WO2019039402A1 - Compound having indenobenzoazole-ring structure, and organic electroluminescence element - Google Patents
Compound having indenobenzoazole-ring structure, and organic electroluminescence element Download PDFInfo
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- WO2019039402A1 WO2019039402A1 PCT/JP2018/030545 JP2018030545W WO2019039402A1 WO 2019039402 A1 WO2019039402 A1 WO 2019039402A1 JP 2018030545 W JP2018030545 W JP 2018030545W WO 2019039402 A1 WO2019039402 A1 WO 2019039402A1
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 108
- 238000005401 electroluminescence Methods 0.000 title 1
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 136
- 125000001424 substituent group Chemical group 0.000 claims abstract description 134
- 239000000463 material Substances 0.000 claims abstract description 74
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 48
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 44
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 44
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 238000002347 injection Methods 0.000 claims abstract description 34
- 239000007924 injection Substances 0.000 claims abstract description 34
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 30
- 125000004431 deuterium atom Chemical group 0.000 claims abstract description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 25
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 20
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 114
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 57
- -1 triphenylsilyl group Chemical group 0.000 claims description 43
- 230000000903 blocking effect Effects 0.000 claims description 34
- RXXXUIOZOITBII-UHFFFAOYSA-N indeno[1,2-g]indole Chemical group C1=C2C=CC=CC2=C2C1=C1N=CC=C1C=C2 RXXXUIOZOITBII-UHFFFAOYSA-N 0.000 claims description 34
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 26
- 239000012044 organic layer Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims description 13
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 13
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 13
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 150000001975 deuterium Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 17
- 150000002894 organic compounds Chemical class 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 26
- 239000010408 film Substances 0.000 description 19
- 150000001721 carbon Chemical group 0.000 description 17
- 238000007740 vapor deposition Methods 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 13
- 230000005525 hole transport Effects 0.000 description 12
- 238000000151 deposition Methods 0.000 description 11
- 230000008021 deposition Effects 0.000 description 11
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical group C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 5
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- ZVFQEOPUXVPSLB-UHFFFAOYSA-N 3-(4-tert-butylphenyl)-4-phenyl-5-(4-phenylphenyl)-1,2,4-triazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C(N1C=2C=CC=CC=2)=NN=C1C1=CC=C(C=2C=CC=CC=2)C=C1 ZVFQEOPUXVPSLB-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000004322 quinolinols Chemical class 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 0 *C(*C1=*)=NC1=I**=* Chemical compound *C(*C1=*)=NC1=I**=* 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001454 anthracenes Chemical class 0.000 description 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000001041 indolyl group Chemical group 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 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
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000001544 thienyl group Chemical group 0.000 description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 3
- 125000006617 triphenylamine group Chemical group 0.000 description 3
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 3
- 235000019798 tripotassium phosphate Nutrition 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 2
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 2
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 150000001556 benzimidazoles Chemical class 0.000 description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001716 carbazoles Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 125000005956 isoquinolyl group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000007978 oxazole derivatives Chemical class 0.000 description 2
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 2
- 150000005041 phenanthrolines Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- 125000001725 pyrenyl group Chemical group 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- DETFWTCLAIIJRZ-UHFFFAOYSA-N triphenyl-(4-triphenylsilylphenyl)silane Chemical compound C1=CC=CC=C1[Si](C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 DETFWTCLAIIJRZ-UHFFFAOYSA-N 0.000 description 2
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- YQOLEILXOBUDMU-KRWDZBQOSA-N (4R)-5-[(6-bromo-3-methyl-2-pyrrolidin-1-ylquinoline-4-carbonyl)amino]-4-(2-chlorophenyl)pentanoic acid Chemical compound CC1=C(C2=C(C=CC(=C2)Br)N=C1N3CCCC3)C(=O)NC[C@H](CCC(=O)O)C4=CC=CC=C4Cl YQOLEILXOBUDMU-KRWDZBQOSA-N 0.000 description 1
- STPKWKPURVSAJF-LJEWAXOPSA-N (4r,5r)-5-[4-[[4-(1-aza-4-azoniabicyclo[2.2.2]octan-4-ylmethyl)phenyl]methoxy]phenyl]-3,3-dibutyl-7-(dimethylamino)-1,1-dioxo-4,5-dihydro-2h-1$l^{6}-benzothiepin-4-ol Chemical compound O[C@H]1C(CCCC)(CCCC)CS(=O)(=O)C2=CC=C(N(C)C)C=C2[C@H]1C(C=C1)=CC=C1OCC(C=C1)=CC=C1C[N+]1(CC2)CCN2CC1 STPKWKPURVSAJF-LJEWAXOPSA-N 0.000 description 1
- PXLYGWXKAVCTPX-UHFFFAOYSA-N 1,2,3,4,5,6-hexamethylidenecyclohexane Chemical class C=C1C(=C)C(=C)C(=C)C(=C)C1=C PXLYGWXKAVCTPX-UHFFFAOYSA-N 0.000 description 1
- DJMOXMNDXFFONV-UHFFFAOYSA-N 1,3-dimethyl-7-[2-(n-methylanilino)ethyl]purine-2,6-dione Chemical compound C1=NC=2N(C)C(=O)N(C)C(=O)C=2N1CCN(C)C1=CC=CC=C1 DJMOXMNDXFFONV-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
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 1
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- ZABORCXHTNWZRV-UHFFFAOYSA-N 10-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]phenoxazine Chemical compound O1C2=CC=CC=C2N(C2=CC=C(C=C2)C2=NC(=NC(=N2)C2=CC=CC=C2)C2=CC=CC=C2)C2=C1C=CC=C2 ZABORCXHTNWZRV-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- IVCGJOSPVGENCT-UHFFFAOYSA-N 1h-pyrrolo[2,3-f]quinoline Chemical class N1=CC=CC2=C(NC=C3)C3=CC=C21 IVCGJOSPVGENCT-UHFFFAOYSA-N 0.000 description 1
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- RKVIAZWOECXCCM-UHFFFAOYSA-N 2-carbazol-9-yl-n,n-diphenylaniline Chemical compound C1=CC=CC=C1N(C=1C(=CC=CC=1)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 RKVIAZWOECXCCM-UHFFFAOYSA-N 0.000 description 1
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-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
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 1
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 1
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- MZYDBGLUVPLRKR-UHFFFAOYSA-N 9-(3-carbazol-9-ylphenyl)carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=CC=C1 MZYDBGLUVPLRKR-UHFFFAOYSA-N 0.000 description 1
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- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
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- 238000010549 co-Evaporation Methods 0.000 description 1
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- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 229940126142 compound 16 Drugs 0.000 description 1
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- 229940125844 compound 46 Drugs 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 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 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
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- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
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- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- KPTRDYONBVUWPD-UHFFFAOYSA-N naphthalen-2-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CC=C21 KPTRDYONBVUWPD-UHFFFAOYSA-N 0.000 description 1
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- 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
- XEXYATIPBLUGSF-UHFFFAOYSA-N phenanthro[9,10-b]pyridine-2,3,4,5,6,7-hexacarbonitrile Chemical group N1=C(C#N)C(C#N)=C(C#N)C2=C(C(C#N)=C(C(C#N)=C3)C#N)C3=C(C=CC=C3)C3=C21 XEXYATIPBLUGSF-UHFFFAOYSA-N 0.000 description 1
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- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- UMLDUMMLRZFROX-UHFFFAOYSA-N pyridin-2-ylboronic acid Chemical compound OB(O)C1=CC=CC=N1 UMLDUMMLRZFROX-UHFFFAOYSA-N 0.000 description 1
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- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
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- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical class [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003967 siloles Chemical class 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
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- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
Definitions
- the present invention relates to a compound and an element suitable for an organic electroluminescent element (hereinafter referred to as an organic EL element) which is a self-emission element suitable for various display devices, and more specifically, to have a benzoazole ring structure
- the present invention relates to a compound and an organic EL device using the compound.
- the organic EL element is a self light emitting element, it is brighter than the liquid crystal element and has excellent visibility and clear display, and therefore, active research has been conducted.
- Eastman Kodak Company C.I. W. Tang et al. Made the organic EL device using the organic material practical by developing a laminated structure device in which various functions are shared by the respective materials. They stack phosphors capable of transporting electrons and organic substances capable of transporting holes, and inject both charges into the phosphor layer to emit light, with a voltage of 10 V or less A high luminance of 1000 cd / m 2 or more can be obtained (see, for example, Patent Document 1 and Patent Document 2).
- Non-Patent Document 3 An element utilizing light emission by thermally activated delayed fluorescence (TADF) has also been developed.
- TADF thermally activated delayed fluorescence
- the light emitting layer can also be produced by doping a charge transporting compound generally called a host material with a fluorescent compound, a phosphorescent compound, or a material that emits delayed fluorescence.
- a charge transporting compound generally called a host material with a fluorescent compound, a phosphorescent compound, or a material that emits delayed fluorescence.
- the selection of the organic material in the organic EL element has a great influence on various characteristics such as the efficiency and durability of the element. (For example, refer to Non-Patent Document 2)
- the charge injected from both electrodes is recombined in the light emitting layer to obtain light emission, it is important how efficiently both holes and electrons are transferred to the light emitting layer.
- the electron injection property is enhanced, the mobility is increased, the hole blocking property for blocking holes injected from the anode is further enhanced, and the probability that holes and electrons recombine is improved, and further generated in the light emitting layer By trapping the excitons, high efficiency light emission can be obtained. Therefore, the role of the electron transport material is important, and there is a demand for an electron transport material having high electron injection property, high electron mobility, high hole blocking property, and high durability to holes.
- the heat resistance and the amorphous property of the material are also important with respect to the lifetime of the element.
- the heat generated at the time of device operation causes thermal decomposition even at low temperatures, and the materials deteriorate.
- crystallization of a thin film occurs even for a short time, and the device is degraded. Therefore, the material to be used is required to have high heat resistance and good amorphousness.
- a typical light emitting material tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq3) is generally used also as an electron transport material, but its electron transfer is slow, and its work function is 5.6 eV, so it is positive. The hole blocking performance is not sufficient.
- TAZ 4-bis(triphenyl) -4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole
- TAZ has a large work function of 6.6 eV and high hole blocking ability, it has an electron-transporting hole blocking layer laminated on the cathode side of a fluorescent light emitting layer or a phosphorescent light emitting layer prepared by vacuum deposition or coating. And contributes to high efficiency of the organic EL element (see, for example, Non-Patent Document 4).
- Non-Patent Document 5 Low electron transportability is a major issue in TAZ, and it has been necessary to produce an organic EL device in combination with an electron transport material having higher electron transportability (see, for example, Non-Patent Document 5).
- BCP has a large work function of 6.7 eV and high hole blocking ability, it has a low glass transition point (Tg) of 83 ° C., so the thin film lacks stability and functions sufficiently as a hole blocking layer. I can not say that.
- An object of the present invention is an organic compound having excellent electron injection / transport performance, hole blocking ability, and excellent stability in a thin film state as a material for organic EL devices having high efficiency and high durability. It is another object of the present invention to provide a highly efficient and highly durable organic EL device using this compound.
- the physical properties that the organic compound to be provided by the present invention should have include (1) good electron injection characteristics, (2) high electron mobility, and (3) hole blocking ability. It can be mentioned that it is excellent, (4) that the thin film state is stable, and (5) that it is excellent in heat resistance. Further, the physical characteristics that the organic EL element to be provided by the present invention should have include (1) high luminous efficiency and high power efficiency, (2) low luminous initiation voltage, and (3) practical driving The low voltage and (4) long life can be mentioned.
- the present inventors have the ability to coordinate the nitrogen atom of the benzoazole ring having electron affinity to a metal and the excellent heat resistance. Pay attention to designing and chemically synthesizing a compound having a benzoazole ring structure, and trial manufacture of various organic EL devices using the compound, and as a result of earnestly evaluating the characteristics of the device, the present invention is completed.
- the present invention is a compound represented by the following general formula (1) and having an indenobenzoazole ring structure.
- a 1 to A 4 may be the same as or different from each other, and are a hydrogen atom, a deuterium atom or a carbon atom having a substituent, a carbon atom having a substituted or unsubstituted aromatic hydrocarbon group, a substitution Or a carbon atom having a non-substituted aromatic heterocyclic group, a carbon atom having a substituted or non-substituted fused polycyclic aromatic group, or a nitrogen atom
- Y 1 represents a hydrogen atom, a deuterium atom, a substituted or non-substituted Aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted fused polycyclic aromatic group, linear group having 1 to 6 carbon atoms which may have a substituent Or a branched alkyl group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a linear or
- (A-1) (Wherein, the broken line is a bonding site, and R 1 and R 2 may be the same or different from each other, and may have a substituent, a linear or branched alkyl having 1 to 6 carbon atoms) Represents a group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent.
- Ar 1 represents a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a trimethylsilyl group, a triphenylsilyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, A substituted or unsubstituted fused polycyclic aromatic group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, the number of carbon atoms which may have a substituent 5 to 10 cycloalkyl groups, or Represents a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and m represents an integer of 0 to 5.
- the same Ar 1 's bound to a plurality of benzene rings may be the same as or different from each other, and the benzene ring and the substituent substituted on the benzene ring, or the substituents substituted on the same benzene ring may be a single bond And may combine with each other to form a ring via a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom)
- the present invention is also a compound having an indenobenzoazole ring structure, wherein the general formula (1) described in [1] is represented by the following general formula (2).
- a 5 and A 6 may be the same or different, and are hydrogen atoms, deuterium atoms or carbon atoms having a substituent, carbon atoms having a substituted or unsubstituted aromatic hydrocarbon group, substituted or no.
- Y 2 is a hydrogen atom, a deuterium atom, a substituted or unsubstituted aromatic Hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted fused polycyclic aromatic group, and optionally substituted linear or branched C 1 to C 6 carbon atoms
- X is an oxygen source R 3 and R 4 may be the same as or different from each other, and may have a substituent, a linear or branched alkyl group having 1 to 6 carbon atoms, or a
- the same Ar 2 's bound to a plurality of benzene rings may be the same or different from each other, and the benzene ring and the substituent substituted to the benzene ring, or the substituents substituted to the same benzene ring may be a single bond And may combine with each other to form a ring via a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom)
- the present invention is also a compound having an indenobenzoazole ring structure, wherein the general formula (2) described in [2] is represented by the following general formula (3).
- a 7 and A 8 may be identical to or different from each other, and are a hydrogen atom, a deuterium atom or a carbon atom having a substituent, a carbon atom having a substituted or unsubstituted aromatic hydrocarbon group, a substitution Or a carbon atom having a substituted or unsubstituted aromatic heterocyclic group, or a carbon atom having a substituted or unsubstituted fused polycyclic aromatic group
- Y 3 represents a hydrogen atom, a deuterium atom, or a substituted or unsubstituted aromatic group
- Ar 3 When o is an integer of 2 or more, a plurality of these are bonded to the same benzene ring Ar 3 may be identical to or different from each other, and may be a benzene ring and a substituent substituted on the benzene ring, or a plurality of substituents substituted on the same benzene ring may be a single bond, a substituted or an unsubstituted one They may be bonded to each other via a methylene group, an oxygen atom or a sulfur atom to form a ring).
- the present invention is also a compound having an indenobenzoazole ring structure, wherein the general formula (3) described in [3] is represented by the following general formula (4).
- Y 4 represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, a substituent
- R 7 represents a linear or branched alkenyl group having 2 to 6 carbon atoms
- X represents an oxygen atom or a sulfur atom
- R 7 and R 8 may be the same as or different from each other
- p represents an integer of 0 to 5. Is an integer of 2 or more If, Ar 4 which plurality bonded to the same benzene ring may be the same or different from each other. Further, a benzene ring and a benzene ring substituted substituent or substituents each other is more substituted in the same benzene ring, May be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring)
- the present invention is a compound having an indenobenzoazole ring structure, wherein the general formula (4) described in the claim [4] is represented by the following general formula (5).
- R 9 and R 10 may be identical to or different from each other, and may have a substituent, a linear or 1 to 6 carbon atoms, A branched alkyl group, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, or an optionally substituted linear or branched chain having 2 to 6 carbon atoms
- Ar 6 represents a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a trimethylsilyl group, a triphenylsilyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic group
- q is 2 or more.
- a plurality of Ar 6 bonded to the same benzene ring may be the same or different from each other, and a benzene ring and a substituent substituted on the benzene ring, or a plurality of substituents on the same benzene ring
- the substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring, provided that Ar 7 and Ar 8 are a hydrogen atom or a deuterium atom. Except)
- the present invention is a compound having an indenobenzoazole ring structure, wherein the general formula (5) described in [5] is represented by the following general formula (6).
- R 11 and R 12 may be the same as or different from each other, and have a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent
- a substituent Represents an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, or a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent
- Ar 9 represents deuterium Atom, fluorine atom, chlorine atom, cyano group, nitro group, trimethylsilyl group, triphenylsilyl group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensation
- Polycyclic aromatic group linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent
- Have a group or a substituent R 10 represents
- a plurality of benzene rings may be attached to the same benzene ring Ar 9 which is bonded individually may be the same as or different from each other, and the benzene ring and the substituent substituted to the benzene ring, or the substituents substituted to the same benzene ring may be a single bond, or may be substituted or absent They may be bonded to each other via a substituted methylene group, an oxygen atom or a sulfur atom to form a ring, provided that Ar 10 and Ar 11 are other than a hydrogen atom or a deuterium atom.
- the present invention provides an organic EL device having a pair of electrodes and at least one organic layer sandwiched therebetween, wherein the indenobenzoazole according to any one of the above [1] to [6].
- a compound having a ring structure is used as a constituent material of at least one organic layer.
- the present invention is the organic EL element according to the above-mentioned [7], wherein the organic layer in which the compound having the above indenobenzoazole ring structure is used is an electron transport layer.
- the present invention is also the organic EL element according to the above-mentioned [7], wherein the organic layer in which the compound having the above indenobenzoazole ring structure is used is a hole blocking layer.
- the present invention is the organic EL element according to the above-mentioned [7], wherein the organic layer in which the compound having the above indenobenzoazole ring structure is used is a light emitting layer.
- the present invention is the organic EL device according to the above [7], wherein the organic layer in which the compound having the above indenobenzoazole ring structure is used is an electron injection layer.
- a carbon atom having a substituent a “carbon atom having a substituted aromatic hydrocarbon group” represented by A 1 to A 6 in the general formulas (1) to (6), a “substituted aromatic heterocyclic group”
- Specific examples of the "substituent" of the "carbon atom having” or the “carbon atom having a substituted fused polycyclic aromatic group” include a deuterium atom, a cyano group, a nitro group; a fluorine atom, a chlorine atom, a bromine atom and an iodine Halogen atoms such as atoms; silyl groups such as trimethylsilyl group and triphenylsilyl group; linear or branched alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; methyloxy group, ethyloxy group And C 1 -C 6 linear or branched alkyloxy group such as propyloxy group; alkenyl
- Substituted or unsubstituted aromatic hydrocarbon group represented by Y 1 to Y 4 in the general formulas (1) to (4), “substituted or unsubstituted aromatic heterocyclic group”, or “substituted or unsubstituted As the “aromatic hydrocarbon group”, the “aromatic heterocyclic group” or the “fused polycyclic aromatic group” in the substituted fused polycyclic aromatic group, there can be mentioned A in the general formulas (1) to (6) 1 are represented by a 6 "aromatic hydrocarbon group", “aromatic heterocyclic group” or can be given the same as those shown with respect to the "condensed polycyclic aromatic group", also a mode which can be taken , I can mention the same thing.
- Substituted aromatic hydrocarbon group represented by Y 1 to Y 4 in the general formulas (1) to (4), “substituted aromatic heterocyclic group”, “substituted fused polycyclic aromatic group”, “substituted A linear or branched alkyl group having 1 to 6 carbon atoms which may have a group, a "cycloalkyl group having a carbon number of 5 to 10 which may have a substituent," or Examples of the “substituent” of “optionally substituted linear or branched alkenyl group having 2 to 6 carbon atoms” include A 1 to A in the general formulas (1) to (6). The same thing as what was shown regarding "substituent" represented by 6 can be mentioned, and the aspect which can take can mention the same thing.
- Substituted or unsubstituted aromatic hydrocarbon group “substituted or unsubstituted aromatic heterocyclic group” represented by Ar 1 to Ar 11 in the general formulas (1) to (6), or “substituted or unsubstituted As the “aromatic hydrocarbon group”, the “aromatic heterocyclic group” or the “fused polycyclic aromatic group” in the substituted fused polycyclic aromatic group, there can be mentioned A in the general formulas (1) to (6) 1 are represented by a 6 "aromatic hydrocarbon group", “aromatic heterocyclic group” or can be given the same as those shown with respect to the "condensed polycyclic aromatic group", also a mode which can be taken , I can mention the same thing.
- Substituted aromatic hydrocarbon group “substituted aromatic heterocyclic group”, “substituted fused polycyclic aromatic group”, “substituted” represented by Ar 1 to Ar 11 in the general formulas (1) to (6)
- a linear or branched alkyl group having 1 to 6 carbon atoms which may have a group, a "cycloalkyl group having a carbon number of 5 to 10 which may have a substituent," or Examples of the “substituent” of “optionally substituted linear or branched alkenyl group having 2 to 6 carbon atoms” include A 1 to A in the general formulas (1) to (6).
- the same thing as what was shown regarding "substituent" represented by 6 can be mentioned, and the aspect which can take can mention the same thing.
- substituents include the same ones as described for “substituents” represented by A 1 to A 6 in the general formulas (1) to (6), and the possible embodiments are also as follows: I can mention the same thing.
- the compound having an indenobenzoazole ring structure represented by the general formula (1) which is suitably used for the organic EL device of the present invention, is a compound of an electron injection layer, an electron transport layer or a hole blocking layer of an organic EL device. It can be used as a constituent material. It is a compound having high electron mobility and a preferable material of the electron injection layer or the electron transport layer.
- the organic EL device of the present invention uses a material for an organic EL device which is excellent in electron injection / transport performance, thin film stability and durability, it can be seen from the electron transport layer as compared with the conventional organic EL device.
- the electron transport efficiency to the light emitting layer is improved, the light emission efficiency is improved, the driving voltage is lowered, and the durability of the organic EL element can be improved. It has become possible to realize organic EL devices with high efficiency, low drive voltage, and long life.
- the organic EL device of the present invention efficiently injects electrons from the electron transport layer to the light emitting layer by selecting a compound having a specific indenobenzoazole ring structure capable of effectively expressing the role of electron injection / transport
- a compound having a specific indenobenzoazole ring structure capable of effectively expressing the role of electron injection / transport
- the luminous efficiency, the driving voltage, and the durability of the conventional organic EL element can be improved.
- FIG. 2 shows the structures of Exemplary Compound 1 to Exemplary Compound 15 of the present invention.
- FIG. 2 shows the structures of Exemplary Compound 16 to Exemplary Compound 30 of the present invention.
- FIG. 16 shows the structures of Exemplary Compound 31 to Exemplary Compound 45 of the present invention.
- FIG. 17 shows the structures of Exemplary Compound 46 to Exemplary Compound 60 of the present invention.
- FIG. 17 shows the structures of Exemplary Compound 61 to Exemplary Compound 74 of the present invention.
- FIG. 31 shows the structures of Exemplary Compound 75 to Exemplary Compound 89 of the present invention.
- FIG. 16 shows structures of Exemplary Compound 90 to Exemplary Compound 107 of the present invention.
- FIG. 16 shows structures of Exemplary Compound 108 to Exemplary Compound 122 of the present invention.
- FIG. 16 shows the structures of Exemplary Compound 123 to Exemplary Compound 137 of the present invention.
- FIG. 16 shows the structures of Exemplary Compound 138 to Exemplary Compound 152 of the present invention.
- FIG. 16 shows the structures of Exemplary Compound 153 to Exemplary Compound 167 of the present invention.
- FIG. 16 shows structures of Exemplary Compound 168 to Exemplary Compound 176 of the present invention. It is the figure which showed the organic EL element structure of Examples 6-8 and Comparative Examples 1-3.
- the compounds having a benzoazole ring structure of the present invention are novel compounds. These compounds can be synthesized, for example, according to methods known per se as follows (see, for example, Patent Documents 5 and 6, Non-patent Documents 6 and 7).
- Purification of the compound having an indenobenzoazole ring structure represented by the general formulas (1) to (6) is purification by column chromatography, adsorption purification with silica gel, activated carbon, activated clay or the like, recrystallization or crystallization method with a solvent , Sublimation purification method and the like. Identification of the compounds was performed by NMR analysis. Melting point, glass transition point (Tg) and work function were measured as physical property values. The melting point is an index of vapor deposition property, the glass transition point (Tg) is an index of stability of the thin film state, and the work function is an index of hole transporting property or hole blocking property.
- the melting point and the glass transition point (Tg) were measured with a powder using a high sensitivity differential scanning calorimeter (DSC3100SA, manufactured by Bruker AXS).
- the work function was obtained by preparing a thin film of 100 nm on an ITO substrate and using an ionization potential measurement device (PYS-202, manufactured by Sumitomo Heavy Industries, Ltd.).
- the structure of the organic EL device of the present invention comprises, in order on the substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode, and hole transport.
- Those having an electron blocking layer between the layer and the light emitting layer and those having a hole blocking layer between the light emitting layer and the electron transport layer can be mentioned.
- a structure which combines a hole injection layer and a hole transport layer a structure which combines an electron injection layer and an electron transport layer It can also be done.
- an electrode material having a large work function such as ITO or gold is used.
- a hole injection layer of the organic EL device of the present invention in addition to a porphyrin compound represented by copper phthalocyanine, a starburst type triphenylamine derivative, having two or more triphenylamine structures or carbazolyl structures in the molecule,
- an acceptor heterocyclic compound such as hexacyanoazatriphenylene or a coated polymer material may be used. it can.
- These materials can be formed into a thin film by a known method such as a spin coat method or an ink jet method other than the vapor deposition method.
- NPD N, N'-diphenyl-N, N'-di (m-tolyl) -benzidine
- NPD N, N'-diphenyl-N Benzidine derivatives such as N, N'-di ( ⁇ -naphthyl) -benzidine (hereinafter abbreviated as NPD), N, N, N ', N'-tetrabiphenylyl benzidine, 1,1-bis [(di-4) -Tolylamino) phenyl] cyclohexane (hereinafter abbreviated as TAPC), a molecule having two or more triphenylamine structures or carbazolyl structures in the molecule, each of which is a single bond or a divalent group having no hetero atom
- TAPC 1,1-bis [(di-4) -Tolylamino) phenyl] cyclohexane
- PEDOT poly (3,4-ethylenedioxythiophene)
- PSS poly (styrene sulfonate)
- a material in which trisbromophenylamine hexachloroantimony, a radialene derivative is further P-doped to a material usually used in the layer, A high molecular compound having a structure of a benzidine derivative such as TPD in its partial structure can be used.
- TCTA 4,4 ′, 4 ′ ′-tri (N-carbazolyl) triphenylamine
- TCTA 9,9-bis [4- (carbazole-) 9-yl) phenyl] fluorene
- mCP 1,3-bis (carbazol-9-yl) benzene
- Ad 2,2-bis (4-carbazol-9-ylphenyl) adamantane
- triphenylsilyl groups represented by 9- [4- (carbazol-9-yl) phenyl] -9- [4- (triphenylsilyl) phenyl] -9H-fluorene.
- compounds having electron blocking activity such as compounds having a triarylamine structure.
- these may be formed separately, they may be used as a single layer formed by mixing with other materials, and layers formed separately by the above plurality of materials may be used together by the above plurality of materials.
- a stacked structure of layers formed by mixing and forming a film or layers formed by mixing and forming a single film of the above plurality of materials may be employed. These materials can be formed into a thin film by a known method such as a spin coat method or an ink jet method other than the vapor deposition method.
- the light emitting layer of the organic EL device of the present invention in addition to the metal complex of quinolinol derivative including Alq 3 in addition to the compound having the indenobenzoazole ring structure of the present invention, various metal complexes, anthracene derivative, bisstyryl Benzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives and the like can be used.
- the light emitting layer may be composed of a host material and a dopant material. Anthracene derivative is preferably used as the host material, but the light emission including the compound having an indenobenzoazole ring structure of the present invention.
- a heterocyclic compound having an indole ring as a partial structure of a condensed ring a heterocyclic compound having a carbazole ring as a partial structure of a condensed ring, a carbazole derivative, a thiazole derivative, a benzimidazole derivative, a polydialkyl fluorene derivative, etc.
- a dopant material quinacridone, coumarin, rubrene, perylene and derivatives thereof, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives and the like can be used.
- these may be formed separately, they may be used as a single layer formed by mixing with other materials, layers formed separately by the above plural materials, and by the above plural materials
- a stacked structure of layers formed by mixing and forming a film or layers formed by mixing and forming a single film of the above plurality of materials may be employed.
- a phosphorescence material as a light emitting material.
- a phosphorescence light emitter a phosphorescence light emitter of metal complex such as iridium and platinum can be used.
- a green phosphor such as Ir (ppy) 3
- a blue phosphor such as FIrpic or FIr 6
- a red phosphor such as Btp 2 Ir (acac), or the like may be used as the host material.
- CBP 4,4'-di (N-carbazolyl) biphenyl
- carbazole derivatives such as TCTA and mCP
- CBP 4,4'-di (N-carbazolyl) biphenyl
- carbazole derivatives such as TCTA and mCP
- UGH2 triphenylsilyl
- a -1H-benzimidazole) hereinafter abbreviated as TPBI
- TPBI -1H-benzimidazole
- Non-Patent Document 3 a material that emits delayed fluorescence such as PICCB, such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN, as a light-emitting material.
- PICCB a material that emits delayed fluorescence
- CC2TA a material that emits delayed fluorescence
- PXZ-TRZ a material that emits delayed fluorescence
- 4CzIPN a material that emits delayed fluorescence
- These materials can be thin film-formed by a known method such as a spin coating method or an inkjet method in addition to the vapor deposition method.
- phenanthroline derivatives such as vasocuproin (hereinafter abbreviated as BCP) and metals of quinolinol derivatives such as BAlq
- BCP vasocuproin
- metals of quinolinol derivatives such as BAlq
- various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, and other compounds having a hole blocking function can be used. These materials may double as the material of the electron transport layer. Although these may be formed separately, they may be used as a single layer formed by mixing with other materials, and layers formed separately by the above plurality of materials may be used together by the above plurality of materials.
- a stacked structure of layers formed by mixing and forming a film or layers formed by mixing and forming a single film of the above plurality of materials may be employed. These materials can be formed into a thin film by a known method such as a spin coat method or an ink jet method other than the vapor deposition method.
- metal complexes of quinolinol derivatives including Alq 3 and BAlq, various metal complexes, and triazole derivatives as an electron transport layer of the organic EL device of the present invention Triazine derivatives, oxadiazole derivatives, pyridine derivatives, benzimidazole derivatives, thiadiazole derivatives, anthracene derivatives, carbodiimide derivatives, quinoxaline derivatives, pyridoindole derivatives, phenanthroline derivatives, silole derivatives and the like can be used.
- these may be formed separately, they may be used as a single layer formed by mixing with other materials, and layers formed separately by the above plurality of materials may be used together by the above plurality of materials.
- a stacked structure of layers formed by mixing and forming a film or layers formed by mixing and forming a single film of the above plurality of materials may be employed.
- These materials can be formed into a thin film by a known method such as a spin coat method or an ink jet method other than the vapor deposition method.
- alkali metal salts such as lithium fluoride and cesium fluoride
- alkaline earth metal salts such as magnesium fluoride
- Metal complexes of quinolinol derivatives such as lithium quinolinol
- metal oxides such as aluminum oxide, or metals such as ytterbium (Yb), samarium (Sm), calcium (Ca), strontium (Sr), cesium (Cs), etc.
- Yb ytterbium
- Sm samarium
- Ca calcium
- Cs cesium
- a material generally used in the layer may be further N-doped with a metal such as cesium.
- an electrode material having a low work function such as aluminum or an alloy having a lower work function such as a magnesium silver alloy, a magnesium indium alloy, or an aluminum magnesium alloy is used as an electrode material.
- the melting point and the glass transition point of the indenobenzoazole compound represented by the general formula (1) were measured by a high-sensitivity differential scanning calorimeter (DSC3100SA, manufactured by Bruker AXS). Melting point glass transition point Compound of Example 1 269 ° C. 136 ° C. The compound of Example 2 256 ° C 127 ° C Compound of Example 3 353 ° C 178 ° C
- the compound having an indenobenzoazole ring structure represented by the general formula (1) has a glass transition point of 100 ° C. or more, which indicates that the thin film state is stable.
- the compound having an indenobenzoazole ring structure represented by the general formula (1) has a work function larger than the work function 5.5 eV of general hole transport materials such as NPD and TPD, and a large hole Has a blocking ability.
- the organic EL device has a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, and a hole blocking layer on an ITO electrode previously formed as a transparent anode 2 on a glass substrate 1.
- the layer 6, the electron transport layer 7, the electron injection layer 8, and the cathode (aluminum electrode) 9 were sequentially deposited and manufactured.
- the glass substrate 1 on which ITO having a film thickness of 50 nm was formed was subjected to ultrasonic cleaning for 20 minutes in isopropyl alcohol and then dried for 10 minutes on a hot plate heated to 200 ° C. Thereafter, UV ozone treatment was carried out for 15 minutes, and then the ITO-attached glass substrate was mounted in a vacuum deposition machine, and the pressure was reduced to 0.001 Pa or less.
- a compound (HTM-1) of the following structural formula was formed as a hole transport layer 4 to have a film thickness of 60 nm.
- Binary vapor deposition was performed at a vapor deposition rate to form a film thickness of 20 nm.
- Lithium fluoride was formed as the electron injection layer 8 to a film thickness of 1 nm on the hole blocking and electron transporting layers 6 and 7. Finally, aluminum was deposited 100 nm to form a cathode 9. The characteristics of the produced organic EL device were measured at room temperature in the air. Table 1 summarizes the measurement results of the light emission characteristics when a direct current voltage is applied to the manufactured organic EL element.
- Example 6 the compound (Compound-4) of Example 2 is used instead of the compound (Compound-105) of Example 1 of the present invention as the material of the hole blocking layer / electron transport layer 6 and 7 and the deposition rate ratio
- the characteristics of the produced organic EL device were measured in the air at normal temperature. Table 1 summarizes the measurement results of the light emission characteristics when a direct current voltage is applied to the manufactured organic EL element.
- the device life was measured using the organic EL devices produced in Examples 6 to 8 and Comparative Examples 1 to 3, and the results are shown in Table 1.
- the device life is equivalent to 95% when the light emission luminance is 1900 cd / m 2 (when the initial luminance is 100% when constant current driving is performed with the light emission luminance at the start of light emission (initial luminance) 2000 cd / m 2 : The time to decay to 95%) was measured.
- the driving voltage when a current having a current density of 10 mA / cm 2 is applied is 3.81 of the organic EL elements of Comparative Examples 1 to 3 using the compounds ETM-2 to 4 of the above structural formula.
- the voltage was lowered to 3.37 to 3.60 V with respect to ⁇ 4.05 V.
- the luminous efficiency is improved to 8.58 to 8.87 cd / A for the organic EL devices of Examples 6 to 8 as compared with 7.40 to 7.68 cd / A for the organic EL devices of Comparative Examples 1 to 3.
- the organic EL devices of Examples 6 to 8 are as large as 7.48 to 8.14 lm / W, compared with 5.96 to 6.30 lm / W of the organic EL devices of Comparative Examples 1 to 3. Improved.
- the organic EL elements of Examples 6 to 8 greatly extend the life to 129 to 149 hours, compared with 35 to 55 hours for the organic EL elements of Comparative Examples 1 to 3. There is.
- the organic EL device of the present invention is superior to the devices using the compounds ETM-2 to 4 of the above structural formula in luminous efficiency and power efficiency, and can realize an organic EL device having a long life. all right.
- the compound having a specific indenobenzoazole ring structure of the present invention is excellent as a compound for an organic EL device because it has good electron injection characteristics, excellent hole blocking ability, and stable thin film state. There is.
- By manufacturing an organic EL element using the compound high efficiency can be obtained, driving voltage can be reduced, and durability can be improved. For example, it has become possible to expand to home appliances and lighting applications.
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Abstract
[Problem] The purpose of the present invention is to provide, as a material for an organic EL element having high efficiency and high durability, an organic compound having excellent electron injection and transportation performance, capability to block positive holes, and excellent characteristics which are highly stable in a thin-film form, and in addition, to provide an organic EL element having high efficiency and high durability using the compound. [Solution] This compound has an indenobenzoazole-ring structure represented by general formula (1). (In the formula, A1-A4 may be the same or different and each represent a carbon atom having a hydrogen atom, a deuterium atom, or a substituent, a carbon atom having a substituted or unsubstituted aromatic hydrocarbon group, a carbon atom having a substituted or unsubstituted aromatic heterocyclic group, a carbon atom having a substituted or unsubstituted condensed polycyclic aromatic group, or a nitrogen atom, Y1 represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, an optionally substituted straight-chain or branched alkyl group having 1-6 carbon atoms, an optionally substituted cycloalkyl group having 5-10 carbon atoms, or an optionally substituted straight-chain or branched alkenyl group having 2-6 carbon atoms, and X represents an oxygen atom or a sulfur atom, provided that one site between adjacent carbon atoms of A1-A4 is represented by structural formula (A-1)).
Description
本発明は、各種の表示装置に好適な自発光素子である有機エレクトロルミネッセンス素子（以下、有機ＥＬ素子と略称する）に適した化合物と素子に関するものであリ、詳しくはベンゾアゾール環構造を有する化合物と、該化合物を用いた有機ＥＬ素子に関するものである。
The present invention relates to a compound and an element suitable for an organic electroluminescent element (hereinafter referred to as an organic EL element) which is a self-emission element suitable for various display devices, and more specifically, to have a benzoazole ring structure The present invention relates to a compound and an organic EL device using the compound.
有機ＥＬ素子は自己発光性素子であるため、液晶素子に比べて明るく視認性に優れ、鮮明な表示が可能であることから、活発な研究がなされてきた。
Since the organic EL element is a self light emitting element, it is brighter than the liquid crystal element and has excellent visibility and clear display, and therefore, active research has been conducted.
１９８７年にイーストマン・コダック社のＣ．Ｗ．Ｔａｎｇらは各種の役割を各材料に分担した積層構造素子を開発することにより有機材料を用いた有機ＥＬ素子を実用的なものにした。彼らは電子を輸送することのできる蛍光体と正孔を輸送することのできる有機物とを積層し、両方の電荷を蛍光体の層の中に注入して発光させることにより、１０Ｖ以下の電圧で１０００ｃｄ／ｍ２以上の高輝度が得られるようになった（例えば、特許文献１および特許文献２参照）。
In 1987, Eastman Kodak Company C.I. W. Tang et al. Made the organic EL device using the organic material practical by developing a laminated structure device in which various functions are shared by the respective materials. They stack phosphors capable of transporting electrons and organic substances capable of transporting holes, and inject both charges into the phosphor layer to emit light, with a voltage of 10 V or less A high luminance of 1000 cd / m 2 or more can be obtained (see, for example, Patent Document 1 and Patent Document 2).
現在まで、有機ＥＬ素子の実用化のために多くの改良がなされ、積層構造の各種の役割をさらに細分化して、基板上に順次に、陽極、正孔注入層、正孔輸送層、発光層、電子輸送層、電子注入層、陰極を設けた電界発光素子によって高効率と耐久性が達成されるようになってきた（例えば、非特許文献1参照）。
Until now, many improvements have been made for the practical use of organic EL elements, and the various roles of the laminated structure are further subdivided, and an anode, a hole injection layer, a hole transport layer, a light emitting layer are sequentially formed on the substrate. High efficiency and durability have been achieved by an electroluminescent device provided with an electron transport layer, an electron injection layer, and a cathode (see, for example, Non-Patent Document 1).
また、発光効率の更なる向上を目的として三重項励起子の利用が試みられ、燐光発光性化合物の利用が検討されている（例えば、非特許文献２参照）。
そして、熱活性化遅延蛍光（ＴＡＤＦ）による発光を利用する素子も開発されている。２０１１年に九州大学の安達らは、熱活性化遅延蛍光材料を用いた素子によって５．３％の外部量子効率を実現させた。（例えば、非特許文献３参照） In addition, utilization of triplet excitons has been attempted for the purpose of further improvement of luminous efficiency, and utilization of phosphorescent compounds has been studied (see, for example, Non-Patent Document 2).
And, an element utilizing light emission by thermally activated delayed fluorescence (TADF) has also been developed. In 2011, Adachi et al. Of Kyushu University realized an external quantum efficiency of 5.3% by a device using a thermally activated delayed fluorescent material. (For example, refer to Non-Patent Document 3)
そして、熱活性化遅延蛍光（ＴＡＤＦ）による発光を利用する素子も開発されている。２０１１年に九州大学の安達らは、熱活性化遅延蛍光材料を用いた素子によって５．３％の外部量子効率を実現させた。（例えば、非特許文献３参照） In addition, utilization of triplet excitons has been attempted for the purpose of further improvement of luminous efficiency, and utilization of phosphorescent compounds has been studied (see, for example, Non-Patent Document 2).
And, an element utilizing light emission by thermally activated delayed fluorescence (TADF) has also been developed. In 2011, Adachi et al. Of Kyushu University realized an external quantum efficiency of 5.3% by a device using a thermally activated delayed fluorescent material. (For example, refer to Non-Patent Document 3)
発光層は、一般的にホスト材料と称される電荷輸送性の化合物に、蛍光性化合物や燐光発光性化合物または遅延蛍光を放射する材料をドープして作製することもできる。前記非特許文献に記載されているように、有機ＥＬ素子における有機材料の選択は、その素子の効率や耐久性など諸特性に大きな影響を与える。（例えば、非特許文献２参照）
The light emitting layer can also be produced by doping a charge transporting compound generally called a host material with a fluorescent compound, a phosphorescent compound, or a material that emits delayed fluorescence. As described in the non-patent document, the selection of the organic material in the organic EL element has a great influence on various characteristics such as the efficiency and durability of the element. (For example, refer to Non-Patent Document 2)
有機ＥＬ素子においては、両電極から注入された電荷が発光層で再結合して発光が得られるが、正孔、電子の両電荷を如何に効率良く発光層に受け渡すかが重要である。
電子注入性を高め、その移動度を高め、更に陽極から注入された正孔をブロックする正孔阻止性を高め、正孔と電子が再結合する確率を向上させ、更に発光層内で生成した励起子を閉じ込めることによって、高効率発光を得ることができる。そのため電子輸送材料の果たす役割は重要であり、電子注入性が高く、電子移動度が大きく、正孔阻止性が高く、さらには正孔に対する耐久性が高い電子輸送材料が求められている。 In the organic EL element, although the charge injected from both electrodes is recombined in the light emitting layer to obtain light emission, it is important how efficiently both holes and electrons are transferred to the light emitting layer.
The electron injection property is enhanced, the mobility is increased, the hole blocking property for blocking holes injected from the anode is further enhanced, and the probability that holes and electrons recombine is improved, and further generated in the light emitting layer By trapping the excitons, high efficiency light emission can be obtained. Therefore, the role of the electron transport material is important, and there is a demand for an electron transport material having high electron injection property, high electron mobility, high hole blocking property, and high durability to holes.
電子注入性を高め、その移動度を高め、更に陽極から注入された正孔をブロックする正孔阻止性を高め、正孔と電子が再結合する確率を向上させ、更に発光層内で生成した励起子を閉じ込めることによって、高効率発光を得ることができる。そのため電子輸送材料の果たす役割は重要であり、電子注入性が高く、電子移動度が大きく、正孔阻止性が高く、さらには正孔に対する耐久性が高い電子輸送材料が求められている。 In the organic EL element, although the charge injected from both electrodes is recombined in the light emitting layer to obtain light emission, it is important how efficiently both holes and electrons are transferred to the light emitting layer.
The electron injection property is enhanced, the mobility is increased, the hole blocking property for blocking holes injected from the anode is further enhanced, and the probability that holes and electrons recombine is improved, and further generated in the light emitting layer By trapping the excitons, high efficiency light emission can be obtained. Therefore, the role of the electron transport material is important, and there is a demand for an electron transport material having high electron injection property, high electron mobility, high hole blocking property, and high durability to holes.
また、素子の寿命に関しては材料の耐熱性やアモルファス性も重要である。耐熱性が低い材料では、素子駆動時に生じる熱により、低い温度でも熱分解が起こり、材料が劣化する。アモルファス性が低い材料では、短い時間でも薄膜の結晶化が起こり、素子が劣化してしまう。そのため使用する材料には耐熱性が高く、アモルファス性が良好な性質が求められる。
Further, the heat resistance and the amorphous property of the material are also important with respect to the lifetime of the element. In materials with low heat resistance, the heat generated at the time of device operation causes thermal decomposition even at low temperatures, and the materials deteriorate. In a material with low amorphousness, crystallization of a thin film occurs even for a short time, and the device is degraded. Therefore, the material to be used is required to have high heat resistance and good amorphousness.
代表的な発光材料であるトリス（８－ヒドロキシキノリン）アルミニウム（以後、Ａｌｑ３と略称する）は電子輸送材料としても一般的に用いられるが、電子移動が遅く、また仕事関数が５．６ｅＶなので正孔阻止性能が十分とは言えない。
A typical light emitting material tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq3) is generally used also as an electron transport material, but its electron transfer is slow, and its work function is 5.6 eV, so it is positive. The hole blocking performance is not sufficient.
電子注入性や移動度などの特性を改良した化合物として、ベンゾトリアゾール構造を有する化合物が提案されているが（例えば、特許文献３）、これらの化合物をまたは電子輸送層に用いた素子では、発光効率などの改良はされているものの、未だ十分とはいえず、さらなる低駆動電圧化や、さらなる高発光効率化が求められている。
Although compounds having a benzotriazole structure have been proposed as compounds having improved properties such as electron injection properties and mobility (for example, Patent Document 3), in devices using these compounds or in an electron transport layer, light emission is obtained. Although improvements in efficiency and the like have been made, it is not sufficient yet, and further reduction in drive voltage and further improvement in luminous efficiency are required.
また、正孔阻止性に優れた電子輸送材料として、３－（４－ビフェニリル）－４－フェニル－５－（４－ｔ－ブチルフェニル）－１，２，４－トリアゾール（以後、ＴＡＺと略称する）が提案されている（例えば、特許文献４参照）。
Further, 3- (4-biphenylyl) -4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole (hereinafter abbreviated as TAZ) as an electron transporting material excellent in hole blocking properties Have been proposed (see, for example, Patent Document 4).
ＴＡＺは仕事関数が６．６ｅＶと大きく正孔阻止能力が高いために、真空蒸着や塗布などによって作製される蛍光発光層や燐光発光層の、陰極側に積層する電子輸送性の正孔阻止層として使用され、有機ＥＬ素子の高効率化に寄与している（例えば、非特許文献４参照）。
Since TAZ has a large work function of 6.6 eV and high hole blocking ability, it has an electron-transporting hole blocking layer laminated on the cathode side of a fluorescent light emitting layer or a phosphorescent light emitting layer prepared by vacuum deposition or coating. And contributes to high efficiency of the organic EL element (see, for example, Non-Patent Document 4).
しかし電子輸送性が低いことがＴＡＺにおける大きな課題であり、より電子輸送性の高い電子輸送材料と組み合わせて、有機ＥＬ素子を作製することが必要であった（例えば、非特許文献５参照）。
However, low electron transportability is a major issue in TAZ, and it has been necessary to produce an organic EL device in combination with an electron transport material having higher electron transportability (see, for example, Non-Patent Document 5).
また、ＢＣＰにおいても仕事関数が６．７ｅＶと大きく正孔阻止能力が高いものの、ガラス転移点(Ｔｇ)が８３℃と低いことから、薄膜の安定性に乏しく、正孔阻止層として十分に機能しているとは言えない。
In addition, although BCP has a large work function of 6.7 eV and high hole blocking ability, it has a low glass transition point (Tg) of 83 ° C., so the thin film lacks stability and functions sufficiently as a hole blocking layer. I can not say that.
いずれの材料も膜安定性が不足しており、もしくは正孔を阻止する機能が不十分である。有機ＥＬ素子の素子特性を改善させるために、電子の注入・輸送性能と正孔阻止能力に優れ、薄膜状態での安定性が高い有機化合物が求められている。
Both materials have poor film stability or have insufficient hole blocking function. In order to improve the device characteristics of the organic EL device, an organic compound which is excellent in electron injection / transport performance and hole blocking ability and has high stability in a thin film state is required.
本発明の目的は高効率、高耐久性の有機ＥＬ素子用材料として、電子注入・輸送性能に優れ、正孔阻止能力を有し、薄膜状態での安定性が高い優れた特性を有する有機化合物を提供し、更にこの化合物を用いて、高効率、高耐久性の有機ＥＬ素子を提供することにある。
An object of the present invention is an organic compound having excellent electron injection / transport performance, hole blocking ability, and excellent stability in a thin film state as a material for organic EL devices having high efficiency and high durability. It is another object of the present invention to provide a highly efficient and highly durable organic EL device using this compound.
本発明が提供しようとする有機化合物が具備すべき物理的な特性としては、（１）電子の注入特性が良いこと、（２）電子の移動度が大きいこと、（３）正孔阻止能力に優れること、（４）薄膜状態が安定であること、（５）耐熱性に優れていることをあげることができる。また、本発明が提供しようとする有機ＥＬ素子が具備すべき物理的な特性としては、（１）発光効率および電力効率が高いこと、（２）発光開始電圧が低いこと、（３）実用駆動電圧が低いこと、（４）長寿命であること、をあげることができる。
The physical properties that the organic compound to be provided by the present invention should have include (1) good electron injection characteristics, (2) high electron mobility, and (3) hole blocking ability. It can be mentioned that it is excellent, (4) that the thin film state is stable, and (5) that it is excellent in heat resistance. Further, the physical characteristics that the organic EL element to be provided by the present invention should have include (1) high luminous efficiency and high power efficiency, (2) low luminous initiation voltage, and (3) practical driving The low voltage and (4) long life can be mentioned.
そこで本発明者らは上記の目的を達成するために、電子親和性であるベンゾアゾール環の窒素原子が金属に配位する能力を有していることと、耐熱性に優れているということに着目して、ベンゾアゾール環構造を有する化合物を設計して化学合成し、該化合物を用いて種々の有機ＥＬ素子を試作し、素子の特性評価を鋭意行なった結果、本発明を完成するに至った。
Therefore, in order to achieve the above object, the present inventors have the ability to coordinate the nitrogen atom of the benzoazole ring having electron affinity to a metal and the excellent heat resistance. Pay attention to designing and chemically synthesizing a compound having a benzoazole ring structure, and trial manufacture of various organic EL devices using the compound, and as a result of earnestly evaluating the characteristics of the device, the present invention is completed. The
［１］すなわち本発明は、下記一般式（１）で表される、インデノベンゾアゾール環構造を有する化合物である。
[1] That is, the present invention is a compound represented by the following general formula (1) and having an indenobenzoazole ring structure.
（式中、Ａ１～Ａ４は相互に同一でも異なっていてもよく、水素原子、重水素原子もしくは置換基を有する炭素原子、置換もしくは無置換の芳香族炭化水素基を有する炭素原子、置換もしくは無置換の芳香族複素環基を有する炭素原子、置換もしくは無置換の縮合多環芳香族基を有する炭素原子、または窒素原子を表し、Ｙ１は水素原子、重水素原子、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ｘは酸素原子または硫黄原子を表す。但し、Ａ１～Ａ４の内、隣接し合う炭素原子の１カ所を下記構造式（Ａ－１）とする。）
(Wherein, A 1 to A 4 may be the same as or different from each other, and are a hydrogen atom, a deuterium atom or a carbon atom having a substituent, a carbon atom having a substituted or unsubstituted aromatic hydrocarbon group, a substitution Or a carbon atom having a non-substituted aromatic heterocyclic group, a carbon atom having a substituted or non-substituted fused polycyclic aromatic group, or a nitrogen atom, and Y 1 represents a hydrogen atom, a deuterium atom, a substituted or non-substituted Aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted fused polycyclic aromatic group, linear group having 1 to 6 carbon atoms which may have a substituent Or a branched alkyl group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a linear or branched chain having 2 to 6 carbon atoms which may have a substituent Represents an alkenyl group of Represents an oxygen atom or a sulfur atom, provided that one of the adjacent carbon atoms among A 1 to
（式中、破線部を結合部位とし、Ｒ１、Ｒ２は相互に同一でも異なっていてもよく、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ１は重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、トリメチルシリル基、トリフェニルシリル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、ｍは０～５の整数を表す。ｍが２以上の整数である場合、同一のベンゼン環に複数個結合するＡｒ１は相互に同一でも異なってもよい。また、ベンゼン環とベンゼン環に置換された置換基、または同一のベンゼン環に複数置換された置換基同士が、単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成してもよい。）
(Wherein, the broken line is a bonding site, and R 1 and
［２］また本発明は、［１］記載の前記一般式（１）が下記一般式（２）で表される、インデノベンゾアゾール環構造を有する化合物である。
[2] The present invention is also a compound having an indenobenzoazole ring structure, wherein the general formula (1) described in [1] is represented by the following general formula (2).
（式中、Ａ５、Ａ６は相互に同一でも異なっていてもよく、水素原子、重水素原子もしくは置換基を有する炭素原子、置換もしくは無置換の芳香族炭化水素基を有する炭素原子、置換もしくは無置換の芳香族複素環基を有する炭素原子、置換もしくは無置換の縮合多環芳香族基を有する炭素原子、または窒素原子を表し、Ｙ２は水素原子、重水素原子、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ｘは酸素原子または硫黄原子を表し、Ｒ３、Ｒ４は相互に同一でも異なっていてもよく、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ２は重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、トリメチルシリル基、トリフェニルシリル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、ｎは０～５の整数を表す。ｎが２以上の整数である場合、同一のベンゼン環に複数個結合するＡｒ２は相互に同一でも異なってもよい。また、ベンゼン環とベンゼン環に置換された置換基、または同一のベンゼン環に複数置換された置換基同士が、単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成してもよい。）
(Wherein,
［３］また本発明は、［２］記載の前記一般式（２）が下記一般式（３）で表される、インデノベンゾアゾール環構造を有する化合物。
[3] The present invention is also a compound having an indenobenzoazole ring structure, wherein the general formula (2) described in [2] is represented by the following general formula (3).
（式中、Ａ７、Ａ８は相互に同一でも異なっていてもよく、水素原子、重水素原子もしくは置換基を有する炭素原子、置換もしくは無置換の芳香族炭化水素基を有する炭素原子、置換もしくは無置換の芳香族複素環基を有する炭素原子、または置換もしくは無置換の縮合多環芳香族基を有する炭素原子を表し、Ｙ３は水素原子、重水素原子、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ｘは酸素原子または硫黄原子を表し、Ｒ５、Ｒ６は相互に同一でも異なっていてもよく、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ３は重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、トリメチルシリル基、トリフェニルシリル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、ｏは０～５の整数を表す。ｏが２以上の整数である場合、同一のベンゼン環に複数個結合するＡｒ３は相互に同一でも異なってもよい。また、ベンゼン環とベンゼン環に置換された置換基、または同一のベンゼン環に複数置換された置換基同士が、単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成してもよい。）
(Wherein, A 7 and A 8 may be identical to or different from each other, and are a hydrogen atom, a deuterium atom or a carbon atom having a substituent, a carbon atom having a substituted or unsubstituted aromatic hydrocarbon group, a substitution Or a carbon atom having a substituted or unsubstituted aromatic heterocyclic group, or a carbon atom having a substituted or unsubstituted fused polycyclic aromatic group, and Y 3 represents a hydrogen atom, a deuterium atom, or a substituted or unsubstituted aromatic group A hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, an optionally substituted linear or
［４］また本発明は、［３］記載の前記一般式（３）が下記一般式（４）で表される、インデノベンゾアゾール環構造を有する化合物である。
[4] The present invention is also a compound having an indenobenzoazole ring structure, wherein the general formula (3) described in [3] is represented by the following general formula (4).
（式中、Ｙ４は水素原子、重水素原子、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ｘは酸素原子または硫黄原子を表し、Ｒ７、Ｒ８は相互に同一でも異なっていてもよく、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ４は重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、トリメチルシリル基、トリフェニルシリル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ５水素原子、重水素原子、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表し、ｐは０～５の整数を表す。ｐが２以上の整数である場合、同一のベンゼン環に複数個結合するＡｒ４は相互に同一でも異なってもよい。また、ベンゼン環とベンゼン環に置換された置換基、または同一のベンゼン環に複数置換された置換基同士が、単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成してもよい。）
(Wherein Y 4 represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, a substituent A linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a substituent R 7 represents a linear or branched alkenyl group having 2 to 6 carbon atoms, X represents an oxygen atom or a sulfur atom, and R 7 and R 8 may be the same as or different from each other; A linear or branched alkyl group having 1 to 6 carbon atoms which may have, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a substituent A straight or branched chain having 2 to 6 carbon atoms Represents an alkenyl group, and Ar 4 represents a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a trimethylsilyl group, a triphenylsilyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic group A heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a substituent A cycloalkyl group having 5 to 10 carbon atoms, or a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, Ar 5 hydrogen atom, deuterium atom Represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted fused polycyclic aromatic group, and p represents an integer of 0 to 5. p represents an integer of 0 to 5. Is an integer of 2 or more If, Ar 4 which plurality bonded to the same benzene ring may be the same or different from each other. Further, a benzene ring and a benzene ring substituted substituent or substituents each other is more substituted in the same benzene ring, May be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring)
［５］また本発明は、請求項［４］記載の前記一般式（４）が下記一般式（５）で表される、インデノベンゾアゾール環構造を有する化合物。
[5] Further, the present invention is a compound having an indenobenzoazole ring structure, wherein the general formula (4) described in the claim [4] is represented by the following general formula (5).
（式中、Ｘは酸素原子または硫黄原子を表し、Ｒ９、Ｒ１０は相互に同一でも異なっていてもよく、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ６は重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、トリメチルシリル基、トリフェニルシリル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ７、Ａｒ８は相互に同一でも異なっていてもよく、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表し、ｑは０～５の整数を表す。ｑが２以上の整数である場合、同一のベンゼン環に複数個結合するＡｒ６は相互に同一でも異なってもよい。また、ベンゼン環とベンゼン環に置換された置換基、または同一のベンゼン環に複数置換された置換基同士が、単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成してもよい。但し、Ａｒ７、Ａｒ８は水素原子、重水素原子以外とする。）
(Wherein, X represents an oxygen atom or a sulfur atom, and R 9 and R 10 may be identical to or different from each other, and may have a substituent, a linear or 1 to 6 carbon atoms, A branched alkyl group, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, or an optionally substituted linear or branched chain having 2 to 6 carbon atoms Represents an alkenyl group, Ar 6 represents a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a trimethylsilyl group, a triphenylsilyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic group A heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, or a substituent Cycloal having 5 to 10 carbon atoms And a straight or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and Ar 7 and Ar 8 may be identical to or different from each other, and may be substituted or substituted Represents an unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted fused polycyclic aromatic group, q represents an integer of 0 to 5. q is 2 or more. When it is an integer, a plurality of Ar 6 bonded to the same benzene ring may be the same or different from each other, and a benzene ring and a substituent substituted on the benzene ring, or a plurality of substituents on the same benzene ring The substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring, provided that Ar 7 and Ar 8 are a hydrogen atom or a deuterium atom. Except)
［６］また本発明は、［５］記載の前記一般式（５）が下記一般式（６）で表される、インデノベンゾアゾール環構造を有する化合物。
[6] Moreover, the present invention is a compound having an indenobenzoazole ring structure, wherein the general formula (5) described in [5] is represented by the following general formula (6).
（式中、Ｒ１１、Ｒ１２は相互に同一でも異なっていてもよく、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ９は重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、トリメチルシリル基、トリフェニルシリル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ１０、Ａｒ１１は相互に同一でも異なっていてもよく、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表し、ｒは０～５の整数を表す。ｒが２以上の整数である場合、同一のベンゼン環に複数個結合するＡｒ９は相互に同一でも異なってもよい。また、ベンゼン環とベンゼン環に置換された置換基、または同一のベンゼン環に複数置換された置換基同士が、単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成してもよい。但し、Ａｒ１０、Ａｒ１１は水素原子、重水素原子以外とする。）
(Wherein, R 11 and R 12 may be the same as or different from each other, and have a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a substituent Represents an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, or a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and Ar 9 represents deuterium Atom, fluorine atom, chlorine atom, cyano group, nitro group, trimethylsilyl group, triphenylsilyl group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensation Polycyclic aromatic group, linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, cycloalkyl having 5 to 10 carbon atoms which may have a substituent Have a group or a substituent R 10 represents a linear or branched alkenyl group having 2 to 6 carbon atoms, and Ar 10 and Ar 11 may be the same as or different from each other, and are substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted Represents an unsubstituted aromatic heterocyclic group or a substituted or unsubstituted fused polycyclic aromatic group, and r represents an integer of 0 to 5. When r is an integer of 2 or more, a plurality of benzene rings may be attached to the same benzene ring Ar 9 which is bonded individually may be the same as or different from each other, and the benzene ring and the substituent substituted to the benzene ring, or the substituents substituted to the same benzene ring may be a single bond, or may be substituted or absent They may be bonded to each other via a substituted methylene group, an oxygen atom or a sulfur atom to form a ring, provided that Ar 10 and Ar 11 are other than a hydrogen atom or a deuterium atom.
［７］また、本発明は、一対の電極とその間に挟まれた少なくとも一層の有機層を有する有機ＥＬ素子において、上記［１］～［６］のいずれか一項に記載のインデノベンゾアゾール環構造を有する化合物が、少なくとも１つの有機層の構成材料として用いられていることを特徴とする有機ＥＬ素子である。
[7] Further, the present invention provides an organic EL device having a pair of electrodes and at least one organic layer sandwiched therebetween, wherein the indenobenzoazole according to any one of the above [1] to [6]. A compound having a ring structure is used as a constituent material of at least one organic layer.
［８］また、本発明は、前記インデノベンゾアゾール環構造を有する化合物が用いられている有機層が電子輸送層である上記［７］記載の有機ＥＬ素子である。
[8] Further, the present invention is the organic EL element according to the above-mentioned [7], wherein the organic layer in which the compound having the above indenobenzoazole ring structure is used is an electron transport layer.
［９］また、本発明は、前記インデノベンゾアゾール環構造を有する化合物が用いられている有機層が正孔阻止層である上記［７］記載の有機ＥＬ素子である。
[9] The present invention is also the organic EL element according to the above-mentioned [7], wherein the organic layer in which the compound having the above indenobenzoazole ring structure is used is a hole blocking layer.
［１０］また、本発明は、前記インデノベンゾアゾール環構造を有する化合物が用いられている有機層が発光層である上記［７］記載の有機ＥＬ素子である。
[10] Further, the present invention is the organic EL element according to the above-mentioned [7], wherein the organic layer in which the compound having the above indenobenzoazole ring structure is used is a light emitting layer.
［１１）また、本発明は、前記インデノベンゾアゾール環構造を有する化合物が用いられている有機層が電子注入層である上記［７］記載の有機ＥＬ素子である。
[11] Further, the present invention is the organic EL device according to the above [7], wherein the organic layer in which the compound having the above indenobenzoazole ring structure is used is an electron injection layer.
一般式（１）～（６）中のＡ１～Ａ６で表される「置換もしくは無置換の芳香族炭化水素基を有する炭素原子」、「置換もしくは無置換の芳香族複素環基を有する炭素原子」または「置換もしくは無置換の縮合多環芳香族基を有する炭素原子」における「芳香族炭化水素基」、「芳香族複素環基」または「縮合多環芳香族基」としては、具体的に、フェニル基、ビフェニリル基、ターフェニリル基、ナフチル基、アントラセニル基、フェナントレニル基、フルオレニル基、スピロビフルオレニル基、インデニル基、ピレニル基、ペリレニル基、フルオランテニル基、トリフェニレニル基、ピリジル基、ピリミジニル基、トリアジニル基、フリル基、ピロリル基、チエニル基、キノリル基、イソキノリル基、ベンゾフラニル基、ベンゾチエニル基、インドリル基、カルバゾリル基、ベンゾオキサゾリル基、ベンゾチアゾリル基、キノキサリニル基、ベンゾイミダゾリル基、ピラゾリル基、ジベンゾフラニル基、ジベンゾチエニル基、ナフチリジニル基、フェナントロリニル基、アクリジニル基、およびカルボリニル基などの他に、炭素数６～３０からなるアリール基、または炭素数２～２０からなるヘテロアリール基から選択される。
It has “a carbon atom having a substituted or unsubstituted aromatic hydrocarbon group” represented by A 1 to A 6 in the general formulas (1) to (6), and “a substituted or unsubstituted aromatic heterocyclic group” As the "aromatic hydrocarbon group", the "aromatic heterocyclic group" or the "fused polycyclic aromatic group" in the carbon atom or the "carbon atom having a substituted or unsubstituted fused polycyclic aromatic group", Phenyl, biphenylyl, terphenylyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, spirobifluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, triphenylenyl, pyridyl , Pyrimidinyl group, triazinyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl Group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalinyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, naphthyridinyl group, phenanthrolinyl group, acridinyl group, and carborinyl group In addition to the above, the aryl group is selected from an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms.
一般式（１）～（６）中のＡ１～Ａ６で表される「置換基を有する炭素原子」、「置換芳香族炭化水素基を有する炭素原子」、「置換芳香族複素環基を有する炭素原子」または「置換縮合多環芳香族基を有する炭素原子」における「置換基」としては、具体的に、重水素原子、シアノ基、ニトロ基；フッ素原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子；トリメチルシリル基、トリフェニルシリル基などのシリル基；メチル基、エチル基、プロピル基などの炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基；メチルオキシ基、エチルオキシ基、プロピルオキシ基などの炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基；ビニル基、アリル基などのアルケニル基；フェニルオキシ基、トリルオキシ基などのアリールオキシ基；ベンジルオキシ基、フェネチルオキシ基などのアリールアルキルオキシ基；フェニル基、ビフェニリル基、ターフェニリル基、ナフチル基、アントラセニル基、フェナントレニル基、フルオレニル基、スピロビフルオレニル基、インデニル基、ピレニル基、ペリレニル基、フルオランテニル基、トリフェニレニル基などの芳香族炭化水素基もしくは縮合多環芳香族基；ピリジル基、チエニル基、フリル基、ピロリル基、キノリル基、イソキノリル基、ベンゾフラニル基、ベンゾチエニル基、インドリル基、カルバゾリル基、ベンゾオキサゾリル基、ベンゾチアゾリル基、キノキサリニル基、ベンゾイミダゾリル基、ピラゾリル基、ジベンゾフラニル基、ジベンゾチエニル基、カルボリニル基などの芳香族複素環基のような基をあげることができ、これらの置換基はさらに、前記例示した置換基が置換していても良い。また、これらの置換基と置換したベンゼン環または同一のベンゼン環に複数置換された置換基同士が単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成していてもよい。
“A carbon atom having a substituent,” a “carbon atom having a substituted aromatic hydrocarbon group” represented by A 1 to A 6 in the general formulas (1) to (6), a “substituted aromatic heterocyclic group” Specific examples of the "substituent" of the "carbon atom having" or the "carbon atom having a substituted fused polycyclic aromatic group" include a deuterium atom, a cyano group, a nitro group; a fluorine atom, a chlorine atom, a bromine atom and an iodine Halogen atoms such as atoms; silyl groups such as trimethylsilyl group and triphenylsilyl group; linear or branched alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; methyloxy group, ethyloxy group And C 1 -C 6 linear or branched alkyloxy group such as propyloxy group; alkenyl group such as vinyl group and allyl group; phenyloxy group, tolyloxy group Which aryloxy group; arylalkyloxy group such as benzyloxy group, phenethyloxy group; phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, spirobifluorenyl group, indenyl group, Aromatic hydrocarbon group such as pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group or fused polycyclic aromatic group; pyridyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzo And aromatic heterocyclic groups such as thienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalinyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, carborinyl group, etc. Una can be mentioned groups wherein the substituents Furthermore, the exemplified substituents may be substituted. Further, a benzene ring substituted with these substituents or a plurality of substituents substituted with the same benzene ring are bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring You may form.
一般式（１）～（４）中のＹ１～Ｙ４で表される「置換もしくは無置換の芳香族炭化水素基」、「置換もしくは無置換の芳香族複素環基」または「置換もしくは無置換の縮合多環芳香族基」における「芳香族炭化水素基」、「芳香族複素環基」または「縮合多環芳香族基」としては、前記一般式（１）～（６）中のＡ１～Ａ６で表される「芳香族炭化水素基」、「芳香族複素環基」または「縮合多環芳香族基」に関して示したものと同様のものをあげることができ、とりうる態様も、同様のものをあげることができる。
“Substituted or unsubstituted aromatic hydrocarbon group” represented by Y 1 to Y 4 in the general formulas (1) to (4), “substituted or unsubstituted aromatic heterocyclic group”, or “substituted or unsubstituted As the “aromatic hydrocarbon group”, the “aromatic heterocyclic group” or the “fused polycyclic aromatic group” in the substituted fused polycyclic aromatic group, there can be mentioned A in the general formulas (1) to (6) 1 are represented by a 6 "aromatic hydrocarbon group", "aromatic heterocyclic group" or can be given the same as those shown with respect to the "condensed polycyclic aromatic group", also a mode which can be taken , I can mention the same thing.
一般式（１）～（４）中のＹ１～Ｙ４で表される「置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基」、「置換基を有していてもよい炭素原子数５～１０のシクロアルキル基」、または「置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基」における「炭素原子数１～６の直鎖状もしくは分岐状のアルキル基」、「炭素原子数５～１０のシクロアルキル基」、または「炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基」としては、具体的に、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｎ－ヘキシル基、シクロペンチル基、シクロヘキシル基、１－アダマンチル基、２－アダマンチル基、ビニル基、アリル基、イソプロペニル基、および２－ブテニル基などをあげることができる。
“C1-C6 linear or branched alkyl group optionally having substituent (s)” represented by Y 1 to Y 4 in the general formulas (1) to (4), “substituted” A “C5-C10 cycloalkyl group which may have a group” or “a C2-C6 linear or branched alkenyl group which may have a substituent” A linear or branched alkyl group having 1 to 6 carbon atoms, "a cycloalkyl group having 5 to 10 carbon atoms", or a "linear or branched alkenyl group having 2 to 6 carbon atoms" Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, A cyclopentyl group, a cyclohexyl group, - adamantyl group, 2-adamantyl group, a vinyl group, an allyl group, and the like isopropenyl group, and 2-butenyl.
一般式（１）～（４）中のＹ１～Ｙ４で表される「置換芳香族炭化水素基」、「置換芳香族複素環基」、「置換縮合多環芳香族基」、「置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基」、「置換基を有していてもよい炭素原子数５～１０のシクロアルキル基」、または「置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基」における「置換基」としては、前記一般式（１）～（６）中のＡ１～Ａ６で表される「置換基」に関して示したものと同様のものをあげることができ、とりうる態様も、同様のものをあげることができる。
“Substituted aromatic hydrocarbon group” represented by Y 1 to Y 4 in the general formulas (1) to (4), “substituted aromatic heterocyclic group”, “substituted fused polycyclic aromatic group”, “substituted A linear or branched alkyl group having 1 to 6 carbon atoms which may have a group, a "cycloalkyl group having a carbon number of 5 to 10 which may have a substituent," or Examples of the “substituent” of “optionally substituted linear or branched alkenyl group having 2 to 6 carbon atoms” include A 1 to A in the general formulas (1) to (6). The same thing as what was shown regarding "substituent" represented by 6 can be mentioned, and the aspect which can take can mention the same thing.
一般式（１）～（６）中のＡｒ１～Ａｒ１１で表される「置換もしくは無置換の芳香族炭化水素基」、「置換もしくは無置換の芳香族複素環基」または「置換もしくは無置換の縮合多環芳香族基」における「芳香族炭化水素基」、「芳香族複素環基」または「縮合多環芳香族基」としては、前記一般式（１）～（６）中のＡ１～Ａ６で表される「芳香族炭化水素基」、「芳香族複素環基」または「縮合多環芳香族基」に関して示したものと同様のものをあげることができ、とりうる態様も、同様のものをあげることができる。
“Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” represented by Ar 1 to Ar 11 in the general formulas (1) to (6), or “substituted or unsubstituted As the “aromatic hydrocarbon group”, the “aromatic heterocyclic group” or the “fused polycyclic aromatic group” in the substituted fused polycyclic aromatic group, there can be mentioned A in the general formulas (1) to (6) 1 are represented by a 6 "aromatic hydrocarbon group", "aromatic heterocyclic group" or can be given the same as those shown with respect to the "condensed polycyclic aromatic group", also a mode which can be taken , I can mention the same thing.
一般式（１）～（６）中のＡｒ１～Ａｒ１１で表される「置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基」、「置換基を有していてもよい炭素原子数５～１０のシクロアルキル基」、または「置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基」における「炭素原子数１～６の直鎖状もしくは分岐状のアルキル基」、「炭素原子数５～１０のシクロアルキル基」、または「炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基」としては、前記一般式（１）～（４）中のＹ１～Ｙ４で表される「炭素原子数１～６の直鎖状もしくは分岐状のアルキル基」、「炭素原子数５～１０のシクロアルキル基」、または「炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基」に関して示したものと同様のものをあげることができ、とりうる態様も、同様のものをあげることができる。
“C1-C6 linear or branched alkyl group optionally having substituent (s)” represented by Ar 1 to Ar 11 in the general formulas (1) to (6), “substituted” A “C5-C10 cycloalkyl group which may have a group” or “a C2-C6 linear or branched alkenyl group which may have a substituent” A linear or branched alkyl group having 1 to 6 carbon atoms, "a cycloalkyl group having 5 to 10 carbon atoms", or a "linear or branched alkenyl group having 2 to 6 carbon atoms" And Y represents a linear or branched alkyl group having 1 to 6 carbon atoms represented by Y 1 to Y 4 in the general formulas (1) to (4); Or a linear or branched alkenylene having 2 to 6 carbon atoms May be mentioned those similar to that shown with respect to group ", aspects that can be taken can also be mentioned those similar.
一般式（１）～（６）中のＡｒ１～Ａｒ１１で表される「置換芳香族炭化水素基」、「置換芳香族複素環基」、「置換縮合多環芳香族基」、「置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基」、「置換基を有していてもよい炭素原子数５～１０のシクロアルキル基」、または「置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基」における「置換基」としては、前記一般式（１）～（６）中のＡ１～Ａ６で表される「置換基」に関して示したものと同様のものをあげることができ、とりうる態様も、同様のものをあげることができる。
“Substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group”, “substituted fused polycyclic aromatic group”, “substituted” represented by Ar 1 to Ar 11 in the general formulas (1) to (6) A linear or branched alkyl group having 1 to 6 carbon atoms which may have a group, a "cycloalkyl group having a carbon number of 5 to 10 which may have a substituent," or Examples of the “substituent” of “optionally substituted linear or branched alkenyl group having 2 to 6 carbon atoms” include A 1 to A in the general formulas (1) to (6). The same thing as what was shown regarding "substituent" represented by 6 can be mentioned, and the aspect which can take can mention the same thing.
一般式（１）～（６）中のＲ１～Ｒ１２で表される「置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基」、「置換基を有していてもよい炭素原子数５～１０のシクロアルキル基」、または「置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基」における「炭素原子数１～６の直鎖状もしくは分岐状のアルキル基」、「炭素原子数５～１０のシクロアルキル基」、または「炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基」としては、前記一般式（１）～（４）中のＹ１～Ｙ４で表される「炭素原子数１～６の直鎖状もしくは分岐状のアルキル基」、「炭素原子数５～１０のシクロアルキル基」、または「炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基」に関して示したものと同様のものをあげることができ、とりうる態様も、同様のものをあげることができる。
“C1-C6 linear or branched alkyl group optionally having substituent (s)” represented by R 1 to R 12 in the general formulas (1) to (6), “substituted” A “C5-C10 cycloalkyl group which may have a group” or “a C2-C6 linear or branched alkenyl group which may have a substituent” A linear or branched alkyl group having 1 to 6 carbon atoms, "a cycloalkyl group having 5 to 10 carbon atoms", or a "linear or branched alkenyl group having 2 to 6 carbon atoms" And Y represents a linear or branched alkyl group having 1 to 6 carbon atoms represented by Y 1 to Y 4 in the general formulas (1) to (4); Or a linear or branched alkenyl group having 2 to 6 carbon atoms May be mentioned those similar to that shown with respect to, aspects that can be taken can also be mentioned those similar.
一般式（１）～（６）中のＲ１～Ｒ１２で表される「置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基」、「置換基を有していてもよい炭素原子数５～１０のシクロアルキル基」、または「置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基」における「置換基」としては、前記一般式（１）～（６）中のＡ１～Ａ６で表される「置換基」に関して示したものと同様のものをあげることができ、とりうる態様も、同様のものをあげることができる。
“C1-C6 linear or branched alkyl group optionally having substituent (s)” represented by R 1 to R 12 in the general formulas (1) to (6), “substituted” A “C5-C10 cycloalkyl group which may have a group” or “a C2-C6 linear or branched alkenyl group which may have a substituent” Examples of the “substituent” include the same ones as described for “substituents” represented by A 1 to A 6 in the general formulas (1) to (6), and the possible embodiments are also as follows: I can mention the same thing.
本発明の有機ＥＬ素子に好適に用いられる、前記一般式（１）で表されるインデノベンゾアゾール環構造を有する化合物は、有機ＥＬ素子の電子注入層、電子輸送層または正孔阻止層の構成材料として使用することができる。電子の移動度が高く電子注入層または電子輸送層の材料として好ましい化合物である。
The compound having an indenobenzoazole ring structure represented by the general formula (1), which is suitably used for the organic EL device of the present invention, is a compound of an electron injection layer, an electron transport layer or a hole blocking layer of an organic EL device. It can be used as a constituent material. It is a compound having high electron mobility and a preferable material of the electron injection layer or the electron transport layer.
本発明の有機ＥＬ素子は電子の注入・輸送性能、薄膜の安定性や耐久性に優れた有機ＥＬ素子用の材料を使用しているため、従来の有機ＥＬ素子に比べて、電子輸送層から発光層への電子輸送効率が向上し、発光効率が向上すると共に、駆動電圧が低下して、有機ＥＬ素子の耐久性を向上させることができる。
高効率、低駆動電圧、長寿命の有機ＥＬ素子を実現することが可能となった。 Since the organic EL device of the present invention uses a material for an organic EL device which is excellent in electron injection / transport performance, thin film stability and durability, it can be seen from the electron transport layer as compared with the conventional organic EL device. The electron transport efficiency to the light emitting layer is improved, the light emission efficiency is improved, the driving voltage is lowered, and the durability of the organic EL element can be improved.
It has become possible to realize organic EL devices with high efficiency, low drive voltage, and long life.
高効率、低駆動電圧、長寿命の有機ＥＬ素子を実現することが可能となった。 Since the organic EL device of the present invention uses a material for an organic EL device which is excellent in electron injection / transport performance, thin film stability and durability, it can be seen from the electron transport layer as compared with the conventional organic EL device. The electron transport efficiency to the light emitting layer is improved, the light emission efficiency is improved, the driving voltage is lowered, and the durability of the organic EL element can be improved.
It has become possible to realize organic EL devices with high efficiency, low drive voltage, and long life.
本発明の有機ＥＬ素子は電子の注入・輸送の役割を効果的に発現できる特定のインデノベンゾアゾール環構造を有する化合物を選択したことにより、電子輸送層から発光層へ電子を効率良く注入・輸送できることによって、電子の注入・輸送性能、薄膜の安定性や耐久性に優れ、高効率、低駆動電圧、長寿命の有機ＥＬ素子を実現することができる。
本発明によれば、従来の有機ＥＬ素子の発光効率および駆動電圧、そして耐久性を改良することができる。 The organic EL device of the present invention efficiently injects electrons from the electron transport layer to the light emitting layer by selecting a compound having a specific indenobenzoazole ring structure capable of effectively expressing the role of electron injection / transport By being able to be transported, it is possible to realize an organic EL device which is excellent in electron injection / transport performance, stability and durability of a thin film, high efficiency, low driving voltage and long life.
According to the present invention, the luminous efficiency, the driving voltage, and the durability of the conventional organic EL element can be improved.
本発明によれば、従来の有機ＥＬ素子の発光効率および駆動電圧、そして耐久性を改良することができる。 The organic EL device of the present invention efficiently injects electrons from the electron transport layer to the light emitting layer by selecting a compound having a specific indenobenzoazole ring structure capable of effectively expressing the role of electron injection / transport By being able to be transported, it is possible to realize an organic EL device which is excellent in electron injection / transport performance, stability and durability of a thin film, high efficiency, low driving voltage and long life.
According to the present invention, the luminous efficiency, the driving voltage, and the durability of the conventional organic EL element can be improved.
本発明のベンゾアゾール環構造を有する化合物は新規な化合物である。これら化合物は例えば以下のように、それ自体公知の方法に準じて合成することができる（例えば、特許文献５、６、非特許文献６、７参照）。
The compounds having a benzoazole ring structure of the present invention are novel compounds. These compounds can be synthesized, for example, according to methods known per se as follows (see, for example, Patent Documents 5 and 6, Non-patent Documents 6 and 7).
本発明の有機ＥＬ素子に好適に用いられる、前記一般式（１）で表されるベンゾオキサゾール化合物の中で、好ましい化合物の具体例を以下の図１～図１２に示すが、これらの化合物に限定されるものではない。
Among the benzoxazole compounds represented by the above general formula (1), which are suitably used for the organic EL device of the present invention, specific examples of preferred compounds are shown in FIGS. 1 to 12 below. It is not limited.
一般式（１）～（６）で表されるインデノベンゾアゾール環構造を有する化合物の精製はカラムクロマトグラフによる精製、シリカゲル、活性炭、活性白土等による吸着精製、溶媒による再結晶や晶析法、昇華精製法などによって行った。化合物の同定は、ＮＭＲ分析によって行なった。物性値として、融点、ガラス転移点（Ｔｇ）と仕事関数の測定を行った。融点は蒸着性の指標となるものであり、ガラス転移点（Ｔｇ）は薄膜状態の安定性の指標となり、仕事関数は正孔輸送性や正孔阻止性の指標となるものである。
Purification of the compound having an indenobenzoazole ring structure represented by the general formulas (1) to (6) is purification by column chromatography, adsorption purification with silica gel, activated carbon, activated clay or the like, recrystallization or crystallization method with a solvent , Sublimation purification method and the like. Identification of the compounds was performed by NMR analysis. Melting point, glass transition point (Tg) and work function were measured as physical property values. The melting point is an index of vapor deposition property, the glass transition point (Tg) is an index of stability of the thin film state, and the work function is an index of hole transporting property or hole blocking property.
融点とガラス転移点（Ｔｇ）は、粉体を用いて高感度示差走査熱量計（ブルカー・エイエックスエス製、ＤＳＣ３１００ＳＡ）によって測定した。
The melting point and the glass transition point (Tg) were measured with a powder using a high sensitivity differential scanning calorimeter (DSC3100SA, manufactured by Bruker AXS).
仕事関数は、ＩＴＯ基板の上に１００ｎｍの薄膜を作製して、イオン化ポテンシャル測定装置（住友重機械工業株式会社製、ＰＹＳ－２０２）によって求めた。
The work function was obtained by preparing a thin film of 100 nm on an ITO substrate and using an ionization potential measurement device (PYS-202, manufactured by Sumitomo Heavy Industries, Ltd.).
本発明の有機ＥＬ素子の構造としては、基板上に順次に、陽極、正孔注入層、正孔輸送層、発光層、電子輸送層、電子注入層及び陰極からなるもの、また、正孔輸送層と発光層の間に電子阻止層を有するもの、発光層と電子輸送層の間に正孔阻止層を有するものがあげられる。これらの多層構造においては有機層を何層か省略あるいは兼ねることが可能であり、例えば正孔注入層と正孔輸送層を兼ねた構成とすること、電子注入層と電子輸送層を兼ねた構成とすること、などもできる。また、同一の機能を有する有機層を２層以上積層した構成とすることが可能であり、正孔輸送層を２層積層した構成、発光層を２層積層した構成、電子輸送層を２層積層した構成、などもできる。
The structure of the organic EL device of the present invention comprises, in order on the substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode, and hole transport. Those having an electron blocking layer between the layer and the light emitting layer and those having a hole blocking layer between the light emitting layer and the electron transport layer can be mentioned. In these multilayer structures, it is possible to omit or combine several organic layers. For example, a structure which combines a hole injection layer and a hole transport layer, a structure which combines an electron injection layer and an electron transport layer It can also be done. In addition, it is possible to stack two or more organic layers having the same function, two hole transport layers, two light emitting layers, and two electron transport layers. A stacked configuration, etc. can also be performed.
本発明の有機ＥＬ素子の陽極としては、ＩＴＯや金のような仕事関数の大きな電極材料が用いられる。本発明の有機ＥＬ素子の正孔注入層として、銅フタロシアニンに代表されるポルフィリン化合物のほか、スターバースト型のトリフェニルアミン誘導体、分子中にトリフェニルアミン構造またはカルバゾリル構造を２個以上有し、それぞれが単結合またはヘテロ原子を含まない２価基で連結した構造を有するアリールアミン化合物などの他に、ヘキサシアノアザトリフェニレンのようなアクセプター性の複素環化合物や塗布型の高分子材料を用いることができる。これらの材料は蒸着法の他、スピンコート法やインクジェット法などの公知の方法によって薄膜形成を行うことができる。
As the anode of the organic EL element of the present invention, an electrode material having a large work function such as ITO or gold is used. As a hole injection layer of the organic EL device of the present invention, in addition to a porphyrin compound represented by copper phthalocyanine, a starburst type triphenylamine derivative, having two or more triphenylamine structures or carbazolyl structures in the molecule, In addition to an arylamine compound or the like having a structure in which each is a single bond or a divalent group having no hetero atom, etc., an acceptor heterocyclic compound such as hexacyanoazatriphenylene or a coated polymer material may be used. it can. These materials can be formed into a thin film by a known method such as a spin coat method or an ink jet method other than the vapor deposition method.
本発明の有機ＥＬ素子の正孔輸送層として、Ｎ，Ｎ'－ジフェニル－Ｎ，Ｎ'－ジ（ｍ－トリル）－ベンジジン（以後、ＴＰＤと略称する）やＮ，Ｎ'－ジフェニル－Ｎ，Ｎ'－ジ（α－ナフチル）－ベンジジン（以後、ＮＰＤと略称する）、Ｎ，Ｎ，Ｎ'，Ｎ'－テトラビフェニリルベンジジンなどのベンジジン誘導体、１，１－ビス［(ジ－４－トリルアミノ)フェニル］シクロヘキサン（以後、ＴＡＰＣと略称する）、分子中にトリフェニルアミン構造またはカルバゾリル構造を２個以上有し、それぞれが単結合またはヘテロ原子を含まない２価基で連結した構造を有するアリールアミン化合物などを用いることができる。これらは、単独で成膜しても良いが、他の材料とともに混合して成膜した単層として使用しても良く、上記複数の材料による単独で成膜した層同士、上記複数の材料による混合して成膜した層同士、または上記複数の材料による単独で成膜した層と混合して成膜した層の積層構造としても良い。また、正孔の注入・輸送層として、ポリ（３，４－エチレンジオキシチオフェン）（以後、ＰＥＤＯＴと略称する）／ポリ（スチレンスルフォネート）（以後、ＰＳＳと略称する）などの塗布型の高分子材料を用いることができる。これらの材料は蒸着法の他、スピンコート法やインクジェット法などの公知の方法によって薄膜形成を行うことができる。
As the hole transport layer of the organic EL device of the present invention, N, N'-diphenyl-N, N'-di (m-tolyl) -benzidine (hereinafter abbreviated as TPD) or N, N'-diphenyl-N Benzidine derivatives such as N, N'-di (α-naphthyl) -benzidine (hereinafter abbreviated as NPD), N, N, N ', N'-tetrabiphenylyl benzidine, 1,1-bis [(di-4) -Tolylamino) phenyl] cyclohexane (hereinafter abbreviated as TAPC), a molecule having two or more triphenylamine structures or carbazolyl structures in the molecule, each of which is a single bond or a divalent group having no hetero atom The arylamine compound etc. which it has can be used. Although these may be formed separately, they may be used as a single layer formed by mixing with other materials, and layers formed separately by the above plurality of materials may be used together by the above plurality of materials. A stacked structure of layers formed by mixing and forming a film or layers formed by mixing and forming a single film of the above plurality of materials may be employed. In addition, as a hole injection / transport layer, a coating type such as poly (3,4-ethylenedioxythiophene) (hereinafter referred to as PEDOT) / poly (styrene sulfonate) (hereinafter referred to as PSS), etc. Polymer materials can be used. These materials can be formed into a thin film by a known method such as a spin coat method or an ink jet method other than the vapor deposition method.
また、正孔注入層あるいは正孔輸送層において、該層に通常使用される材料に対し、さらにトリスブロモフェニルアミンヘキサクロルアンチモン、ラジアレン誘導体（例えば、特許文献７参照）をＰドーピングしたものや、ＴＰＤなどのベンジジン誘導体の構造をその部分構造に有する高分子化合物などを用いることができる。
In addition, in the hole injection layer or the hole transport layer, a material in which trisbromophenylamine hexachloroantimony, a radialene derivative (see, for example, Patent Document 7) is further P-doped to a material usually used in the layer, A high molecular compound having a structure of a benzidine derivative such as TPD in its partial structure can be used.
本発明の有機ＥＬ素子の電子阻止層として、４，４'，４''－トリ（Ｎ－カルバゾリル）トリフェニルアミン（以後、ＴＣＴＡと略称する）、９，９－ビス［４－（カルバゾール－９－イル）フェニル］フルオレン、１，３－ビス（カルバゾール－９－イル）ベンゼン（以後、ｍＣＰと略称する）、２，２－ビス（４－カルバゾール－９－イルフェニル）アダマンタン(以後、Ａｄ－Ｃｚと略称する)などのカルバゾール誘導体、９－［４－（カルバゾール－９－イル）フェニル］－９－［４－（トリフェニルシリル）フェニル］－９Ｈ－フルオレンに代表されるトリフェニルシリル基とトリアリールアミン構造を有する化合物などの電子阻止作用を有する化合物を用いることができる。これらは、単独で成膜しても良いが、他の材料とともに混合して成膜した単層として使用しても良く、上記複数の材料による単独で成膜した層同士、上記複数の材料による混合して成膜した層同士、または上記複数の材料による単独で成膜した層と混合して成膜した層の積層構造としても良い。これらの材料は蒸着法の他、スピンコート法やインクジェット法などの公知の方法によって薄膜形成を行うことができる。
As an electron blocking layer of the organic EL device of the present invention, 4,4 ′, 4 ′ ′-tri (N-carbazolyl) triphenylamine (hereinafter abbreviated as TCTA), 9,9-bis [4- (carbazole-) 9-yl) phenyl] fluorene, 1,3-bis (carbazol-9-yl) benzene (hereinafter abbreviated as mCP), 2,2-bis (4-carbazol-9-ylphenyl) adamantane (hereinafter Ad) And triphenylsilyl groups represented by 9- [4- (carbazol-9-yl) phenyl] -9- [4- (triphenylsilyl) phenyl] -9H-fluorene. And compounds having electron blocking activity such as compounds having a triarylamine structure. Although these may be formed separately, they may be used as a single layer formed by mixing with other materials, and layers formed separately by the above plurality of materials may be used together by the above plurality of materials. A stacked structure of layers formed by mixing and forming a film or layers formed by mixing and forming a single film of the above plurality of materials may be employed. These materials can be formed into a thin film by a known method such as a spin coat method or an ink jet method other than the vapor deposition method.
本発明の有機ＥＬ素子の発光層として、本発明のインデノベンゾアゾール環構造を有する化合物のほか、Ａｌｑ３をはじめとするキノリノール誘導体の金属錯体の他、各種の金属錯体、アントラセン誘導体、ビススチリルベンゼン誘導体、ピレン誘導体、オキサゾール誘導体、ポリパラフェニレンビニレン誘導体などを用いることができる。また、発光層をホスト材料とドーパント材料とで構成してもよく、ホスト材料として、アントラセン誘導体が好ましく用いられるが、そのほか、本発明のインデノベンゾアゾール環構造を有する化合物を初めとする前記発光材料に加え、インドール環を縮合環の部分構造として有する複素環化合物、カルバゾール環を縮合環の部分構造として有する複素環化合物、カルバゾール誘導体、チアゾール誘導体、ベンズイミダゾール誘導体、ポリジアルキルフルオレン誘導体などを用いることができる。またドーパント材料としては、キナクリドン、クマリン、ルブレン、ペリレンおよびそれらの誘導体、ベンゾピラン誘導体、ローダミン誘導体、アミノスチリル誘導体などを用いることができる。これらは、単独で成膜してもよいが、他の材料とともに混合して成膜した単層として使用してもよく、上記複数の材料による単独で成膜した層同士、上記複数の材料による混合して成膜した層同士、または上記複数の材料による単独で成膜した層と混合して成膜した層の積層構造としてもよい。
As the light emitting layer of the organic EL device of the present invention, in addition to the metal complex of quinolinol derivative including Alq 3 in addition to the compound having the indenobenzoazole ring structure of the present invention, various metal complexes, anthracene derivative, bisstyryl Benzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives and the like can be used. The light emitting layer may be composed of a host material and a dopant material. Anthracene derivative is preferably used as the host material, but the light emission including the compound having an indenobenzoazole ring structure of the present invention. In addition to the materials, a heterocyclic compound having an indole ring as a partial structure of a condensed ring, a heterocyclic compound having a carbazole ring as a partial structure of a condensed ring, a carbazole derivative, a thiazole derivative, a benzimidazole derivative, a polydialkyl fluorene derivative, etc. Can. As the dopant material, quinacridone, coumarin, rubrene, perylene and derivatives thereof, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives and the like can be used. Although these may be formed separately, they may be used as a single layer formed by mixing with other materials, layers formed separately by the above plural materials, and by the above plural materials A stacked structure of layers formed by mixing and forming a film or layers formed by mixing and forming a single film of the above plurality of materials may be employed.
また、発光材料として燐光発光体を使用することも可能である。燐光発光体としては、イリジウムや白金などの金属錯体の燐光発光体を使用することができる。Ｉｒ（ｐｐｙ）３などの緑色の燐光発光体、ＦＩｒｐｉｃ、ＦＩｒ６などの青色の燐光発光体、Ｂｔｐ２Ｉｒ（ａｃａｃ）などの赤色の燐光発光体などが用いられ、このときのホスト材料としては正孔注入・輸送性のホスト材料として４，４'－ジ（Ｎ－カルバゾリル）ビフェニル（以後、ＣＢＰと略称する）やＴＣＴＡ、ｍＣＰなどのカルバゾール誘導体などに加え、本発明のベンゾアゾール環構造とピリドインドール環構造を有する化合物を用いることができる。電子輸送性のホスト材料として、ｐ－ビス（トリフェニルシリル）ベンゼン(以後、ＵＧＨ２と略称する)や２，２',２''－(１，３，５－フェニレン)－トリス（１－フェニル－１Ｈ－ベンズイミダゾール）（以後、ＴＰＢIと略称する）などを用いることができ、高性能の有機ＥＬ素子を作製することができる。
It is also possible to use a phosphorescence material as a light emitting material. As a phosphorescence light emitter, a phosphorescence light emitter of metal complex such as iridium and platinum can be used. A green phosphor such as Ir (ppy) 3 , a blue phosphor such as FIrpic or FIr 6, a red phosphor such as Btp 2 Ir (acac), or the like may be used as the host material. In addition to 4,4'-di (N-carbazolyl) biphenyl (hereinafter abbreviated as CBP) and carbazole derivatives such as TCTA and mCP as a hole injection / transport host material, the benzoazole ring structure of the present invention and pyri Compounds having a doindole ring structure can be used. P-Bis (triphenylsilyl) benzene (hereinafter abbreviated as UGH2) or 2,2 ′, 2 ′ ′-(1,3,5-phenylene) -tris (1-phenyl) as an electron transporting host material A -1H-benzimidazole) (hereinafter abbreviated as TPBI) or the like can be used, and a high-performance organic EL element can be manufactured.
燐光性の発光材料のホスト材料へのドープは濃度消光を避けるため、発光層全体に対して1～３０重量パーセントの範囲で、共蒸着によってドープすることが好ましい。
It is preferable to dope the host material with the phosphorescent light emitting material by co-evaporation in the range of 1 to 30 weight percent with respect to the entire light emitting layer in order to avoid concentration quenching.
また、発光材料としてＰＩＣ－ＴＲＺ、ＣＣ２ＴＡ、ＰＸＺ－ＴＲＺ、４ＣｚＩＰＮなどのＣＤＣＢ誘導体などの遅延蛍光を放射する材料を使用することも可能である。（例えば、非特許文献３参照）これらの材料は蒸着法の他、スピンコート法やインクジェット法などの公知の方法によって薄膜形成を行うことができる。
In addition, it is also possible to use a material that emits delayed fluorescence such as PICCB, such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN, as a light-emitting material. (See, for example, Non-Patent Document 3) These materials can be thin film-formed by a known method such as a spin coating method or an inkjet method in addition to the vapor deposition method.
本発明の有機ＥＬ素子の正孔阻止層として、本発明のインデノベンゾアゾール環構造を有する化合物のほか、バソクプロイン（以後、ＢＣＰと略称する）などのフェナントロリン誘導体や、ＢＡｌｑなどのキノリノール誘導体の金属錯体のほか、各種の希土類錯体、オキサゾール誘導体、トリアゾール誘導体、トリアジン誘導体など、正孔阻止作用を有する化合物を用いることができる。これらの材料は電子輸送層の材料を兼ねてもよい。これらは、単独で成膜しても良いが、他の材料とともに混合して成膜した単層として使用しても良く、上記複数の材料による単独で成膜した層同士、上記複数の材料による混合して成膜した層同士、または上記複数の材料による単独で成膜した層と混合して成膜した層の積層構造としても良い。これらの材料は蒸着法の他、スピンコート法やインクジェット法などの公知の方法によって薄膜形成を行うことができる。
As the hole blocking layer of the organic EL device of the present invention, in addition to the compound having the indenobenzoazole ring structure of the present invention, phenanthroline derivatives such as vasocuproin (hereinafter abbreviated as BCP) and metals of quinolinol derivatives such as BAlq In addition to the complexes, various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, and other compounds having a hole blocking function can be used. These materials may double as the material of the electron transport layer. Although these may be formed separately, they may be used as a single layer formed by mixing with other materials, and layers formed separately by the above plurality of materials may be used together by the above plurality of materials. A stacked structure of layers formed by mixing and forming a film or layers formed by mixing and forming a single film of the above plurality of materials may be employed. These materials can be formed into a thin film by a known method such as a spin coat method or an ink jet method other than the vapor deposition method.
本発明の有機ＥＬ素子の電子輸送層として、本発明のインデノベンゾアゾール環構造を有する化合物のほか、Ａｌｑ３、ＢＡｌｑをはじめとするキノリノール誘導体の金属錯体のほか、各種金属錯体、トリアゾール誘導体、トリアジン誘導体、オキサジアゾール誘導体、ピリジン誘導体、ベンズイミダゾール誘導体、チアジアゾール誘導体、アントラセン誘導体、カルボジイミド誘導体、キノキサリン誘導体、ピリドインドール誘導体、フェナントロリン誘導体、シロール誘導体などを用いることができる。これらは、単独で成膜しても良いが、他の材料とともに混合して成膜した単層として使用しても良く、上記複数の材料による単独で成膜した層同士、上記複数の材料による混合して成膜した層同士、または上記複数の材料による単独で成膜した層と混合して成膜した層の積層構造としても良い。これらの材料は蒸着法の他、スピンコート法やインクジェット法などの公知の方法によって薄膜形成を行うことができる。
In addition to the compounds having an indenobenzoazole ring structure of the present invention, metal complexes of quinolinol derivatives including Alq 3 and BAlq, various metal complexes, and triazole derivatives, as an electron transport layer of the organic EL device of the present invention Triazine derivatives, oxadiazole derivatives, pyridine derivatives, benzimidazole derivatives, thiadiazole derivatives, anthracene derivatives, carbodiimide derivatives, quinoxaline derivatives, pyridoindole derivatives, phenanthroline derivatives, silole derivatives and the like can be used. Although these may be formed separately, they may be used as a single layer formed by mixing with other materials, and layers formed separately by the above plurality of materials may be used together by the above plurality of materials. A stacked structure of layers formed by mixing and forming a film or layers formed by mixing and forming a single film of the above plurality of materials may be employed. These materials can be formed into a thin film by a known method such as a spin coat method or an ink jet method other than the vapor deposition method.
本発明の有機ＥＬ素子の電子注入層として、本発明のインデノベンゾアゾール環構造を有する化合物のほか、フッ化リチウム、フッ化セシウムなどのアルカリ金属塩、フッ化マグネシウムなどのアルカリ土類金属塩、リチウムキノリノールなどのキノリノール誘導体の金属錯体、酸化アルミニウムなどの金属酸化物、あるいはイッテルビウム（Ｙｂ）、サマリウム（Ｓｍ）、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）、セシウム（Ｃｓ）などの金属などを用いることができるが、電子輸送層と陰極の好ましい選択においては、これを省略することができる。
As the electron injection layer of the organic EL device of the present invention, in addition to the compound having the indenobenzoazole ring structure of the present invention, alkali metal salts such as lithium fluoride and cesium fluoride, alkaline earth metal salts such as magnesium fluoride , Metal complexes of quinolinol derivatives such as lithium quinolinol, metal oxides such as aluminum oxide, or metals such as ytterbium (Yb), samarium (Sm), calcium (Ca), strontium (Sr), cesium (Cs), etc. However, in the preferred selection of the electron transport layer and the cathode this can be omitted.
さらに、電子注入層あるいは電子輸送層において、該層に通常使用される材料に対し、さらにセシウムなどの金属をＮドーピングしたものを用いることができる。
Furthermore, in the electron injection layer or the electron transport layer, a material generally used in the layer may be further N-doped with a metal such as cesium.
本発明の有機ＥＬ素子の陰極として、アルミニウムのような仕事関数の低い電極材料や、マグネシウム銀合金、マグネシウムインジウム合金、アルミニウムマグネシウム合金のような、より仕事関数の低い合金が電極材料として用いられる。
As a cathode of the organic EL device of the present invention, an electrode material having a low work function such as aluminum or an alloy having a lower work function such as a magnesium silver alloy, a magnesium indium alloy, or an aluminum magnesium alloy is used as an electrode material.
以下、本発明の実施の形態について、実施例により具体的に説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。
EXAMPLES Hereinafter, the embodiments of the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
＜１０、１０－ジメチル－２－｛４－（ナフタレン－２－イル）－フェニル｝－４－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール（化合物－１０５）の合成＞
反応容器に１０、１０－ジメチル－２－（４－クロロフェニル）－４－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール：６．０ｇ、２－ナフタレンボロン酸：３．１ｇ、トリス（ジベンジリデンアセトン）ジパラジウム（０）：０．６ｇ、トリシクロヘキシルホスフィン：０．７ｇ、リン酸三カリウム５．０ｇを仕込み、１，４－ジオキサン／Ｈ２Ｏ混合溶媒下にて一晩還流撹拌した。放冷した後、分液、水層から酢酸エチルにて抽出を行った後、濃縮、得られた粗生成物をカラムクロマトグラフ（担体：シリカゲル、溶離液：ジクロロメタン／酢酸エチル）によって精製を行うことで、１０、１０－ジメチル－２－｛４－（ナフタレン－２－イル）－フェニル｝－４－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール（化合物－１０５）の白色粉体：３．７ｇ（収率５２％）を得た。 <10, 10-Dimethyl-2- {4- (naphthalen-2-yl) -phenyl} -4- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzoxazole ( Synthesis of Compound-105)>
In a reaction vessel, 10, 10-dimethyl-2- (4-chlorophenyl) -4- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzoxazole: 6.0 g, 2- Naphthalene boronic acid: 3.1 g, tris (dibenzylideneacetone) dipalladium (0): 0.6 g, tricyclohexyl phosphine: 0.7 g, 5.0 g of tripotassium phosphate is charged, 1,4-dioxane / H 2 The mixture was stirred at reflux overnight under a mixed solvent of O. After cooling, liquid separation, extraction from the aqueous layer with ethyl acetate, concentration and purification of the obtained crude product by column chromatography (carrier: silica gel, eluent: dichloromethane / ethyl acetate) Thus, 10, 10-dimethyl-2- {4- (naphthalen-2-yl) -phenyl} -4- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzo White powder of oxazole (compound-105): 3.7 g (yield 52%) was obtained.
反応容器に１０、１０－ジメチル－２－（４－クロロフェニル）－４－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール：６．０ｇ、２－ナフタレンボロン酸：３．１ｇ、トリス（ジベンジリデンアセトン）ジパラジウム（０）：０．６ｇ、トリシクロヘキシルホスフィン：０．７ｇ、リン酸三カリウム５．０ｇを仕込み、１，４－ジオキサン／Ｈ２Ｏ混合溶媒下にて一晩還流撹拌した。放冷した後、分液、水層から酢酸エチルにて抽出を行った後、濃縮、得られた粗生成物をカラムクロマトグラフ（担体：シリカゲル、溶離液：ジクロロメタン／酢酸エチル）によって精製を行うことで、１０、１０－ジメチル－２－｛４－（ナフタレン－２－イル）－フェニル｝－４－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール（化合物－１０５）の白色粉体：３．７ｇ（収率５２％）を得た。 <10, 10-Dimethyl-2- {4- (naphthalen-2-yl) -phenyl} -4- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzoxazole ( Synthesis of Compound-105)>
In a reaction vessel, 10, 10-dimethyl-2- (4-chlorophenyl) -4- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzoxazole: 6.0 g, 2- Naphthalene boronic acid: 3.1 g, tris (dibenzylideneacetone) dipalladium (0): 0.6 g, tricyclohexyl phosphine: 0.7 g, 5.0 g of tripotassium phosphate is charged, 1,4-dioxane / H 2 The mixture was stirred at reflux overnight under a mixed solvent of O. After cooling, liquid separation, extraction from the aqueous layer with ethyl acetate, concentration and purification of the obtained crude product by column chromatography (carrier: silica gel, eluent: dichloromethane / ethyl acetate) Thus, 10, 10-dimethyl-2- {4- (naphthalen-2-yl) -phenyl} -4- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzo White powder of oxazole (compound-105): 3.7 g (yield 52%) was obtained.
得られた白色粉体についてＮＭＲを使用して構造を同定した。
１Ｈ－ＮＭＲ（ＣＤＣｌ３）で以下の３０個の水素のシグナルを検出した。
δ（ｐｐｍ）＝９．０６（１Ｈ）、８．６８（１Ｈ）、８．３２（２Ｈ）、８．１２（１Ｈ）、８．０７（１Ｈ）、７．９９（１Ｈ）、７．９８－７．７６（９Ｈ）、７．６３（２Ｈ）、７．５８－７．３３（６Ｈ）、１．４４（６Ｈ）。 The structure of the resulting white powder was identified using NMR.
The following 30 hydrogen signals were detected by 1 H-NMR (CDCl 3 ).
δ (ppm) = 9.06 (1 H), 8.68 (1 H), 8.32 (2 H), 8.12 (1 H), 8.07 (1 H), 7.99 (1 H), 7.98 -7.76 (9 H), 7.63 (2 H), 7.58-7.33 (6 H), 1.44 (6 H).
１Ｈ－ＮＭＲ（ＣＤＣｌ３）で以下の３０個の水素のシグナルを検出した。
δ（ｐｐｍ）＝９．０６（１Ｈ）、８．６８（１Ｈ）、８．３２（２Ｈ）、８．１２（１Ｈ）、８．０７（１Ｈ）、７．９９（１Ｈ）、７．９８－７．７６（９Ｈ）、７．６３（２Ｈ）、７．５８－７．３３（６Ｈ）、１．４４（６Ｈ）。 The structure of the resulting white powder was identified using NMR.
The following 30 hydrogen signals were detected by 1 H-NMR (CDCl 3 ).
δ (ppm) = 9.06 (1 H), 8.68 (1 H), 8.32 (2 H), 8.12 (1 H), 8.07 (1 H), 7.99 (1 H), 7.98 -7.76 (9 H), 7.63 (2 H), 7.58-7.33 (6 H), 1.44 (6 H).
＜１０、１０－ジメチル－４－（ビフェニル－４－イル）－２－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール（化合物－４）の合成＞
反応容器に１０、１０－ジメチル－２－（４－クロロフェニル）－４－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール：１５．０ｇ、３－ピリジルボロン酸：４．８ｇ、トリス（ジベンジリデンアセトン）ジパラジウム（０）：０．７ｇ、トリシクロヘキシルホスフィン：０．８ｇ、リン酸三カリウム：５．０ｇを仕込み、１，４－ジオキサン／Ｈ２Ｏ混合溶媒下にて一晩還流撹拌した。放冷した後、分液抽出を行った後、濃縮して粗生成物を得た。粗生成物をカラムクロマトグラフ（担体：シリカゲル、溶離液：ジクロロメタン／酢酸エチル）によって精製を行うことで、１０、１０－ジメチル－４－（ビフェニル－４－イル）－２－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール（化合物－４）の白色粉体：６．７ｇ（収率４１％）を得た。 Synthesis of <10, 10-dimethyl-4- (biphenyl-4-yl) -2- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzoxazole (compound 4) >
In a reaction vessel, 10,10-dimethyl-2- (4-chlorophenyl) -4- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzoxazole: 15.0 g, 3- Charge pyridylboronic acid: 4.8 g, tris (dibenzylideneacetone) dipalladium (0): 0.7 g, tricyclohexylphosphine: 0.8 g, tripotassium phosphate: 5.0 g, 1,4-dioxane / H The mixture was stirred at reflux overnight under a mixed solvent of 2 O. The mixture was allowed to cool, separated and extracted, and concentrated to give a crude product. The crude product is purified by column chromatography (carrier: silica gel, eluent: dichloromethane / ethyl acetate) to give 10, 10-dimethyl-4- (biphenyl-4-yl) -2- {4- (pyridyl) White powder of -3-yl) -phenyl} -indeno [1,2, g] benzoxazole (Compound 4): 6.7 g (yield 41%) was obtained.
反応容器に１０、１０－ジメチル－２－（４－クロロフェニル）－４－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール：１５．０ｇ、３－ピリジルボロン酸：４．８ｇ、トリス（ジベンジリデンアセトン）ジパラジウム（０）：０．７ｇ、トリシクロヘキシルホスフィン：０．８ｇ、リン酸三カリウム：５．０ｇを仕込み、１，４－ジオキサン／Ｈ２Ｏ混合溶媒下にて一晩還流撹拌した。放冷した後、分液抽出を行った後、濃縮して粗生成物を得た。粗生成物をカラムクロマトグラフ（担体：シリカゲル、溶離液：ジクロロメタン／酢酸エチル）によって精製を行うことで、１０、１０－ジメチル－４－（ビフェニル－４－イル）－２－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール（化合物－４）の白色粉体：６．７ｇ（収率４１％）を得た。 Synthesis of <10, 10-dimethyl-4- (biphenyl-4-yl) -2- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzoxazole (compound 4) >
In a reaction vessel, 10,10-dimethyl-2- (4-chlorophenyl) -4- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzoxazole: 15.0 g, 3- Charge pyridylboronic acid: 4.8 g, tris (dibenzylideneacetone) dipalladium (0): 0.7 g, tricyclohexylphosphine: 0.8 g, tripotassium phosphate: 5.0 g, 1,4-dioxane / H The mixture was stirred at reflux overnight under a mixed solvent of 2 O. The mixture was allowed to cool, separated and extracted, and concentrated to give a crude product. The crude product is purified by column chromatography (carrier: silica gel, eluent: dichloromethane / ethyl acetate) to give 10, 10-dimethyl-4- (biphenyl-4-yl) -2- {4- (pyridyl) White powder of -3-yl) -phenyl} -indeno [1,2, g] benzoxazole (Compound 4): 6.7 g (yield 41%) was obtained.
得られた白色粉体についてＮＭＲを使用して構造を同定した。
１Ｈ－ＮＭＲ（ＣＤＣｌ３）で以下の２８個の水素のシグナルを検出した。
δ（ｐｐｍ）＝８．９２（１Ｈ）、８．６５（１Ｈ）、８．３２（２Ｈ）、７．９８（１Ｈ）、７．９４（１Ｈ）、７．８８－７．７６（５Ｈ）、７．７０（２Ｈ）、７．５７（２Ｈ）、７．５２（２Ｈ）、７．４７－７．３３（５Ｈ）、１．４４（６Ｈ）。 The structure of the resulting white powder was identified using NMR.
The following 28 hydrogen signals were detected by 1 H-NMR (CDCl 3).
δ (ppm) = 8.92 (1 H), 8.65 (1 H), 8.32 (2 H), 7.98 (1 H), 7.94 (1 H), 7.88-7.76 (5 H) 7.70 (2H), 7.57 (2H), 7.52 (2H), 7.47-7.33 (5H), 1.44 (6H).
１Ｈ－ＮＭＲ（ＣＤＣｌ３）で以下の２８個の水素のシグナルを検出した。
δ（ｐｐｍ）＝８．９２（１Ｈ）、８．６５（１Ｈ）、８．３２（２Ｈ）、７．９８（１Ｈ）、７．９４（１Ｈ）、７．８８－７．７６（５Ｈ）、７．７０（２Ｈ）、７．５７（２Ｈ）、７．５２（２Ｈ）、７．４７－７．３３（５Ｈ）、１．４４（６Ｈ）。 The structure of the resulting white powder was identified using NMR.
The following 28 hydrogen signals were detected by 1 H-NMR (CDCl 3).
δ (ppm) = 8.92 (1 H), 8.65 (1 H), 8.32 (2 H), 7.98 (1 H), 7.94 (1 H), 7.88-7.76 (5 H) 7.70 (2H), 7.57 (2H), 7.52 (2H), 7.47-7.33 (5H), 1.44 (6H).
＜１０、１０－ジメチル－２－｛４－（ナフタレン－１－イル）－フェニル｝－４－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール（化合物－１３２）の合成＞
反応容器に１０、１０－ジメチル－２－（４－クロロフェニル）－４－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール：１０．５ｇ、カルバゾール：５．４ｇ、トリス（ジベンジリデンアセトン）ジパラジウム（０）：１．０ｇ、トリシクロヘキシルホスフィン：１．２ｇ、リン酸三カリウム：８．７ｇを仕込み、１，４－ジオキサン／Ｈ２Ｏ混合溶媒下にて一晩還流撹拌した。放冷した後、分液、水層から酢酸エチルにて抽出を行った後、濃縮、得られた粗生成物をカラムクロマトグラフ（担体：シリカゲル、溶離液：ジクロロメタン／酢酸エチル）によって精製を行うことで、１０、１０－ジメチル－２－｛４－（ナフタレン－１－イル）－フェニル｝－４－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール（化合物－１３２）の白色粉体：３．１ｇ（収率４６％）を得た。 <10, 10-Dimethyl-2- {4- (naphthalen-1-yl) -phenyl} -4- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzoxazole ( Synthesis of Compound -132)>
In a reaction vessel, 10,10-dimethyl-2- (4-chlorophenyl) -4- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzoxazole: 10.5 g, carbazole: Charge 5.4 g, tris (dibenzylideneacetone) dipalladium (0): 1.0 g, tricyclohexyl phosphine: 1.2 g, tripotassium phosphate: 8.7 g, and add 1,4-dioxane / H 2 O mixed solvent The mixture was stirred at reflux overnight. After cooling, liquid separation, extraction from the aqueous layer with ethyl acetate, concentration and purification of the obtained crude product by column chromatography (carrier: silica gel, eluent: dichloromethane / ethyl acetate) 10, 10-Dimethyl-2- {4- (naphthalen-1-yl) -phenyl} -4- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzo White powder of oxazole (compound-132): 3.1 g (yield 46%) was obtained.
反応容器に１０、１０－ジメチル－２－（４－クロロフェニル）－４－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール：１０．５ｇ、カルバゾール：５．４ｇ、トリス（ジベンジリデンアセトン）ジパラジウム（０）：１．０ｇ、トリシクロヘキシルホスフィン：１．２ｇ、リン酸三カリウム：８．７ｇを仕込み、１，４－ジオキサン／Ｈ２Ｏ混合溶媒下にて一晩還流撹拌した。放冷した後、分液、水層から酢酸エチルにて抽出を行った後、濃縮、得られた粗生成物をカラムクロマトグラフ（担体：シリカゲル、溶離液：ジクロロメタン／酢酸エチル）によって精製を行うことで、１０、１０－ジメチル－２－｛４－（ナフタレン－１－イル）－フェニル｝－４－｛４－（ピリジル－３－イル）－フェニル｝－インデノ［１、２、ｇ］ベンゾオキサゾール（化合物－１３２）の白色粉体：３．１ｇ（収率４６％）を得た。 <10, 10-Dimethyl-2- {4- (naphthalen-1-yl) -phenyl} -4- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzoxazole ( Synthesis of Compound -132)>
In a reaction vessel, 10,10-dimethyl-2- (4-chlorophenyl) -4- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzoxazole: 10.5 g, carbazole: Charge 5.4 g, tris (dibenzylideneacetone) dipalladium (0): 1.0 g, tricyclohexyl phosphine: 1.2 g, tripotassium phosphate: 8.7 g, and add 1,4-dioxane / H 2 O mixed solvent The mixture was stirred at reflux overnight. After cooling, liquid separation, extraction from the aqueous layer with ethyl acetate, concentration and purification of the obtained crude product by column chromatography (carrier: silica gel, eluent: dichloromethane / ethyl acetate) 10, 10-Dimethyl-2- {4- (naphthalen-1-yl) -phenyl} -4- {4- (pyridyl-3-yl) -phenyl} -indeno [1,2, g] benzo White powder of oxazole (compound-132): 3.1 g (yield 46%) was obtained.
得られた白色粉体についてＮＭＲを使用して構造を同定した。
１Ｈ－ＮＭＲ（ＣＤＣｌ３）で以下の３５個の水素のシグナルを検出した。
δ（ｐｐｍ）＝８．５２（２Ｈ）、８．１９（４Ｈ）、７．９４（１Ｈ）、７．９２（１Ｈ）、７．８２（１Ｈ）、７．５７（４Ｈ）、７．５３－７．３２（１６Ｈ）、１．３８（６Ｈ）。 The structure of the resulting white powder was identified using NMR.
The following 35 hydrogen signals were detected by 1 H-NMR (CDCl 3 ).
δ (ppm) = 8.52 (2 H), 8.19 (4 H), 7.94 (1 H), 7.92 (1 H), 7.82 (1 H), 7.57 (4 H), 7.53 -7.32 (16H), 1.38 (6H).
１Ｈ－ＮＭＲ（ＣＤＣｌ３）で以下の３５個の水素のシグナルを検出した。
δ（ｐｐｍ）＝８．５２（２Ｈ）、８．１９（４Ｈ）、７．９４（１Ｈ）、７．９２（１Ｈ）、７．８２（１Ｈ）、７．５７（４Ｈ）、７．５３－７．３２（１６Ｈ）、１．３８（６Ｈ）。 The structure of the resulting white powder was identified using NMR.
The following 35 hydrogen signals were detected by 1 H-NMR (CDCl 3 ).
δ (ppm) = 8.52 (2 H), 8.19 (4 H), 7.94 (1 H), 7.92 (1 H), 7.82 (1 H), 7.57 (4 H), 7.53 -7.32 (16H), 1.38 (6H).
一般式（１）で表されるインデノベンゾアゾール化合物について、高感度示差走査熱量計（ブルカー・エイエックスエス製、ＤＳＣ３１００ＳＡ）によって融点とガラス転移点を測定した。
融点 ガラス転移点
実施例１の化合物 ２６９ ℃ １３６ ℃
実施例２の化合物 ２５６ ℃ １２７ ℃
実施例３の化合物 ３５３ ℃ １７８ ℃ The melting point and the glass transition point of the indenobenzoazole compound represented by the general formula (1) were measured by a high-sensitivity differential scanning calorimeter (DSC3100SA, manufactured by Bruker AXS).
Melting point glass transition point
Compound of Example 1 269 ° C. 136 ° C.
The compound of Example 2 256 ° C 127 ° C
Compound of Example 3 353 ° C 178 ° C
融点 ガラス転移点
実施例１の化合物 ２６９ ℃ １３６ ℃
実施例２の化合物 ２５６ ℃ １２７ ℃
実施例３の化合物 ３５３ ℃ １７８ ℃ The melting point and the glass transition point of the indenobenzoazole compound represented by the general formula (1) were measured by a high-sensitivity differential scanning calorimeter (DSC3100SA, manufactured by Bruker AXS).
Melting point glass transition point
Compound of Example 1 269 ° C. 136 ° C.
The compound of Example 2 256 ° C 127 ° C
Compound of Example 3 353 ° C 178 ° C
一般式（１）で表されるインデノベンゾアゾール環構造を有する化合物は１００℃以上のガラス転移点を有しており、薄膜状態が安定であることを示すものである。
The compound having an indenobenzoazole ring structure represented by the general formula (1) has a glass transition point of 100 ° C. or more, which indicates that the thin film state is stable.
一般式（１）で表されるインデノベンゾアゾール環構造を有する化合物を用いて、ＩＴＯ基板の上に膜厚１００ｎｍの蒸着膜を作製して、イオン化ポテンシャル測定装置（住友重機械工業株式会社製、ＰＹＳ－２０２）によって仕事関数を測定した。
仕事関数
実施例１の化合物 ６．２６ ｅＶ
実施例２の化合物 ６．３８ ｅＶ
実施例３の化合物 ６．２５ ｅＶ Using a compound having an indenobenzoazole ring structure represented by the general formula (1), a vapor deposited film having a film thickness of 100 nm is prepared on an ITO substrate, and an ionization potential measuring device (manufactured by Sumitomo Heavy Industries, Ltd.) , PYS-202) measured the work function.
Compound of work function example 1 6.26 eV
Compound of Example 2 6.38 eV
Compound of Example 3 6.25 eV
仕事関数
実施例１の化合物 ６．２６ ｅＶ
実施例２の化合物 ６．３８ ｅＶ
実施例３の化合物 ６．２５ ｅＶ Using a compound having an indenobenzoazole ring structure represented by the general formula (1), a vapor deposited film having a film thickness of 100 nm is prepared on an ITO substrate, and an ionization potential measuring device (manufactured by Sumitomo Heavy Industries, Ltd.) , PYS-202) measured the work function.
Compound of work function example 1 6.26 eV
Compound of Example 2 6.38 eV
Compound of Example 3 6.25 eV
一般式（１）で表されるインデノベンゾアゾール環構造を有する化合物はＮＰＤ、ＴＰＤなどの一般的な正孔輸送材料がもつ仕事関数５．５ｅＶより大きい値を有しており、大きな正孔阻止能力を有している。
The compound having an indenobenzoazole ring structure represented by the general formula (1) has a work function larger than the work function 5.5 eV of general hole transport materials such as NPD and TPD, and a large hole Has a blocking ability.
有機ＥＬ素子は、図１３に示すように、ガラス基板１上に透明陽極２としてＩＴＯ電極をあらかじめ形成したものの上に、正孔注入層３、正孔輸送層４、発光層５、正孔阻止層６、電子輸送層７、電子注入層８、陰極（アルミニウム電極）９の順に蒸着して作製した。
As shown in FIG. 13, the organic EL device has a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, and a hole blocking layer on an ITO electrode previously formed as a transparent anode 2 on a glass substrate 1. The layer 6, the electron transport layer 7, the electron injection layer 8, and the cathode (aluminum electrode) 9 were sequentially deposited and manufactured.
具体的には、膜厚５０ｎｍのＩＴＯを成膜したガラス基板１をイソプロピルアルコール中にて超音波洗浄を２０分間行った後、２００℃に加熱したホットプレート上にて１０分間乾燥を行った。その後、ＵＶオゾン処理を１５分間行った後、このＩＴＯ付きガラス基板を真空蒸着機内に取り付け、０．００１Ｐａ以下まで減圧した。続いて、透明陽極２を覆うように正孔注入層３として、下記構造式の電子アクセプター（Acceptor－１）と下記構造式の化合物（ＨＴＭ－１）を、蒸着速度比がAcceptor－１：化合物（ＨＴＭ－１）＝３：９７となる蒸着速度で二元蒸着を行い、膜厚１０ｎｍとなるように形成した。この正孔注入層３の上に、正孔輸送層４として下記構造式の化合物（ＨＴＭ－１）を膜厚６０ｎｍとなるように形成した。この正孔輸送層４の上に、発光層５として下記構造式の化合物ＥＭＤ－１と下記構造式の化合物ＥＭＨ－１を、蒸着速度比がＥＭＤ－１：ＥＭＨ－１＝５：９５となる蒸着速度で二元蒸着を行い、膜厚２０ｎｍとなるように形成した。この発光層５の上に、正孔阻止層兼電子輸送層６および７として本発明実施例１の化合物（化合物－１０５）と下記構造式の化合物ＥＴＭ－１を、蒸着速度比が本発明実施例１の化合物（化合物－１０５）：ＥＴＭ－１＝５０：５０となる蒸着速度で二元蒸着を行い、膜厚３０ｎｍとなるように形成した。この正孔阻止層兼電子輸送層６および７の上に、電子注入層８としてフッ化リチウムを膜厚１ｎｍとなるように形成した。最後に、アルミニウムを１００ｎｍ蒸着して陰極９を形成した。作製した有機ＥＬ素子について、大気中、常温で特性測定を行った。作製した有機ＥＬ素子に直流電圧を印加したときの発光特性の測定結果を表１にまとめて示した。
Specifically, the glass substrate 1 on which ITO having a film thickness of 50 nm was formed was subjected to ultrasonic cleaning for 20 minutes in isopropyl alcohol and then dried for 10 minutes on a hot plate heated to 200 ° C. Thereafter, UV ozone treatment was carried out for 15 minutes, and then the ITO-attached glass substrate was mounted in a vacuum deposition machine, and the pressure was reduced to 0.001 Pa or less. Subsequently, as the hole injection layer 3 so as to cover the transparent anode 2, the electron acceptor (Acceptor-1) of the following structural formula and the compound (HTM-1) of the following structural formula have a deposition rate ratio of Acceptor-1: compound Binary vapor deposition was performed at a deposition rate of (HTM-1) = 3: 97 to form a film thickness of 10 nm. On this hole injection layer 3, a compound (HTM-1) of the following structural formula was formed as a hole transport layer 4 to have a film thickness of 60 nm. On this hole transport layer 4, the compound EMD-1 of the following structural formula and the compound EMH-1 of the following structural formula as the light emitting layer 5 have a deposition rate ratio of EMD-1: EMH-1 = 5: 95. Binary vapor deposition was performed at a vapor deposition rate to form a film thickness of 20 nm. On this light emitting layer 5, the compound of the example 1 of the present invention (compound-105) and the compound ETM-1 of the following structural formula were used as the hole blocking and electron transporting layers 6 and 7, and the deposition rate ratio of the present invention is Binary vapor deposition was carried out at a vapor deposition rate of the compound of Example 1 (compound-105): ETM-1 = 50: 50, to form a film thickness of 30 nm. Lithium fluoride was formed as the electron injection layer 8 to a film thickness of 1 nm on the hole blocking and electron transporting layers 6 and 7. Finally, aluminum was deposited 100 nm to form a cathode 9. The characteristics of the produced organic EL device were measured at room temperature in the air. Table 1 summarizes the measurement results of the light emission characteristics when a direct current voltage is applied to the manufactured organic EL element.
実施例６において、正孔阻止層兼電子輸送層６および７の材料として本発明実施例１の化合物（化合物－１０５）に代えて実施例２の化合物（化合物－４）を用い、蒸着速度比が（化合物－４）：ＥＴＭ－１＝５０：５０となる蒸着速度で二元蒸着を行った以外は、同様の条件で有機ＥＬ素子を作製した。作製した有機ＥＬ素子について、大気中、常温で特性測定を行なった。作製した有機ＥＬ素子に直流電圧を印加したときの発光特性の測定結果を表１にまとめて示した。
In Example 6, the compound (Compound-4) of Example 2 is used instead of the compound (Compound-105) of Example 1 of the present invention as the material of the hole blocking layer / electron transport layer 6 and 7 and the deposition rate ratio An organic EL device was manufactured under the same conditions except that binary vapor deposition was performed at a deposition rate of (compound 4): ETM-1 = 50: 50. The characteristics of the produced organic EL device were measured in the air at normal temperature. Table 1 summarizes the measurement results of the light emission characteristics when a direct current voltage is applied to the manufactured organic EL element.
実施例６において、正孔阻止層兼電子輸送層６および７の材料として本発明実施例１の化合物（化合物－１０５）に代えて実施例３の化合物（化合物－１３２）を用い、蒸着速度比が（化合物－１３２）：ＥＴＭ－１＝５０：５０となる蒸着速度で二元蒸着を行った以外は、同様の条件で有機ＥＬ素子を作製した。作製した有機ＥＬ素子について、大気中、常温で特性測定を行なった。作製した有機ＥＬ素子に直流電圧を印加したときの発光特性の測定結果を表１にまとめて示した。
In Example 6, the compound of Example 3 (Compound-132) in place of the compound of the Example 1 of the present invention (Compound-105) was used as the material of the hole blocking layer-cum- electron transport layer 6 and 7, and the deposition rate ratio was An organic EL device was manufactured under the same conditions except that binary vapor deposition was performed at a deposition rate of (compound-132): ETM-1 = 50: 50. The characteristics of the produced organic EL device were measured in the air at normal temperature. Table 1 summarizes the measurement results of the light emission characteristics when a direct current voltage is applied to the manufactured organic EL element.
［比較例１］
比較のために、実施例６において、正孔阻止層兼電子輸送層６および７の材料として本発明実施例１の化合物（化合物－１０５）に代えて、下記構造式の化合物ＥＴＭ－２（例えば、特許文献８参照）を用い、蒸着速度比がＥＴＭ－２：ＥＴＭ－１＝５０：５０となる蒸着速度で二元蒸着を行った以外は、同様の条件で有機ＥＬ素子を作製した。作製した有機ＥＬ素子について、大気中、常温で特性測定を行なった。作製した有機ＥＬ素子に直流電圧を印加したときの発光特性の測定結果を表１にまとめて示した。 Comparative Example 1
For comparison, instead of the compound of the present invention example 1 (compound-105) as the material of the hole blocking layer-cum- electron transport layers 6 and 7 in example 6, a compound ETM-2 of the following structural formula (for example, An organic EL device was produced under the same conditions as in Patent Document 8 except that binary deposition was performed at a deposition rate of ETM-2: ETM-1 = 50: 50. The characteristics of the produced organic EL device were measured in the air at normal temperature. Table 1 summarizes the measurement results of the light emission characteristics when a direct current voltage is applied to the manufactured organic EL element.
比較のために、実施例６において、正孔阻止層兼電子輸送層６および７の材料として本発明実施例１の化合物（化合物－１０５）に代えて、下記構造式の化合物ＥＴＭ－２（例えば、特許文献８参照）を用い、蒸着速度比がＥＴＭ－２：ＥＴＭ－１＝５０：５０となる蒸着速度で二元蒸着を行った以外は、同様の条件で有機ＥＬ素子を作製した。作製した有機ＥＬ素子について、大気中、常温で特性測定を行なった。作製した有機ＥＬ素子に直流電圧を印加したときの発光特性の測定結果を表１にまとめて示した。 Comparative Example 1
For comparison, instead of the compound of the present invention example 1 (compound-105) as the material of the hole blocking layer-cum-
［比較例２］
比較のために、実施例６において、正孔阻止層兼電子輸送層６および７の材料として本発明実施例１の化合物（化合物－１０５）に代えて、下記構造式の化合物ＥＴＭ－３（例えば、特許文献８参照）を用い、蒸着速度比がＥＴＭ－３：ＥＴＭ－１＝５０：５０となる蒸着速度で二元蒸着を行った以外は、同様の条件で有機ＥＬ素子を作製した。作製した有機ＥＬ素子について、大気中、常温で特性測定を行なった。作製した有機ＥＬ素子に直流電圧を印加したときの発光特性の測定結果を表１にまとめて示した。 Comparative Example 2
For comparison, instead of the compound of the present invention example 1 (compound-105) as the material of the hole blocking layer-cum- electron transport layers 6 and 7 in example 6, a compound ETM-3 of the following structural formula (e.g. An organic EL device was produced under the same conditions as in Patent Document 8 except that binary vapor deposition was performed at a vapor deposition rate of ETM-3: ETM-1 = 50: 50. The characteristics of the produced organic EL device were measured in the air at normal temperature. Table 1 summarizes the measurement results of the light emission characteristics when a direct current voltage is applied to the manufactured organic EL element.
比較のために、実施例６において、正孔阻止層兼電子輸送層６および７の材料として本発明実施例１の化合物（化合物－１０５）に代えて、下記構造式の化合物ＥＴＭ－３（例えば、特許文献８参照）を用い、蒸着速度比がＥＴＭ－３：ＥＴＭ－１＝５０：５０となる蒸着速度で二元蒸着を行った以外は、同様の条件で有機ＥＬ素子を作製した。作製した有機ＥＬ素子について、大気中、常温で特性測定を行なった。作製した有機ＥＬ素子に直流電圧を印加したときの発光特性の測定結果を表１にまとめて示した。 Comparative Example 2
For comparison, instead of the compound of the present invention example 1 (compound-105) as the material of the hole blocking layer-cum-
［比較例３］
比較のために、実施例６において、正孔阻止層兼電子輸送層６および７の材料として本発明実施例１の化合物（化合物－１０５）に代えて、下記構造式の化合物ＥＴＭ－４（例えば、特許文献８参照）を用い、蒸着速度比がＥＴＭ－４：ＥＴＭ－１＝５０：５０となる蒸着速度で二元蒸着を行った以外は、同様の条件で有機ＥＬ素子を作製した。作製した有機ＥＬ素子について、大気中、常温で特性測定を行なった。作製した有機ＥＬ素子に直流電圧を印加したときの発光特性の測定結果を表１にまとめて示した。 Comparative Example 3
For comparison, instead of the compound of the present invention example 1 (compound-105) as a material of the hole blocking layer-cum- electron transport layers 6 and 7 in Example 6, a compound ETM-4 of the following structural formula (e.g. An organic EL device was produced under the same conditions as in Patent Document 8 except that binary vapor deposition was performed at a deposition rate of ETM-4: ETM-1 = 50: 50. The characteristics of the produced organic EL device were measured in the air at normal temperature. Table 1 summarizes the measurement results of the light emission characteristics when a direct current voltage is applied to the manufactured organic EL element.
比較のために、実施例６において、正孔阻止層兼電子輸送層６および７の材料として本発明実施例１の化合物（化合物－１０５）に代えて、下記構造式の化合物ＥＴＭ－４（例えば、特許文献８参照）を用い、蒸着速度比がＥＴＭ－４：ＥＴＭ－１＝５０：５０となる蒸着速度で二元蒸着を行った以外は、同様の条件で有機ＥＬ素子を作製した。作製した有機ＥＬ素子について、大気中、常温で特性測定を行なった。作製した有機ＥＬ素子に直流電圧を印加したときの発光特性の測定結果を表１にまとめて示した。 Comparative Example 3
For comparison, instead of the compound of the present invention example 1 (compound-105) as a material of the hole blocking layer-cum-
実施例６～８および比較例１～３で作製した有機ＥＬ素子を用いて、素子寿命を測定した結果を表１にまとめて示した。素子寿命は、発光開始時の発光輝度（初期輝度）を２０００ｃｄ／ｍ２として定電流駆動を行った時、発光輝度が１９００ｃｄ／ｍ２（初期輝度を１００％とした時の９５％に相当：９５％減衰）に減衰するまでの時間として測定した。
The device life was measured using the organic EL devices produced in Examples 6 to 8 and Comparative Examples 1 to 3, and the results are shown in Table 1. The device life is equivalent to 95% when the light emission luminance is 1900 cd / m 2 (when the initial luminance is 100% when constant current driving is performed with the light emission luminance at the start of light emission (initial luminance) 2000 cd / m 2 : The time to decay to 95%) was measured.
表１に示す様に、電流密度１０ｍＡ／ｃｍ２の電流を流したときの駆動電圧は、前記構造式の化合物ＥＴＭ－２～４を用いた比較例１～３の有機ＥＬ素子の３．８１～４．０５Ｖに対し、実施例６～８の有機ＥＬ素子では３．３７～３．６０Ｖと低電圧化した。また、発光効率においては、比較例１～３の有機ＥＬ素子の７．４０～７．６８ｃｄ／Ａに対し、実施例６～８の有機ＥＬ素子では８．５８～８．８７ｃｄ／Ａと向上し、電力効率においても、比較例１～３の有機ＥＬ素子の５．９６～６．３０ｌｍ／Ｗに対し、実施例６～８の有機ＥＬ素子では７．４８～８．１４ｌｍ／Ｗと大きく向上した。特に、素子寿命（９５％減衰）においては、比較例１～３の有機ＥＬ素子における３５～５５時間に対し、実施例６～８の有機ＥＬ素子では１２９～１４９時間と、大きく長寿命化している。
As shown in Table 1, the driving voltage when a current having a current density of 10 mA / cm 2 is applied is 3.81 of the organic EL elements of Comparative Examples 1 to 3 using the compounds ETM-2 to 4 of the above structural formula. In the organic EL elements of Examples 6 to 8, the voltage was lowered to 3.37 to 3.60 V with respect to ̃4.05 V. In addition, the luminous efficiency is improved to 8.58 to 8.87 cd / A for the organic EL devices of Examples 6 to 8 as compared with 7.40 to 7.68 cd / A for the organic EL devices of Comparative Examples 1 to 3. In the power efficiency, the organic EL devices of Examples 6 to 8 are as large as 7.48 to 8.14 lm / W, compared with 5.96 to 6.30 lm / W of the organic EL devices of Comparative Examples 1 to 3. Improved. In particular, with respect to the element life (95% attenuation), the organic EL elements of Examples 6 to 8 greatly extend the life to 129 to 149 hours, compared with 35 to 55 hours for the organic EL elements of Comparative Examples 1 to 3. There is.
このように本発明の有機ＥＬ素子は、前記構造式の化合物ＥＴＭ－２～４を用いた素子と比較して、発光効率および電力効率に優れており、長寿命の有機ＥＬ素子を実現できることがわかった。
Thus, the organic EL device of the present invention is superior to the devices using the compounds ETM-2 to 4 of the above structural formula in luminous efficiency and power efficiency, and can realize an organic EL device having a long life. all right.
本発明の、特定のインデノベンゾアゾール環構造を有する化合物は、電子の注入特性が良く、正孔阻止能力に優れており、薄膜状態が安定であるため、有機ＥＬ素子用の化合物として優れている。該化合物を用いて有機ＥＬ素子を作製することにより、高い効率を得ることができると共に、駆動電圧を低下させることができ、耐久性を改善させることができる。例えば、家庭電化製品や照明の用途への展開が可能となった。
The compound having a specific indenobenzoazole ring structure of the present invention is excellent as a compound for an organic EL device because it has good electron injection characteristics, excellent hole blocking ability, and stable thin film state. There is. By manufacturing an organic EL element using the compound, high efficiency can be obtained, driving voltage can be reduced, and durability can be improved. For example, it has become possible to expand to home appliances and lighting applications.
１ ガラス基板
２ 透明陽極
３ 正孔注入層
４ 正孔輸送層
５ 発光層
６ 正孔阻止層
７ 電子輸送層
８ 電子注入層
９ 陰極 1glass substrate 2 transparent anode 3 hole injection layer 4 hole transport layer 5 light emitting layer 6 hole blocking layer 7 electron transport layer 8 electron injection layer 9 cathode
２ 透明陽極
３ 正孔注入層
４ 正孔輸送層
５ 発光層
６ 正孔阻止層
７ 電子輸送層
８ 電子注入層
９ 陰極 1
Claims (11)
- 下記一般式（１）で表される、インデノベンゾアゾール環構造を有する化合物。
（式中、Ａ１～Ａ４は相互に同一でも異なっていてもよく、水素原子、重水素原子もしくは置換基を有する炭素原子、置換もしくは無置換の芳香族炭化水素基を有する炭素原子、置換もしくは無置換の芳香族複素環基を有する炭素原子、置換もしくは無置換の縮合多環芳香族基を有する炭素原子、または窒素原子を表し、Ｙ１は水素原子、重水素原子、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ｘは酸素原子または硫黄原子を表す。但し、Ａ１～Ａ４の内、隣接し合う炭素原子の１カ所を下記構造式（Ａ－１）とする。）
（式中、破線部を結合部位とし、Ｒ１、Ｒ２は相互に同一でも異なっていてもよく、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ１は重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、トリメチルシリル基、トリフェニルシリル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、ｍは０～５の整数を表す。ｍが２以上の整数である場合、同一のベンゼン環に複数個結合するＡｒ１は相互に同一でも異なってもよい。また、ベンゼン環とベンゼン環に置換された置換基、または同一のベンゼン環に複数置換された置換基同士が、単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成してもよい。） The compound which has an indeno benzo azole ring structure represented by following General formula (1).
(Wherein, A 1 to A 4 may be the same as or different from each other, and are a hydrogen atom, a deuterium atom or a carbon atom having a substituent, a carbon atom having a substituted or unsubstituted aromatic hydrocarbon group, a substitution Or a carbon atom having a non-substituted aromatic heterocyclic group, a carbon atom having a substituted or non-substituted fused polycyclic aromatic group, or a nitrogen atom, and Y 1 represents a hydrogen atom, a deuterium atom, a substituted or non-substituted Aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted fused polycyclic aromatic group, linear group having 1 to 6 carbon atoms which may have a substituent Or a branched alkyl group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a linear or branched chain having 2 to 6 carbon atoms which may have a substituent Represents an alkenyl group of Represents an oxygen atom or a sulfur atom provided that one of adjacent carbon atoms among A 1 to A 4 is represented by the following structural formula (A-1).
(Wherein, the broken line is a bonding site, and R 1 and R 2 may be the same or different from each other, and may have a substituent, a linear or branched C 1 to C 6 carbon atom, An alkyl group, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, or an optionally substituted linear or branched alkenyl group having 2 to 6 carbon atoms Ar 1 represents a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a trimethylsilyl group, a triphenylsilyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group , Substituted or unsubstituted fused polycyclic aromatic group, linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, carbon atom which may have a substituent Several 5-10 cycloalkyl groups, or Represents a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, m represents an integer of 0 to 5. When m is an integer of 2 or more, the same Ar 1 's bound to a plurality of benzene rings may be the same as or different from each other, and the benzene ring and the substituent substituted on the benzene ring, or the substituents substituted on the same benzene ring may be a single bond And may combine with each other to form a ring via a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom) - 請求項１記載の前記一般式（１）が下記一般式（２）で表される、インデノベンゾアゾール環構造を有する化合物。
（式中、Ａ５、Ａ６は相互に同一でも異なっていてもよく、水素原子、重水素原子もしくは置換基を有する炭素原子、置換もしくは無置換の芳香族炭化水素基を有する炭素原子、置換もしくは無置換の芳香族複素環基を有する炭素原子、置換もしくは無置換の縮合多環芳香族基を有する炭素原子、または窒素原子を表し、Ｙ２は水素原子、重水素原子、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ｘは酸素原子または硫黄原子を表し、Ｒ３、Ｒ４は相互に同一でも異なっていてもよく、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ２は重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、トリメチルシリル基、トリフェニルシリル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、ｎは０～５の整数を表す。ｎが２以上の整数である場合、同一のベンゼン環に複数個結合するＡｒ２は相互に同一でも異なってもよい。また、ベンゼン環とベンゼン環に置換された置換基、または同一のベンゼン環に複数置換された置換基同士が、単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成してもよい。） A compound having an indenobenzoazole ring structure, wherein the general formula (1) according to claim 1 is represented by the following general formula (2).
(Wherein A 5 and A 6 may be the same or different from each other, and are hydrogen atoms, deuterium atoms or carbon atoms having a substituent, carbon atoms having a substituted or unsubstituted aromatic hydrocarbon group, substitution Or a carbon atom having a non-substituted aromatic heterocyclic group, a carbon atom having a substituted or non-substituted fused polycyclic aromatic group, or a nitrogen atom, and Y 2 is a hydrogen atom, a deuterium atom, a substituted or non-substituted Aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, a linear or branched chain having 1 to 6 carbon atoms which may have a substituent A branched alkyl group, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, or an optionally substituted linear or branched chain having 2 to 6 carbon atoms Represents an alkenyl group, X is oxygen R 3 and R 4 may be the same as or different from each other, and may have a substituent, a linear or branched alkyl group having 1 to 6 carbon atoms, or a substituent A cycloalkyl group having 5 to 10 carbon atoms which may have a group, or a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, Ar 2 Is a deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group, trimethylsilyl group, triphenylsilyl group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, or substituted or substituted Unsubstituted fused polycyclic aromatic group, linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, 5 to carbon atom which may have a substituent 10 cycloalkyl groups, also Represents a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and n represents an integer of 0 to 5. When n is an integer of 2 or more, they are the same. Ar 2 which is bonded to a plurality of benzene rings may be the same as or different from each other, and the benzene ring and the substituent substituted to the benzene ring, or the substituents substituted to the same benzene ring may be single They may be combined with each other to form a ring via a bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom.) - 請求項２記載の前記一般式（２）が下記一般式（３）で表される、インデノベンゾアゾール環構造を有する化合物。
（式中、Ａ７、Ａ８は相互に同一でも異なっていてもよく、水素原子、重水素原子もしくは置換基を有する炭素原子、置換もしくは無置換の芳香族炭化水素基を有する炭素原子、置換もしくは無置換の芳香族複素環基を有する炭素原子、または置換もしくは無置換の縮合多環芳香族基を有する炭素原子を表し、Ｙ３は水素原子、重水素原子、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ｘは酸素原子または硫黄原子を表し、Ｒ５、Ｒ６は相互に同一でも異なっていてもよく、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ３は重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、トリメチルシリル基、トリフェニルシリル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、ｏは０～５の整数を表す。ｏが２以上の整数である場合、同一のベンゼン環に複数個結合するＡｒ３は相互に同一でも異なってもよい。また、ベンゼン環とベンゼン環に置換された置換基、または同一のベンゼン環に複数置換された置換基同士が、単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成してもよい。） A compound having an indenobenzoazole ring structure, wherein the general formula (2) according to claim 2 is represented by the following general formula (3).
(Wherein, A 7 and A 8 may be identical to or different from each other, and are a hydrogen atom, a deuterium atom or a carbon atom having a substituent, a carbon atom having a substituted or unsubstituted aromatic hydrocarbon group, a substitution Or a carbon atom having a substituted or unsubstituted aromatic heterocyclic group, or a carbon atom having a substituted or unsubstituted fused polycyclic aromatic group, and Y 3 represents a hydrogen atom, a deuterium atom, or a substituted or unsubstituted aromatic group A hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, an optionally substituted linear or branched C 1 to C 6 carbon atoms An alkyl group, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, or an optionally substituted linear or branched alkenyl group having 2 to 6 carbon atoms X represents an oxygen atom or R 5 and R 6 may be the same or different from each other, and may have a substituent, and may be a linear or branched alkyl group having 1 to 6 carbon atoms, or a substituent Represents an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, or an optionally substituted linear or branched alkenyl group having 2 to 6 carbon atoms, and Ar 3 represents a heavy atom Hydrogen atom, fluorine atom, chlorine atom, cyano group, nitro group, trimethylsilyl group, triphenylsilyl group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted A fused polycyclic aromatic group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cyclo of 5 to 10 carbon atoms which may have a substituent Having an alkyl group or a substituent Represents a linear or branched alkenyl group having 2 to 6 carbon atoms, and o represents an integer of 0 to 5. When o is an integer of 2 or more, a plurality of these are bonded to the same benzene ring Ar 3 may be identical to or different from each other, and may be a benzene ring and a substituent substituted on the benzene ring, or a plurality of substituents substituted on the same benzene ring may be a single bond, a substituted or an unsubstituted one They may be bonded to each other via a methylene group, an oxygen atom or a sulfur atom to form a ring). - 請求項３記載の前記一般式（３）が下記一般式（４）で表される、インデノベンゾアゾール環構造を有する化合物。
（式中、Ｙ４は水素原子、重水素原子、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ｘは酸素原子または硫黄原子を表し、Ｒ７、Ｒ８は相互に同一でも異なっていてもよく、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ４は重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、トリメチルシリル基、トリフェニルシリル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ５は水素原子、重水素原子、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表し、ｐは０～５の整数を表す。ｐが２以上の整数である場合、同一のベンゼン環に複数個結合するＡｒ４は相互に同一でも異なってもよい。また、ベンゼン環とベンゼン環に置換された置換基、または同一のベンゼン環に複数置換された置換基同士が、単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成してもよい。） A compound having an indenobenzoazole ring structure, wherein the general formula (3) according to claim 3 is represented by the following general formula (4).
(Wherein Y 4 represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, a substituent A linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a substituent R 2 represents a linear or branched alkenyl group having 2 to 6 carbon atoms, X represents an oxygen atom or a sulfur atom, and R 7 and R 8 may be the same as or different from each other, and are substituted A linear or branched alkyl group having 1 to 6 carbon atoms which may have a group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a substituent Straight or branched C 2 -C 6 optionally substituted Represents an alkenyl group, Ar 4 represents a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a trimethylsilyl group, a triphenylsilyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic group A heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a substituent A cycloalkyl group having 5 to 10 carbon atoms, or a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, Ar 5 is a hydrogen atom, deuterium Represents an atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted fused polycyclic aromatic group, and p represents an integer of 0 to 5; Is an integer of 2 or more In some cases, Ar 4 which plurality bonded to the same benzene ring may be the same or different from each other. Further, a benzene ring substituted substituent on the benzene ring or the same benzene ring multiply substituted substituents, Each other may bond to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring). - 請求項４記載の前記一般式（４）が下記一般式（５）で表される、インデノベンゾアゾール環構造を有する化合物。
（式中、Ｘは酸素原子または硫黄原子を表し、Ｒ９、Ｒ１０は相互に同一でも異なっていてもよく、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ６は重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、トリメチルシリル基、トリフェニルシリル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ７、Ａｒ８は相互に同一でも異なっていてもよく、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表し、ｑは０～５の整数を表す。ｑが２以上の整数である場合、同一のベンゼン環に複数個結合するＡｒ６は相互に同一でも異なってもよい。また、ベンゼン環とベンゼン環に置換された置換基、または同一のベンゼン環に複数置換された置換基同士が、単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成してもよい。但し、Ａｒ７、Ａｒ８は水素原子、重水素原子以外とする。） A compound having an indenobenzoazole ring structure, wherein the general formula (4) according to claim 4 is represented by the following general formula (5).
(Wherein, X represents an oxygen atom or a sulfur atom, and R 9 and R 10 may be identical to or different from each other, and may have a substituent, a linear or 1 to 6 carbon atoms, A branched alkyl group, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, or an optionally substituted linear or branched chain having 2 to 6 carbon atoms Represents an alkenyl group, Ar 6 represents a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a trimethylsilyl group, a triphenylsilyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic group A heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, or a substituent Cycloal having 5 to 10 carbon atoms And a straight or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and Ar 7 and Ar 8 may be identical to or different from each other, and may be substituted or substituted Represents an unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted fused polycyclic aromatic group, q represents an integer of 0 to 5. q is 2 or more. When it is an integer, a plurality of Ar 6 bonded to the same benzene ring may be the same or different from each other, and a benzene ring and a substituent substituted on the benzene ring, or a plurality of substituents on the same benzene ring The substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring, provided that Ar 7 and Ar 8 are a hydrogen atom or a deuterium atom. Except) - 請求項５記載の前記一般式（５）が下記一般式（６）で表される、インデノベンゾアゾール環構造を有する化合物。
（式中、Ｒ１１、Ｒ１２は相互に同一でも異なっていてもよく、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ９は重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、トリメチルシリル基、トリフェニルシリル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、置換基を有していてもよい炭素原子数１～６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５～１０のシクロアルキル基、または置換基を有していてもよい炭素原子数２～６の直鎖状もしくは分岐状のアルケニル基を表し、Ａｒ１０、Ａｒ１１は相互に同一でも異なっていてもよく、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表し、ｒは０～５の整数を表す。ｒが２以上の整数である場合、同一のベンゼン環に複数個結合するＡｒ９は相互に同一でも異なってもよい。また、ベンゼン環とベンゼン環に置換された置換基、または同一のベンゼン環に複数置換された置換基同士が、単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成してもよい。但し、Ａｒ１０、Ａｒ１１は水素原子、重水素原子以外とする。） A compound having an indenobenzoazole ring structure, wherein the general formula (5) according to claim 5 is represented by the following general formula (6).
(Wherein, R 11 and R 12 may be the same as or different from each other, and have a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a substituent Represents an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, or a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and Ar 9 represents deuterium Atom, fluorine atom, chlorine atom, cyano group, nitro group, trimethylsilyl group, triphenylsilyl group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensation Polycyclic aromatic group, linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, cycloalkyl having 5 to 10 carbon atoms which may have a substituent Have a group or a substituent R 10 represents a linear or branched alkenyl group having 2 to 6 carbon atoms, and Ar 10 and Ar 11 may be the same as or different from each other, and are substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted Represents an unsubstituted aromatic heterocyclic group or a substituted or unsubstituted fused polycyclic aromatic group, and r represents an integer of 0 to 5. When r is an integer of 2 or more, a plurality of benzene rings may be attached to the same benzene ring Ar 9 which is bonded individually may be the same as or different from each other, and the benzene ring and the substituent substituted to the benzene ring, or the substituents substituted to the same benzene ring may be a single bond, or may be substituted or absent They may be bonded to each other via a substituted methylene group, an oxygen atom or a sulfur atom to form a ring, provided that Ar 10 and Ar 11 are other than a hydrogen atom or a deuterium atom. - 一対の電極とその間に挟まれた少なくとも一層の有機層を有する有機エレクトロルミネッセンス素子において、請求項１～６のいずれか一項に記載のインデノベンゾアゾール環構造を有する化合物が、少なくとも１つの有機層の構成材料として用いられていることを特徴とする有機エレクトロルミネッセンス素子。 An organic electroluminescent device having a pair of electrodes and at least one organic layer sandwiched between the pair of electrodes, wherein the compound having an indenobenzoazole ring structure according to any one of claims 1 to 6 comprises at least one organic layer. An organic electroluminescent device characterized in that it is used as a constituent material of a layer.
- 前記インデノベンゾアゾール環構造を有する化合物が用いられている有機層が電子輸送層である請求項７記載の有機エレクトロルミネッセンス素子。 The organic electroluminescent device according to claim 7, wherein the organic layer in which the compound having an indenobenzoazole ring structure is used is an electron transport layer.
- 前記インデノベンゾアゾール環構造を有する化合物が用いられている有機層が正孔阻止層である請求項７記載の有機エレクトロルミネッセンス素子。 The organic electroluminescent device according to claim 7, wherein the organic layer in which the compound having the indenobenzoazole ring structure is used is a hole blocking layer.
- 前記インデノベンゾアゾール環構造を有する化合物が用いられている有機層が発光層である請求項７記載の有機エレクトロルミネッセンス素子。 The organic electroluminescent device according to claim 7, wherein the organic layer in which the compound having the indenobenzoazole ring structure is used is a light emitting layer.
- 前記インデノベンゾアゾール環構造を有する化合物が用いられている有機層が電子注入層である請求項７記載の有機エレクトロルミネッセンス素子。 The organic electroluminescent device according to claim 7, wherein the organic layer in which the compound having the indenobenzoazole ring structure is used is an electron injection layer.
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| WO2015111943A1 (en) * | 2014-01-23 | 2015-07-30 | 주식회사 두산 | Organic compound, and organic electroluminescent device containing same |
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| US20140319473A1 (en) * | 2013-04-25 | 2014-10-30 | Samsung Display Co., Ltd. | Heterocyclic compound and organic light emitting device comprising the same |
| WO2015111943A1 (en) * | 2014-01-23 | 2015-07-30 | 주식회사 두산 | Organic compound, and organic electroluminescent device containing same |
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