったトリ
ス−トリアゾール化合物を２００ｍｇ入れ、一方、同様
の加熱用ボートに下記構造式で示される下記に示す構造
を有するトリス（４−メチル−８−キノリノール）アル
ミニウム錯体を２００ｍｇ入れ、真空チャンバー内を１
×１０-4Ｐａまで減圧した。Examples 5 to 8 The same transparent supporting substrates as in Examples 1 to 4 were subjected to ultrasonic cleaning with ethyl alcohol and then with acetone. The obtained transparent support substrate was dried with dry N 2 gas. Next, the transparent supporting substrate was fixed to a substrate holder of a vacuum evaporation apparatus, and 200 mg of the tris-triazole compound subjected to sublimation purification in Table 1 was placed in a molybdenum resistance heating boat. 200 mg of a tris (4-methyl-8-quinolinol) aluminum complex represented by the following formula and represented by the following formula was put into the vacuum chamber, and 1
The pressure was reduced to × 10 −4 Pa.
【０１０９】[0109]
【化２２】 Embedded image
【０１１０】まず、トリアゾール化合物が入っているボ
ートを２３０〜２４０℃まで加熱し、内容物を０．１〜
０．３ｎｍ／秒の蒸着速度で基板上に蒸着させ、膜厚６
０〜８０ｎｍの正孔注入輸送層を形成した。得られた正
孔注入輸送層を真空チャンバー内からとりだすことな
く、この上にアルミニウム錯体をボート温度２５０℃、
蒸着速度を０．１〜０．２ｎｍ／秒で基板上に蒸着さ
せ、膜厚４０ｎｍの発光層を積層した。この積層板を真
空チャンバーから取り出し、発光層側にステンレススチ
ール製のマスクを接地し、サイドウォールスペーサ基板
ホルダーに固定した。First, the boat containing the triazole compound was heated to 230 to 240 ° C., and the content was reduced to 0.1 to 240 ° C.
Deposited on the substrate at a deposition rate of 0.3 nm / sec.
A hole injection transport layer having a thickness of 0 to 80 nm was formed. Without taking out the obtained hole injecting and transporting layer from the vacuum chamber, an aluminum complex was placed thereon and the boat temperature was set at 250 ° C.
Evaporation was performed on the substrate at an evaporation rate of 0.1 to 0.2 nm / sec, and a light-emitting layer having a thickness of 40 nm was laminated. The laminate was taken out of the vacuum chamber, a stainless steel mask was grounded on the light emitting layer side, and fixed to a sidewall spacer substrate holder.
【０１１１】次いで、タングステンバスケットに銀ワイ
ヤー０．５ｇを入れ、モリブデン製ボートにナグネシウ
ムリボン１ｇを入れ、真空チャンバー内を１×１０-4Ｐ
ａまで減圧し、マグネシウム及び銀を同時に蒸着し、陰
極を成膜して有機ＥＬ素子を作製した。Next, 0.5 g of silver wire was put in a tungsten basket, 1 g of Nagnesium ribbon was put in a boat made of molybdenum, and the inside of the vacuum chamber was 1 × 10 -4 P
The pressure was reduced to a, and magnesium and silver were simultaneously evaporated to form a cathode, thereby producing an organic EL device.
【０１１２】このようにして作製した４種類の有機ＥＬ
素子に印加電圧１２Ｖを印加し、この際の発光輝度及び
発光開始電圧を測定した。また、これら４種類の有機Ｅ
Ｌ素子に使用した各トリス−トリアゾール化合物の正孔
輸送度及びガラス転移点について測定した。その結果を
表７に示す。The four types of organic EL thus prepared
An applied voltage of 12 V was applied to the device, and the emission luminance and emission start voltage at this time were measured. In addition, these four types of organic E
The degree of hole transport and the glass transition point of each tris-triazole compound used in the L element were measured. Table 7 shows the results.
【０１１３】[0113]
【表７】 [Table 7]
【０１１４】実施例５〜８で用いたトリス−トリアゾー
ル化合物は、高いガラス転移点（いいかえると熱安定性
の優位性）及び高い輸送効率（いいかえると発光輝度優
位性）を有する正孔注入輸送化合物であることがわかっ
た。また、発光開始電圧も５〜６Ｖ程度であり、低駆動
電圧で発光が起こり、消費電力の低減、熱上昇の防止、
過剰電流の防止等にも有効であることがわかった。The tris-triazole compounds used in Examples 5 to 8 have a high glass transition point (in other words, superior thermal stability) and high transport efficiency (in other words, superior emission luminance). It turned out to be. The light emission start voltage is also about 5 to 6 V, and light emission occurs at a low drive voltage, reducing power consumption, preventing heat rise,
It was found that it was also effective in preventing excess current.
【０１１５】実施例９〜１０：電子注入輸送層を設けた
系 正孔注入輸送層を、例示化合物３７（ガラス転移点１２
４．５℃）又はＮｏ３１により形成し、さらに陰極と発
光層との間にＮ型ａ−ＳｉＣを３０ｎｍ膜厚でプラズマ
ＣＶＤにより形成した。Examples 9 to 10: System provided with an electron injecting and transporting layer
(4.5 ° C.) or No. 31, and further, N-type a-SiC was formed between the cathode and the light emitting layer to a thickness of 30 nm by plasma CVD.
【０１１６】このようにして、陽極／正孔注入輸送層／
発光層／電子注入輸送層／陰極の構成を有する有機ＥＬ
素子２種類を作製し、発光輝度を測定した。その結果、
Ｎｏ３７は４．５×１０4ｃｄ／ｍ2、Ｎｏ３１は１．２
×１０4ｃｄ／ｍ2と、すぐれた発光輝度を有していた。
また、Ｎｏ３７のそれは未封止の状態で約８０時間の緑
色ＥＬ発光を有していた。Thus, the anode / hole injection / transport layer /
Organic EL having structure of light emitting layer / electron injection / transport layer / cathode
Two types of devices were produced, and the emission luminance was measured. as a result,
No. 37 is 4.5 × 10 4 cd / m 2 , No. 31 is 1.2
It had excellent emission luminance of × 10 4 cd / m 2 .
Further, that of No. 37 had green EL emission for about 80 hours in an unsealed state.
【０１１７】実施例１１：電子注入輸送層を設けた系 実施例５の有機ＥＬ素子において、発光層と陰極との間
にジフェニルキノン化合物を蒸着により２０ｎｍの膜厚
に積層した以外は、実施例５と同様にして有機ＥＬ素子
を作製した。この有機ＥＬ素子の発光輝度、発光開始電
圧を測定した結果、発光開始電圧は４．９Ｖと１０％程
度低くなったが、発光輝度は８７００ｃｄ／ｍ2と余り
差は認められなかった。しかし、電子注入輸送層を設け
ることにより、より低い駆動電圧で、発光がより起こり
やすくなることが分かった。Example 11: System provided with an electron injecting / transporting layer In the organic EL device of Example 5, except that a diphenylquinone compound was laminated between the light emitting layer and the cathode to a thickness of 20 nm by vapor deposition. In the same manner as in Example 5, an organic EL device was produced. As a result of measuring the light emission luminance and the light emission start voltage of this organic EL element, the light emission start voltage was lowered by about 10% to 4.9 V, but the light emission luminance was not significantly different from 8700 cd / m 2 . However, it was found that the provision of the electron injecting and transporting layer facilitates light emission at a lower driving voltage.
【０１１８】実施例１２：電子障壁層を設けた系 図１に示したように、正孔注入輸送層４を、実施例１で
用いた例示化合物３を用いて形成し、さらに発光層２と
正孔注入輸送層４との間に特開６３−２９５６９５号に
記載されている下記構造式で示されるトリフェニルアミ
ン化合物からなる膜厚８０ｎｍの電子障壁層３を蒸着法
によって設けた（図１）。これ以外は実施例１〜４とほ
ぼ同様の方法により陰極５及び陰極１を有する有機ＥＬ
素子を作製した。Example 12: System Provided with Electron Barrier Layer As shown in FIG. 1, a hole injection / transport layer 4 was formed using the exemplified compound 3 used in Example 1, and a light emitting layer 2 was formed. An 80 nm-thick electron barrier layer 3 made of a triphenylamine compound represented by the following structural formula described in JP-A-63-295695 was provided between the hole injection transport layer 4 and the hole injection transport layer 4 (FIG. 1). ). Except for this, an organic EL having a cathode 5 and a cathode 1 is substantially the same as in Examples 1 to 4.
An element was manufactured.
【０１１９】[0119]
【化２３】 Embedded image
【０１２０】この有機ＥＬ素子に、印加電圧７．５Ｖを
印加した際の発光輝度は４．６×１０３ｃｄ／ｍ2 であ
り、小さな印加電圧で高い発光輝度を示した。これによ
り、電子障壁層を新たに設けたことにより、より高効率
の有機ＥＬ素子が実現できることが判明した。The light emission luminance when an applied voltage of 7.5 V was applied to this organic EL device was 4.6 × 103 cd / m 2 , and the light emission luminance was high with a small applied voltage. As a result, it has been found that a more efficient organic EL device can be realized by newly providing an electron barrier layer.
【０１２１】実施例１３：電子障壁層を設けた系 実施例５の有機ＥＬ素子において、正孔注入輸送層と発
光層との間に実施例１２で用いたトリフェニルアミン化
合物からなる膜厚８０ｎｍの電子障壁層を蒸着法によっ
て設けた。これ以外は実施例５とほぼ同様の方法により
有機ＥＬ素子を作製した。Example 13: System provided with an electron barrier layer In the organic EL device of Example 5, a film thickness of 80 nm comprising the triphenylamine compound used in Example 12 between the hole injecting and transporting layer and the light emitting layer Was provided by an evaporation method. Except for this, an organic EL device was manufactured in substantially the same manner as in Example 5.
【０１２２】この有機ＥＬ素子の発光開始電圧、発光輝
度を実施例５と同様に測定した結果、発光開始電圧は
５．３Ｖとあまり差は認められなかったが、発光輝度は
９８００ｃｄ／ｍ2 と、１０％以上も上昇した。また、
発光効率も１．６Ｌｍ／Ｗから１．８Ｌｍ／Ｗに上昇し
た。これにより、電子障壁層を新たに設けたことによ
り、より高効率の有機ＥＬ素子が実現できることが判明
した。The light emission start voltage and the light emission luminance of this organic EL element were measured in the same manner as in Example 5. As a result, the light emission start voltage was 5.3 V and there was not much difference, but the light emission luminance was 9800 cd / m 2 . More than 10%. Also,
The luminous efficiency also increased from 1.6 Lm / W to 1.8 Lm / W. As a result, it has been found that a more efficient organic EL device can be realized by newly providing an electron barrier layer.
【０１２３】[0123]
【発明の効果】本発明によれば、良好な発光効率、高輝
度発光、低駆動電圧での発光、水又は酸素等の物質によ
る化学的及び光、熱等の物理的劣化の小さい有機ＥＬ素
子を提供することが可能となる。According to the present invention, an organic EL device having good luminous efficiency, high-luminance luminescence, luminescence at a low driving voltage, and low physical and chemical deterioration due to a substance such as water or oxygen such as light and heat. Can be provided.
【図１】本発明の有機ＥＬ素子の概略断面図である。FIG. 1 is a schematic sectional view of an organic EL device of the present invention.
１ 陰極 ２ 発光層 ３ 電子障壁層 ４ 正孔注入輸送層 ５ 陽極 Reference Signs List 1 cathode 2 light emitting layer 3 electron barrier layer 4 hole injection / transport layer 5 anode
Claims (10)
６〜１２の置換又は非置換のアリーレン基であり；Ｘは
酸素原子、硫黄原子、−（ＣＨ2 ）n −、−Ｎ（Ｒ3 ）
−又は−ＣＨ（Ｒ4 ）−であり（ここで、ｎは０〜２の
整数であり、Ｒ3は水素原子、炭素数１〜８のアルキル
基、置換又は非置換のフェニル基、メタリル基、アリル
基であり、Ｒ4 は水素原子、炭素数１〜８のアルキル
基、置換又は非置換のフェニル基である）；Ｒ1及びＲ2
は、同一又は異なって、水素原子、炭素数１〜４のアル
キル基、置換又は非置換のアリール基である〕で示され
る１，２，３−トリアゾール化合物。1. A compound of the formula (I) [Wherein, Ar and Ar ′ are the same or different and are a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; X represents an oxygen atom, a sulfur atom, — (CH 2 ) n —, —N ( R 3 )
— Or —CH (R 4 ) — (where n is an integer of 0 to 2, R 3 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, a methallyl group) R 4 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted phenyl group); R 1 and R 2
Are the same or different and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted aryl group].
フェニレン基（ここでＲ5 は水素原子、ハロゲン原子、
メチル基、メトキシ基、トリフロロメチル基）、Ｘが結
合手、Ｒ1及びＲ2が、同一又は異なって、Ｒ6 で置換さ
れたフェニル基（ここで、Ｒ6 は水素原子、ハロゲン原
子、炭素数１〜４のアルキル基、炭素数１〜４のアルコ
キシ基、トリフロロメチル基）であり、下記副式（II） 【化２】 で示される請求項１記載の１，２，３−トリアゾール化
合物。Wherein Ar and Ar 'are phenylene group (wherein R 5 substituted together with R 5 a hydrogen atom, a halogen atom,
A methyl group, a methoxy group, a trifluoromethyl group), X is a bond, R 1 and R 2 are the same or different and are substituted with R 6 , wherein R 6 is a hydrogen atom, a halogen atom, An alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a trifluoromethyl group), and has the following sub-formula (II): The 1,2,3-triazole compound according to claim 1, which is represented by the formula:
が−Ｎ（Ｒ3 ）−（ここで、Ｒ3 は上記と同義であ
る）、Ｒ1及びＲ2が、同一又は異なって、Ｒ6 で置換さ
れたフェニル基（ここで、Ｒ6 は上記と同義）であり、
下記副式（III) 【化３】 で示される請求項１記載の１，２，３−トリアゾール化
合物。3. Ar and Ar ′ are both a phenylene group, X
There -N (R 3) - (wherein, R 3 is as defined above), R 1 and R 2 are the same or different, a phenyl group substituted (wherein in R 6, R 6 is the Synonymous with)
Sub-formula (III) below The 1,2,3-triazole compound according to claim 1, which is represented by the formula:
が−Ｎ（Ｒ3 ）−〔ここで、Ｒ3 は 【化４】 （ここで、Ｒ1及びＲ2は上記と同義）〕であり、下記副
式（VI） 【化５】 で示される請求項１記載の１，２，３−トリアゾール化
合物。4. Ar and Ar ′ are both a phenylene group, X
Is -N (R 3 )-where R 3 is (Wherein R 1 and R 2 have the same meanings as described above)], and the following sub-formula (VI): The 1,2,3-triazole compound according to claim 1, which is represented by the formula:
が−Ｎ（Ｒ3 ）−〔ここで、Ｒ3 は 【化６】 （ここで、Ｒ6 は上記と同義）〕であり、下記副式（VI
I) 【化７】 で示される請求項１記載の１，２，３−トリアゾール化
合物。5. Ar and Ar ′ are both a phenylene group, X
Is -N (R 3 )-where R 3 is (Where R 6 is as defined above)], and the following sub-formula (VI
I) The 1,2,3-triazole compound according to claim 1, which is represented by the formula:
るエタンジオン化合物と、式（Ｖ） Ｈ2ＮＨＮ−Ａｒ−Ｘ−Ａｒ’−ＮＨＮＨ2 ……（Ｖ） （式中、Ａｒ、Ａｒ’及びＸは式（Ｉ）と同義である）
で示されるヒドラジン化合物、又は式（VIII) 【化９】 で示されるトリス−（４−ヒドラジノフェニル）アミン
化合物とを反応させることにより、請求項１記載の式
（Ｉ）の１，２，３−トリアゾール化合物を製造するこ
とを特徴とする１，２，３−トリアゾール化合物の製造
方法。6. A compound of the formula (IV) (Wherein R 1 and R 2 have the same meanings as in formula (I)) and a compound represented by formula (V) H 2 NHN-Ar-X-Ar′-NHNH 2 (V) Wherein Ar, Ar ′ and X have the same meanings as in formula (I).
Or a hydrazine compound represented by the formula (VIII): A 1,2,3-triazole compound of the formula (I) according to claim 1 by reacting the compound with a tris- (4-hydrazinophenyl) amine compound represented by the formula: For producing 3,3-triazole compounds.
（Ｖ）のヒドラジン化合物又は式（VIII) のトリス−
（４−ヒドラジノフェニル）アミン化合物とを、４級ア
ンモニウム塩の存在下で反応させる請求項６記載の１，
２，３−トリアゾール化合物の製造方法。7. An ethanedione compound of the formula (IV) and a hydrazine compound of the formula (V) or a tris-formula of the formula (VIII)
7. The method according to claim 6, wherein the (4-hydrazinophenyl) amine compound is reacted in the presence of a quaternary ammonium salt.
A method for producing a 2,3-triazole compound.
がこの順で積層された有機電界発光素子であって、 前記正孔注入輸送層が、請求項１記載の式（Ｉ）で示さ
れる１，２，３−トリアゾール化合物を含有することを
特徴とする有機電界発光素子。8. An organic electroluminescent device in which an anode, a hole injecting and transporting layer, a light emitting layer, and a cathode are stacked in this order, wherein the hole injecting and transporting layer is represented by the formula (I) according to claim 1. An organic electroluminescent device comprising the indicated 1,2,3-triazole compound.
有する請求項８記載の有機電界発光素子。9. The organic electroluminescent device according to claim 8, further comprising an electron injection / transport layer between the light emitting layer and the cathode.
請求項８又は９記載の有機電界発光素子。10. The organic electroluminescent device according to claim 8, wherein a charge barrier layer is formed facing the light emitting layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10006126A JPH11199567A (en) | 1998-01-14 | 1998-01-14 | 1,2,3-triazole compound, its production and organic electroluminescent element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10006126A JPH11199567A (en) | 1998-01-14 | 1998-01-14 | 1,2,3-triazole compound, its production and organic electroluminescent element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11199567A true JPH11199567A (en) | 1999-07-27 |
Family
ID=11629825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10006126A Pending JPH11199567A (en) | 1998-01-14 | 1998-01-14 | 1,2,3-triazole compound, its production and organic electroluminescent element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11199567A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8034420B2 (en) | 2007-02-06 | 2011-10-11 | Sumitomo Chemical Company, Limited | Benzotriazole compound-containing composition and light-emitting device using the composition |
-
1998
- 1998-01-14 JP JP10006126A patent/JPH11199567A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8034420B2 (en) | 2007-02-06 | 2011-10-11 | Sumitomo Chemical Company, Limited | Benzotriazole compound-containing composition and light-emitting device using the composition |
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