JP6301729B2 - Compound having indoloquinoxaline ring structure and organic electroluminescence device - Google Patents
Compound having indoloquinoxaline ring structure and organic electroluminescence device Download PDFInfo
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- JP6301729B2 JP6301729B2 JP2014099235A JP2014099235A JP6301729B2 JP 6301729 B2 JP6301729 B2 JP 6301729B2 JP 2014099235 A JP2014099235 A JP 2014099235A JP 2014099235 A JP2014099235 A JP 2014099235A JP 6301729 B2 JP6301729 B2 JP 6301729B2
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- unsubstituted aromatic
- condensed polycyclic
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- 150000001875 compounds Chemical class 0.000 title claims description 71
- NXOVZLREWXNIDP-UHFFFAOYSA-N 7h-pyrazino[2,3-c]carbazole Chemical group N1=CC=NC2=C3C4=CC=CC=C4NC3=CC=C21 NXOVZLREWXNIDP-UHFFFAOYSA-N 0.000 title claims description 38
- 238000005401 electroluminescence Methods 0.000 title claims description 20
- 239000010410 layer Substances 0.000 claims description 122
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 74
- 239000000463 material Substances 0.000 claims description 61
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 55
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 230000000903 blocking effect Effects 0.000 claims description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 33
- 229910052801 chlorine Inorganic materials 0.000 claims description 30
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 30
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 30
- 229910052805 deuterium Inorganic materials 0.000 claims description 30
- 125000004431 deuterium atom Chemical group 0.000 claims description 30
- 229910052731 fluorine Inorganic materials 0.000 claims description 30
- 125000001153 fluoro group Chemical group F* 0.000 claims description 30
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 29
- 238000002347 injection Methods 0.000 claims description 25
- 239000007924 injection Substances 0.000 claims description 25
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 23
- 239000012044 organic layer Substances 0.000 claims description 13
- 238000006467 substitution reaction Methods 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 2
- -1 anode Substances 0.000 description 32
- 238000000034 method Methods 0.000 description 27
- 239000010409 thin film Substances 0.000 description 18
- 125000001424 substituent group Chemical group 0.000 description 16
- 230000005525 hole transport Effects 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 229940125904 compound 1 Drugs 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000007740 vapor deposition Methods 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229940125782 compound 2 Drugs 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000001624 naphthyl group Chemical group 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 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 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 125000004076 pyridyl group Chemical group 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 4
- 238000001914 filtration Methods 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
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 3
- 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 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 125000005956 isoquinolyl group Chemical group 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 125000005561 phenanthryl group Chemical group 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000004322 quinolinols Chemical class 0.000 description 3
- 125000005493 quinolyl group Chemical group 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 125000005504 styryl group Chemical group 0.000 description 3
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 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
- 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
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- YJHYDCSMIOBXLS-UHFFFAOYSA-N C1=CC=C(C=C1)N2C3=C(C=C(C=C3)Br)C4=NC5=CC=CC=C5N=C42 Chemical compound C1=CC=C(C=C1)N2C3=C(C=C(C=C3)Br)C4=NC5=CC=CC=C5N=C42 YJHYDCSMIOBXLS-UHFFFAOYSA-N 0.000 description 2
- PKMUHQIDVVOXHQ-HXUWFJFHSA-N C[C@H](C1=CC(C2=CC=C(CNC3CCCC3)S2)=CC=C1)NC(C1=C(C)C=CC(NC2CNC2)=C1)=O Chemical compound C[C@H](C1=CC(C2=CC=C(CNC3CCCC3)S2)=CC=C1)NC(C1=C(C)C=CC(NC2CNC2)=C1)=O PKMUHQIDVVOXHQ-HXUWFJFHSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 0 [C-]*I(c(cc1)ccc1-c1c(cc(cc2)-c(cc3c4nc(cccc5)c5nc44)ccc3[n]4-c3ccccc3)c2c(-c2ccc(*)cc2)c2c1ccc(-c1ccccc1)c2)=C Chemical compound [C-]*I(c(cc1)ccc1-c1c(cc(cc2)-c(cc3c4nc(cccc5)c5nc44)ccc3[n]4-c3ccccc3)c2c(-c2ccc(*)cc2)c2c1ccc(-c1ccccc1)c2)=C 0.000 description 2
- HXGDTGSAIMULJN-UHFFFAOYSA-N acenaphthylene Chemical compound C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000005577 anthracene group Chemical group 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229940126179 compound 72 Drugs 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- BJXYHBKEQFQVES-NWDGAFQWSA-N enpatoran Chemical compound N[C@H]1CN(C[C@H](C1)C(F)(F)F)C1=C2C=CC=NC2=C(C=C1)C#N BJXYHBKEQFQVES-NWDGAFQWSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 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 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000007978 oxazole derivatives Chemical class 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 150000005041 phenanthrolines Chemical class 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
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 125000001725 pyrenyl group Chemical group 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- 239000013638 trimer Substances 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
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- 125000006617 triphenylamine group Chemical group 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VUEGYUOUAAVYAS-JGGQBBKZSA-N (6ar,9s,10ar)-9-(dimethylsulfamoylamino)-7-methyl-6,6a,8,9,10,10a-hexahydro-4h-indolo[4,3-fg]quinoline Chemical compound C1=CC([C@H]2C[C@@H](CN(C)[C@@H]2C2)NS(=O)(=O)N(C)C)=C3C2=CNC3=C1 VUEGYUOUAAVYAS-JGGQBBKZSA-N 0.000 description 1
- MVUDLJXJTYSUGF-UHFFFAOYSA-N (9,10-diphenylanthracen-2-yl)boronic acid Chemical compound C=12C=CC=CC2=C(C=2C=CC=CC=2)C2=CC(B(O)O)=CC=C2C=1C1=CC=CC=C1 MVUDLJXJTYSUGF-UHFFFAOYSA-N 0.000 description 1
- DEVSOMFAQLZNKR-RJRFIUFISA-N (z)-3-[3-[3,5-bis(trifluoromethyl)phenyl]-1,2,4-triazol-1-yl]-n'-pyrazin-2-ylprop-2-enehydrazide Chemical compound FC(F)(F)C1=CC(C(F)(F)F)=CC(C2=NN(\C=C/C(=O)NNC=3N=CC=NC=3)C=N2)=C1 DEVSOMFAQLZNKR-RJRFIUFISA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical class NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
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- 238000009832 plasma treatment Methods 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
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- 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
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- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
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に適した化合物と該素子に関するものであり、詳しくはインドロキノキサリン環構造を有する化合物と、該化合物を用いた有機エレクトロルミネッセンス素子に関するものである。 The present invention relates to a compound suitable for an organic electroluminescence element which is a self-luminous element suitable for various display devices and the element, and more specifically, a compound having an indoloquinoxaline ring structure, and an organic compound using the compound. The present invention relates to an electroluminescence element.
有機エレクトロルミネッセンス素子は自己発光性素子であるため、液晶素子にくらべて明るく視認性に優れ、鮮明な表示が可能であるため、活発な研究がなされてきた。 Since organic electroluminescent elements are self-luminous elements, they have been actively researched because they are brighter and more visible than liquid crystal elements and can display clearly.
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エレクトロルミネッセンス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's C.I. W. Tang et al. Have made organic electroluminescence elements using organic materials practical by developing a laminated structure element that shares various roles with each material. They laminate a phosphor capable of transporting electrons and an organic substance capable of transporting holes, and inject both charges into the phosphor layer to emit light. High luminance of 1000 cd / m 2 or more can be obtained (for example, see Patent Document 1 and Patent Document 2).
現在まで、有機エレクトロルミネッセンス素子の実用化のために多くの改良がなされ、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ている（例えば、非特許文献1参照）。 To date, many improvements have been made for the practical application of organic electroluminescence devices, and various roles have been further subdivided, and sequentially on the substrate, anode, hole injection layer, hole transport layer, light emitting layer, electron High efficiency and durability are achieved by an electroluminescent device provided with a 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、燐光発光体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）
Further, the use of triplet excitons has been attempted for the purpose of further improving the luminous efficiency, and the use of phosphorescent emitters has been studied (for example, see Non-Patent Document 2).
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% with a device using a thermally activated delayed fluorescent material. (For example, see 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、蛍光体や燐光発光体をドープして作製することもできる。上記の非特許文献１および２に記載されているように、有機エレクトロルミネッセンス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。 The light-emitting layer can also be produced by doping a charge transporting compound generally called a host material with a phosphor or a phosphorescent material. As described in Non-Patent Documents 1 and 2 above, selection of an organic material in an organic electroluminescence element greatly affects various characteristics such as efficiency and durability of the element.
有機エレクトロルミネッセンス素子においては、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、電子の移動速度より正孔の移動速度が速いため、正孔の一部が発光層を通り抜けてしまうことによる効率低下が問題となる。そのため電子の移動速度の速い電子輸送材料が求められている。 In the organic electroluminescence device, the light injected from both electrodes is recombined in the light emitting layer to obtain light emission. However, since the hole moving speed is faster than the electron moving speed, some of the holes are in the light emitting layer. There is a problem that the efficiency decreases due to passing through. Therefore, an electron transport material having a high electron moving speed is demanded.
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、電子の移動度が遅く、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。 Tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq 3 ), which is a typical luminescent material, is generally used as an electron transport material, but has a slow electron mobility and a work function of 5. Since it is 6 eV, it cannot be said that the hole blocking performance is sufficient.
正孔の一部が発光層を通り抜けてしまうことを防ぎ、発光層での電荷再結合の確率を向上させる方策には、正孔阻止層を挿入する方法がある。正孔阻止材料としてはこれまでに、トリアゾール誘導体（例えば、特許文献３参照）やバソクプロイン（以後、ＢＣＰと略称する）、アルミニウムの混合配位子錯体［アルミニウム（III）ビス（２−メチル−８−キノリナート）−４−フェニルフェノレート（以後、ＢＡｌｑと略称する）］（例えば、非特許文献２参照）などが提案されている。 As a method for preventing a part of holes from passing through the light emitting layer and improving the probability of charge recombination in the light emitting layer, there is a method of inserting a hole blocking layer. As hole blocking materials, triazole derivatives (see, for example, Patent Document 3), bathocuproine (hereinafter abbreviated as BCP), mixed ligand complexes of aluminum [aluminum (III) bis (2-methyl-8) -Quinolinato) -4-phenylphenolate (hereinafter abbreviated as BAlq)] (for example, see Non-Patent Document 2).
一方、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３参照）。 On the other hand, 3- (4-biphenylyl) -4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole (hereinafter abbreviated as TAZ) as an electron transport material having excellent hole blocking properties. Have been proposed (see, for example, Patent Document 3).
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、有機エレクトロルミネッセンス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, an electron transporting hole blocking layer laminated on the cathode side of a fluorescent light emitting layer or phosphorescent light emitting layer produced by vacuum deposition or coating. And contributes to high efficiency of the organic electroluminescence 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、有機エレクトロルミネッセンス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 problem in TAZ, and it has been necessary to produce an organic electroluminescence element in combination with an electron transport material with 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。 BCP also has a high work function of 6.7 eV and a high hole blocking ability, but its glass transition point (Tg) is as low as 83 ° C., so that the stability of the thin film is poor and it functions sufficiently as a hole blocking layer. I can't 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。有機エレクトロルミネッセンス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。 Any material has insufficient film stability or insufficient function of blocking holes. In order to improve the device characteristics of an organic electroluminescence device, an organic compound having excellent electron injection / transport performance and hole blocking capability and high stability in a thin film state is required.
これらを改良した化合物として、アントラセン環構造とベンズイミダゾール環構造を有する化合物が提案されている（例えば、特許文献４参照）。
しかしながら、これらの化合物を電子注入層または／および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、まだ十分とはいえず、低駆動電圧化や、更なる高発光効率化、特に高電流効率化が求められている。
As compounds obtained by improving these, compounds having an anthracene ring structure and a benzimidazole ring structure have been proposed (see, for example, Patent Document 4).
However, in devices using these compounds in the electron injection layer and / or the electron transport layer, although the light emission efficiency has been improved, it has not been sufficient yet. In particular, there is a demand for higher current efficiency.
本発明の目的は、高効率、高耐久性の有機エレクトロルミネッセンス素子用の材料として、電子の注入・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、さらにこの化合物を用いて、高効率、高耐久性の有機エレクトロルミネッセンス素子を提供することにある。 The object of the present invention is as a material for an organic electroluminescence device with high efficiency and high durability, excellent electron injection / transport performance, hole blocking ability, and excellent stability in a thin film state. It is another object of the present invention to provide an organic electroluminescent device having high efficiency and high durability using the 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）電子の移動速度が速いこと、（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エレクトロルミネッセンス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をあげることができる。 The physical characteristics of the organic compound to be provided by the present invention are as follows: (1) good electron injection characteristics, (2) high electron transfer speed, and (3) hole blocking ability. It can be mentioned that it is excellent and (4) the thin film state is stable. The physical characteristics of the organic electroluminescent device to be provided by the present invention include (1) high luminous efficiency and power efficiency, (2) low emission start voltage, and (3) practical use. It can be mentioned that the drive voltage is low.
そこで本発明者らは上記の目的を達成するために、インドロキノキサリン環構造が高い電子輸送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、インドロキノキサリン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エレクトロルミネッセンス素子を試作し、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 pay attention to the fact that the indoloquinoxaline ring structure has a high electron transporting ability and excellent heat resistance. As a result of designing and chemically synthesizing a compound having a structure, experimentally producing various organic electroluminescence devices using the compound, and intensively evaluating the characteristics of the devices, the present invention has been completed.
１）すなわち本発明は、下記一般式（１）で表されるインドロキノキサリン環構造を有する化合物である。 1) That is, the present invention is a compound having an indoloquinoxaline ring structure represented by the following general formula (1).
（式中、Ａｒ１は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、Ａ、Ｂは同一でも異なってもよく、単結合、あるいは置換もしくは無置換の芳香族炭化水素の２価基、置換もしくは無置換の芳香族複素環の２価基または置換もしくは無置換の縮合多環芳香族の２価基を表し、Ｃは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、Ｒ１〜Ｒ７は、同一でも異なってもよく水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、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、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、Ｒ８は互いに同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、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を表し、ｐ、ｑは、ｐとｑの和が９となる関係を維持しつつ、ｐは７または８を表し、ｑは１または２を表す。） (In the formula, Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and A and B are the same or different. A single bond, a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a divalent group of a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic aromatic divalent group C represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group, and R 1 to R 7 may be the same May be different hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl group, linear or branched alkyl group having 1 to 6 carbon atoms, substituted or unsubstituted aromatic carbonization Hydrogen group, substitution Or an unsubstituted aromatic heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group, R 8 may be the same or different from each other, and may be a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, cyano. A group, a trifluoromethyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, and p and q maintain a relationship where the sum of p and q is 9, p is 7 or 8 and q represents 1 or 2.)
２）また本発明は、下記一般式（１ａ）で表される上記１）記載のインドロキノキサリン環構造を有する化合物である。 2) Moreover, this invention is a compound which has the indoloquinoxaline ring structure of said 1) description represented with the following general formula (1a).
（式中、Ａｒ１は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、Ａ、Ｂは同一でも異なってもよく、単結合、あるいは置換もしくは無置換の芳香族炭化水素の２価基、置換もしくは無置換の芳香族複素環の２価基または置換もしくは無置換の縮合多環芳香族の２価基を表し、Ｃ１、Ｃ２は、同一でも異なっ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、Ｒ１〜Ｒ７は、同一でも異なってもよく水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、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、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、Ｒ８は、互いに同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、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を表し、ｐは７を表す。） (In the formula, Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and A and B are the same or different. A single bond, a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a divalent group of a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic aromatic divalent group C 1 and C 2 may be the same or different and each represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group. R 1 to R 7, which may be the same or different, are a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched group having 1 to 6 carbon atoms Alkyl group, substitution or Represents an unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group, and R 8 may be the same or different from each other, and may be a hydrogen atom, A deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, and p represents 7.
３）また本発明は、下記一般式（１ｂ）で表される上記１）記載のインドロキノキサリン環構造を有する化合物である。 3) Moreover, this invention is a compound which has the indoloquinoxaline ring structure of said 1) description represented with the following general formula (1b).
（式中、Ａｒ１は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、Ａ、Ｂは同一でも異なってもよく、単結合、あるいは置換もしくは無置換の芳香族炭化水素の２価基、置換もしくは無置換の芳香族複素環の２価基または置換もしくは無置換の縮合多環芳香族の２価基を表し、Ｃ１は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、Ｒ１〜Ｒ７は、同一でも異なってもよく水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、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、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、Ｒ８は、互いに同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、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を表し、ｐは８を表す。） (In the formula, Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and A and B are the same or different. A single bond, a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a divalent group of a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic aromatic divalent group C 1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group, and R 1 to R 7 are the same However, they may be different from each other. Hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl group, linear or branched alkyl group having 1 to 6 carbon atoms, substituted or unsubstituted aromatic Hydrocarbon group, Or represents an unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, R 8 may be the same or different, a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano A group, a trifluoromethyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, and p represents 8.)
４）また本発明は、下記一般式（１ａ−１）で表される、上記２）記載のインドロキノキサリン環構造を有する化合物である。 4) Moreover, this invention is a compound which has the indoloquinoxaline ring structure of the said 2) description represented by the following general formula (1a-1).
（式中、Ａｒ１は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、Ａ、Ｂは同一でも異なってもよく、単結合、あるいは置換もしくは無置換の芳香族炭化水素の２価基、置換もしくは無置換の芳香族複素環の２価基または置換もしくは無置換の縮合多環芳香族の２価基を表し、Ｃ１、Ｃ２は、同一でも異なっ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、Ｒ１〜Ｒ７は、同一でも異なってもよく水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、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、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、Ｒ８は、互いに同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、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を表し、ｐは７を表す。） (In the formula, Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and A and B are the same or different. A single bond, a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a divalent group of a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic aromatic divalent group C 1 and C 2 may be the same or different and each represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group. R 1 to R 7, which may be the same or different, are a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched group having 1 to 6 carbon atoms Alkyl group, substitution or Represents an unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group, and R 8 may be the same or different from each other, and may be a hydrogen atom, A deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, and p represents 7.
５）また本発明は、下記一般式（１ａ−２）で表される、上記２）記載のインドロキノキサリン環構造を有する化合物である。 5) Moreover, this invention is a compound which has the indoloquinoxaline ring structure of the said 2) description represented by the following general formula (1a-2).
（式中、Ａｒ１は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、Ａ、Ｂは同一でも異なってもよく、単結合、あるいは置換もしくは無置換の芳香族炭化水素の２価基、置換もしくは無置換の芳香族複素環の２価基または置換もしくは無置換の縮合多環芳香族の２価基を表し、Ｃ１、Ｃ２は、同一でも異なっ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、Ｒ１〜Ｒ７は、同一でも異なってもよく水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、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、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、Ｒ８は、互いに同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、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を表し、ｐは７を表す。） (In the formula, Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and A and B are the same or different. A single bond, a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a divalent group of a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic aromatic divalent group C 1 and C 2 may be the same or different and each represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group. R 1 to R 7, which may be the same or different, are a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched group having 1 to 6 carbon atoms Alkyl group, substitution or Represents an unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group, and R 8 may be the same or different from each other, and may be a hydrogen atom, A deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, and p represents 7.
６）また本発明は、下記一般式（１ａ−３）で表される、上記２）記載のインドロキノキサリン環構造を有する化合物である。 6) Moreover, this invention is a compound which has the indoloquinoxaline ring structure of the said 2) description represented by the following general formula (1a-3).
（式中、Ａｒ１は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、Ａ、Ｂは同一でも異なってもよく、単結合、あるいは置換もしくは無置換の芳香族炭化水素の２価基、置換もしくは無置換の芳香族複素環の２価基または置換もしくは無置換の縮合多環芳香族の２価基を表し、Ｃ１、Ｃ２は、同一でも異なっ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、Ｒ１〜Ｒ７は、同一でも異なってもよく水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、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、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、Ｒ８は、互いに同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、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を表し、ｐは７を表す。） (In the formula, Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and A and B are the same or different. A single bond, a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a divalent group of a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic aromatic divalent group C 1 and C 2 may be the same or different and each represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group. R 1 to R 7, which may be the same or different, are a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched group having 1 to 6 carbon atoms Alkyl group, substitution or Represents an unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group, and R 8 may be the same or different from each other, and may be a hydrogen atom, A deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, and p represents 7.
７）また本発明は、下記一般式（１ｂ−１）で表される、上記３）記載のインドロキノキサリン環構造を有する化合物である。 7) Moreover, this invention is a compound which has the indoloquinoxaline ring structure of the said 3) description represented by the following general formula (1b-1).
（式中、Ａｒ１は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、Ａ、Ｂは同一でも異なってもよく、単結合、あるいは置換もしくは無置換の芳香族炭化水素の２価基、置換もしくは無置換の芳香族複素環の２価基または置換もしくは無置換の縮合多環芳香族の２価基を表し、Ｃ１は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、Ｒ１〜Ｒ７は、同一でも異なってもよく水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、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、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、Ｒ８は、互いに同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、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を表し、ｐは８を表す。） (In the formula, Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and A and B are the same or different. A single bond, a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a divalent group of a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic aromatic divalent group C 1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group, and R 1 to R 7 are the same However, they may be different from each other. Hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl group, linear or branched alkyl group having 1 to 6 carbon atoms, substituted or unsubstituted aromatic Hydrocarbon group, Or represents an unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, R 8 may be the same or different, a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano A group, a trifluoromethyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, and p represents 8.)
８）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エレクトロルミネッセンス素子において、上記１）記載のインドロキノキサリン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である。 8) Further, according to the present invention, in the organic electroluminescence device having a pair of electrodes and at least one organic layer sandwiched between them, the compound having an indoloquinoxaline ring structure described in 1) above is formed of at least one organic layer. It is an organic electroluminescent element characterized by being used as a constituent material.
９）また、本発明は、前記有機層が電子輸送層である、上記８）記載の有機エレクトロルミネッセンス素子である。 9) Moreover, this invention is an organic electroluminescent element of the said 8) description whose said organic layer is an electron carrying layer.
１０）また、本発明は、前記有機層が正孔阻止層である、上記８）記載の有機エレクトロルミネッセンス素子である。 10) Moreover, this invention is an organic electroluminescent element of the said 8) description whose said organic layer is a hole-blocking layer.
１１）また、本発明は、前記有機層が発光層である、上記８）記載の有機エレクトロルミネッセンス素子である。 11) Moreover, this invention is an organic electroluminescent element of the said 8) description whose said organic layer is a light emitting layer.
１２）また、本発明は、前記有機層が電子注入層である、上記８）記載の有機エレクトロルミネッセンス素子である。 12) Moreover, this invention is an organic electroluminescent element of the said 8) description whose said organic layer is an electron injection layer.
一般式（１）中のＡｒ１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、具体的に、フェニル基、ビフェニリル基、ターフェニリル基、テトラキスフェニル基、スチリル基、ナフチル基、アントリル基、アセナフテニル基、フェナントリル基、フルオレニル基、インデニル基、ピレニル基、トリアジル基、ピリジル基、ピリミジル基、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、アクリジニル基のような基をあげることができる。 “Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” or “substituted or unsubstituted condensed polycyclic fragrance represented by Ar 1 in general formula (1) As the “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “fused polycyclic aromatic group” in the “group group”, specifically, phenyl group, biphenylyl group, terphenylyl group, tetrakisphenyl group, styryl group , Naphthyl, anthryl, acenaphthenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, triazyl, pyridyl, pyrimidyl, furyl, pyrrolyl, thienyl, quinolyl, isoquinolyl, benzofuranyl, benzo Thienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalyl, Examples thereof include azoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, naphthyridinyl group, phenanthrolinyl group and acridinyl group.
一般式（１）中のＡｒ１で表される、「置換芳香族炭化水素基」、「置換芳香族複素環基」または「置換縮合多環芳香族基」における「置換基」として、具体的に、重水素原子、フッ素原子、塩素原子、シアノ基、トリフルオロメチル基、水酸基、ニトロ基、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、シクロペンチル基、シクロヘキシル基、炭素原子数１ないし６の直鎖状もしくは分岐状のアルコキシ基、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で置換されたジアルキルアミノ基、フェニル基、ナフチル基、アントリル基、フルオレニル基、スチリル基、ピリジル基、ピリドインドリル基、キノリル基、イソキノリル基、ベンゾチアゾリル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。
ここで、「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」および「炭素原子数１ないし６の直鎖状もしくは分岐状のアルコキシ基」における「アルキル基」部分としては、一般式（１）中のＲ１〜Ｒ7で表される、「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」として例示される基と同じものをあげることができる。
Specific examples of the “substituent” in the “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group” represented by Ar 1 in the general formula (1) Deuterium atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl group, hydroxyl group, nitro group, linear or branched alkyl group having 1 to 6 carbon atoms, cyclopentyl group, cyclohexyl group, carbon atom A linear or branched alkoxy group having 1 to 6 carbon atoms, a dialkylamino group substituted with a linear or branched alkyl group having 1 to 6 carbon atoms, phenyl group, naphthyl group, anthryl group, fluorenyl group , A styryl group, a pyridyl group, a pyridoindolyl group, a quinolyl group, an isoquinolyl group, a benzothiazolyl group, and these substituents are The substituents exemplified above may be substituted.
Here, the “alkyl group” moiety in the “linear or branched alkyl group having 1 to 6 carbon atoms” and the “linear or branched alkoxy group having 1 to 6 carbon atoms” Examples thereof include the same groups as those exemplified as “a linear or branched alkyl group having 1 to 6 carbon atoms” represented by R 1 to R 7 in formula (1).
一般式（１）中のＡ、Ｂで表される、「置換もしくは無置換の芳香族炭化水素の２価基」、「置換もしくは無置換の芳香族複素環の２価基」または「置換もしくは無置換の縮合多環芳香族の２価基」における「置換もしくは無置換の芳香族炭化水素」、「置換もしくは無置換の芳香族複素環」または「置換もしくは無置換の縮合多環芳香族」の「芳香族炭化水素」、「芳香族複素環」または「縮合多環芳香族」としては、具体的に、ベンゼン、ビフェニル、ターフェニル、テトラキスフェニル、スチレン、ナフタレン、アントラセン、アセナフタレン、フルオレン、フェナントレン、インダン、ピレン、ピリジン、ピリミジン、トリアジン、フラン、ピラン、チオフェン、キノリン、イソキノリン、ベンゾフラン、ベンゾチオフェン、インドリン、カルバゾール、カルボリン、ベンゾオキサゾール、ベンゾチアゾール、キノキサリン、ベンゾイミダゾール、ピラゾール、ジベンゾフラン、ジベンゾチオフェン、ナフチリジン、フェナントロリン、アクリジニンなどをあげることができる。
そして、一般式（１）中のＡ、Ｂで表される「置換もしくは無置換の芳香族炭化水素の２価基」、「置換もしくは無置換の芳香族複素環の２価基」または「置換もしくは無置換の縮合多環芳香族の２価基」は、上記「芳香族炭化水素」、「芳香族複素環」または「縮合多環芳香族」から水素原子を２個取り除いてできる２価基を表す。
Represented by A and B in the general formula (1), “a divalent group of a substituted or unsubstituted aromatic hydrocarbon”, “a divalent group of a substituted or unsubstituted aromatic heterocyclic ring” or “substituted or "Substituted or unsubstituted aromatic hydrocarbon", "Substituted or unsubstituted aromatic heterocycle" or "Substituted or unsubstituted condensed polycyclic aromatic" in "Unsubstituted fused polycyclic aromatic divalent group" Specific examples of the “aromatic hydrocarbon”, “aromatic heterocycle” or “fused polycyclic aromatic” of benzene, biphenyl, terphenyl, tetrakisphenyl, styrene, naphthalene, anthracene, acenaphthalene, fluorene, Phenanthrene, indane, pyrene, pyridine, pyrimidine, triazine, furan, pyran, thiophene, quinoline, isoquinoline, benzofuran, benzothiophene, India Emissions, carbazole, can carboline, benzoxazole, benzothiazole, quinoxaline, benzimidazole, pyrazole, dibenzofuran, dibenzothiophene, naphthyridine, phenanthroline, and the like Akurijinin.
In addition, “a divalent group of a substituted or unsubstituted aromatic hydrocarbon”, “a divalent group of a substituted or unsubstituted aromatic heterocycle” represented by A or B in the general formula (1), or “substituted” Alternatively, the “unsubstituted fused polycyclic aromatic divalent group” is a divalent group formed by removing two hydrogen atoms from the above “aromatic hydrocarbon”, “aromatic heterocycle” or “fused polycyclic aromatic”. Represents.
一般式（１）中のＡ、Ｂで表される、「置換もしくは無置換の芳香族炭化水素の２価基」、「置換もしくは無置換の芳香族複素環の２価基」または「置換もしくは無置換の縮合多環芳香族の２価基」における「置換芳香族炭化水素」、「置換芳香族複素環」または「置換縮合多環芳香族」の「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；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；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、フェナントリル基、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；スチリル基、ナフチルビニル基などのアリールビニル基；アセチル基、ベンゾイル基などのアシル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。
Represented by A and B in the general formula (1), “a divalent group of a substituted or unsubstituted aromatic hydrocarbon”, “a divalent group of a substituted or unsubstituted aromatic heterocyclic ring” or “substituted or As the “substituent” of “substituted aromatic hydrocarbon”, “substituted aromatic heterocycle” or “substituted condensed polycyclic aromatic” in “unsubstituted fused polycyclic aromatic divalent group”, specifically, Deuterium atom, cyano group, nitro group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert- A linear or branched alkyl group having 1 to 6 carbon atoms such as butyl group, n-pentyl group, isopentyl group, neopentyl group and n-hexyl group; carbon such as methyloxy group, ethyloxy group and propyloxy group Linear or branched alkyloxy groups having 1 to 6 members; alkenyl groups such as allyl groups; aryloxy groups such as phenyloxy groups and tolyloxy groups; arylalkyloxy groups such as benzyloxy groups and phenethyloxy groups; Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as phenyl, biphenylyl, terphenylyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, triphenylenyl Group: pyridyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, Aromatic heterocyclic groups such as lazolyl group, dibenzofuranyl group, dibenzothienyl group and carbolinyl group; aryl vinyl groups such as styryl group and naphthyl vinyl group; and groups such as acyl groups such as acetyl group and benzoyl group These substituents may be further substituted with the substituents exemplified above.
These 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.
一般式（１）、一般式（１ａ）、一般式（１ｂ）中のＣ、Ｃ１、Ｃ２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、具体的に、上記の一般式（１）中のＡｒ１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」に関して示したものと同様のものをあげることができる。
そして、これらの基は置換基を有していてよく、置換基として、上記の一般式（１）中のＡｒ１で表される「置換芳香族炭化水素基」、「置換芳香族複素環基」または「置換縮合多環芳香族基」における「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。
一般式（１）中のＣ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」は、複数個存在する場合（ｑが２の場合）、互いに同一でも異なってもよい。
Formula (1), the general formula (1a), C in formula (1b), "substituted or unsubstituted aromatic hydrocarbon group" represented by C 1, C 2, "substituted or unsubstituted aromatic As the “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “fused polycyclic aromatic group” in the “aromatic heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic group”, specifically, In the above general formula (1), “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” represented by Ar 1 or “substituted or unsubstituted condensed hydrocarbon group” The same thing as what was shown regarding the "aromatic hydrocarbon group" in the "ring aromatic group", "aromatic heterocyclic group", or "condensed polycyclic aromatic group" can be mention | raise | lifted.
These groups may have a substituent, and examples of the substituent include “substituted aromatic hydrocarbon group” and “substituted aromatic heterocyclic group” represented by Ar 1 in the general formula (1). Or the same as those shown for the “substituent” in the “substituted condensed polycyclic aromatic group”, and the possible embodiments are also the same.
“Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic group” represented by C in formula (1) "May be the same as or different from each other when a plurality of""are present (when q is 2).
一般式（１）中のＲ１〜Ｒ７で表される、「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」としては、具体的に、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、２−メチルプロピル基、ｔ−ブチル基、ｎ−ペンチル基、３−メチルブチル基、ｔｅｒｔ−ペンチル基、ｎ−ヘキシル基、ｉｓｏ−ヘキシル基およびｔｅｒｔ−ヘキシル基をあげることができる。 Specific examples of the “linear or branched alkyl group having 1 to 6 carbon atoms” represented by R 1 to R 7 in the general formula (1) include a methyl group, an ethyl group, n- Propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, t-butyl group, n-pentyl group, 3-methylbutyl group, tert-pentyl group, n-hexyl group, iso-hexyl group and tert -A hexyl group can be mentioned.
一般式（１）中のＲ１〜Ｒ７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、具体的に、上記の一般式（１）中のＡｒ１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」に関して示したものと同様のものをあげることができる。
また、これらの基は置換基を有していてよく、置換基として、上記の一般式（１）中のＡｒ１で表される「置換芳香族炭化水素基」、「置換芳香族複素環基」または「置換縮合多環芳香族基」における「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 or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” represented by R 1 to R 7 in the general formula (1), or “substituted or unsubstituted condensed poly group” The “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “fused polycyclic aromatic group” in the “ring aromatic group” is specifically represented by Ar 1 in the above general formula (1). “Aromatic hydrocarbon group” in “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic group”, The thing similar to what was shown regarding "aromatic heterocyclic group" or "condensed polycyclic aromatic group" can be mention | raise | lifted.
In addition, these groups may have a substituent, and as the substituent, a “substituted aromatic hydrocarbon group” or a “substituted aromatic heterocyclic group” represented by Ar 1 in the general formula (1) above. Or the same as those shown for the “substituent” in the “substituted condensed polycyclic aromatic group”, and the possible embodiments are also the same.
一般式（１）中のＲ８で表される、「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」としては、具体的に、上記の一般式（１）中のＲ１〜Ｒ７で表される、「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」に関して示したものと同様のものをあげることができる。
また、複数個存在するＲ８は、互いに同一でも異なってもよい。
Specific examples of the “linear or branched alkyl group having 1 to 6 carbon atoms” represented by R 8 in the general formula (1) include R 1 in the general formula (1). expressed in to R 7, it may be mentioned the same ones as illustrated for the "straight-chain or branched alkyl group having 1 to 6 carbon atoms."
A plurality of R 8 may be the same as or different from each other.
一般式（１）中のｐ、ｑは、ｐとｑの和（ｐ＋ｑ）が９となる関係を維持するものとし、ｐは７または８を表し、ｑは１または２を表す。 In the general formula (1), p and q maintain the relationship that the sum of p and q (p + q) is 9, p represents 7 or 8, and q represents 1 or 2.
一般式（１）中のＡ、Ｂとしては、芳香族炭化水素の２価基または芳香族複素環の２価基」、もしくは単結合が好ましく、ベンゼンから誘導される２価基またはピリジンから誘導される２価基、もしくは単結合がより好ましく、単結合が特に好ましい。
一般式（１）中のＡｒ１としては、フェニル基、ビフェニル基、ナフチル基、フルオレニル基、ピリジル基、ジベンゾフラニル基、ジベンゾチエニル基が好ましい。
一般式（１）、一般式（１ａ）、一般式（１ｂ）中のＣ、Ｃ１、Ｃ２としては、フェニル基、ビフェニル基、ナフチル基、フェナントリル基、フルオレニル基、ピリジル基、ジベンゾフラニル基、ジベンゾチエニル基が好ましい。
As A and B in the general formula (1), a divalent group of an aromatic hydrocarbon or a divalent group of an aromatic heterocycle ", or a single bond is preferable, derived from a divalent group derived from benzene or pyridine. A divalent group or a single bond is more preferable, and a single bond is particularly preferable.
Ar 1 in the general formula (1) is preferably a phenyl group, a biphenyl group, a naphthyl group, a fluorenyl group, a pyridyl group, a dibenzofuranyl group, or a dibenzothienyl group.
C, C 1 and C 2 in the general formula (1), general formula (1a) and general formula (1b) are phenyl group, biphenyl group, naphthyl group, phenanthryl group, fluorenyl group, pyridyl group, dibenzofuranyl. And a dibenzothienyl group are preferred.
本発明の一般式（１）で表される、インドロキノキサリン環構造を有する化合物は新規な化合物であり、従来の電子輸送材料より電子の移動が速く、優れた正孔の阻止能力を有し、かつ薄膜状態が安定である。 The compound represented by the general formula (1) of the present invention, which has an indoloquinoxaline ring structure, is a novel compound, has faster electron movement than conventional electron transport materials, and has excellent hole blocking ability. In addition, the thin film state is stable.
本発明の一般式（１）で表される、インドロキノキサリン環構造を有する化合物は、有機エレクトロルミネッセンス素子（以後、有機ＥＬ素子と略称する。）の電子注入層および／または電子輸送層の構成材料として使用することができる。従来の材料に比べて電子の注入・移動速度の高い材料を用いることにより、電子輸送層から発光層への電子輸送効率が向上して、発光効率が向上すると共に、駆動電圧が低下して、有機ＥＬ素子の耐久性が向上するという作用を有する。 The compound having an indoloquinoxaline ring structure represented by the general formula (1) of the present invention is a structure of an electron injection layer and / or an electron transport layer of an organic electroluminescence device (hereinafter abbreviated as an organic EL device). Can be used as material. By using a material having a higher electron injection / movement speed than conventional materials, the electron transport efficiency from the electron transport layer to the light emitting layer is improved, the light emission efficiency is improved, and the driving voltage is lowered, It has the effect | action that durability of an organic EL element improves.
本発明の一般式（１）で表される、インドロキノキサリン環構造を有する化合物は、有機ＥＬ素子の正孔阻止層の構成材料としても使用することができる。優れた正孔の阻止能力と共に従来の材料に比べて電子輸送性に優れ、かつ薄膜状態の安定性の高い材料を用いることにより、高い発光効率を有しながら、駆動電圧が低下し、電流耐性が改善されて、有機ＥＬ素子の最大発光輝度が向上するという作用を有する。 The compound having an indoloquinoxaline ring structure represented by the general formula (1) of the present invention can also be used as a constituent material of a hole blocking layer of an organic EL device. By using a material with excellent hole-blocking ability and electron transportability compared to conventional materials and high stability in the thin film state, the driving voltage is lowered and current resistance is maintained while having high luminous efficiency. Is improved and the maximum light emission luminance of the organic EL element is improved.
本発明の一般式（１）で表される、インドロキノキサリン環構造を有する化合物は、有機ＥＬ素子の発光層の構成材料としても使用することができる。従来の材料に比べて電子輸送性に優れ、かつバンドギャップの広い本発明の材料を発光層のホスト材料として用い、ドーパントと呼ばれている蛍光発光体や燐光発光体を担持させて、発光層として用いることにより、駆動電圧が低下し、発光効率が改善された有機ＥＬ素子を実現できるという作用を有する。 The compound having an indoloquinoxaline ring structure represented by the general formula (1) of the present invention can also be used as a constituent material of a light emitting layer of an organic EL device. Using the material of the present invention, which has an excellent electron transporting property and a wide band gap as compared with conventional materials, as a host material of the light emitting layer, a fluorescent light emitting material or a phosphorescent light emitting material called a dopant is supported, and the light emitting layer As a result, it is possible to realize an organic EL element with reduced driving voltage and improved luminous efficiency.
本発明の有機ＥＬ素子は、従来の電子輸送材料より電子の移動が速く、優れた正孔の阻止能力を有し、かつ薄膜状態が安定な、インドロキノキサリン環構造を有する化合物を用いているため、高効率、高耐久性を実現することが可能となった。 The organic EL device of the present invention uses a compound having an indoloquinoxaline ring structure, which has faster electron transfer than conventional electron transport materials, has excellent hole blocking ability, and is stable in a thin film state. Therefore, high efficiency and high durability can be realized.
本発明のインドロキノキサリン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、正孔阻止層あるいは発光層の構成材料として有用であり、正孔阻止能力に優れ、薄膜状態が安定で、耐熱性に優れている。本発明の有機ＥＬ素子は発光効率および電力効率が高く、このことにより素子の実用駆動電圧を低くさせることができる。発光開始電圧を低くさせ、耐久性を改良することができる。 The compound having an indoloquinoxaline ring structure of the present invention is useful as a constituent material of an electron injection layer, an electron transport layer, a hole blocking layer or a light emitting layer of an organic EL device, and has an excellent hole blocking ability and a thin film state. It is stable and has excellent heat resistance. The organic EL device of the present invention has high luminous efficiency and high power efficiency, which can reduce the practical driving voltage of the device. The emission start voltage can be lowered and the durability can be improved.
本発明の一般式（１）で表されるインドロキノキサリン環構造を有する化合物は、新規な化合物であり、これらの化合物は例えば、以下のように合成できる。まず、相当する置換基を有する１，２−ジアミノベンゼン誘導体とイサチン誘導体を酸溶媒下にて反応させることによって相当する置換基を有するインドロキノキサリン誘導体を合成することができる（例えば、特許文献５参照）。このインドロキノキサリン誘導体と、種々の芳香族炭化水素化合物、縮合多環芳香族化合物または芳香族複素環化合物のハロゲン化物とのＵｌｌｍａｎｎ反応、Ｂｕｃｈｗａｒｄ−Ｈａｒｔｗｉｇ反応などの縮合反応を行うことによって、６位にアリール基を導入した、相当する置換基を有するインドロキノキサリン誘導体を合成することができる。このインドロキノキサリン誘導体に対しＮ−ブロモコハク酸イミドなどによるブロモ化を行うことによって、９位がブロモ化されたインドロキノキサリン誘導体を合成することができる。ここで、ブロモ化の試薬、条件を変更することによって、置換位置の異なるブロモ置換体を得ることができる。このブロモ置換体と既知の方法によって合成したアントラセン環構造を有するボロン酸またはボロン酸エステル（例えば、非特許文献６参照）とのＳｕｚｕｋｉカップリングなどのクロスカップリング反応（例えば、非特許文献７参照）を行うことによって、インドロキノキサリン環構造を有する化合物を合成することができる。 The compound having an indoloquinoxaline ring structure represented by the general formula (1) of the present invention is a novel compound, and these compounds can be synthesized, for example, as follows. First, an indoloquinoxaline derivative having a corresponding substituent can be synthesized by reacting a 1,2-diaminobenzene derivative having a corresponding substituent with an isatin derivative in an acid solvent (for example, Patent Document 5). reference). By performing condensation reaction such as Ullmann reaction and Buchward-Hartwig reaction of this indoloquinoxaline derivative with various aromatic hydrocarbon compounds, condensed polycyclic aromatic compounds or halides of aromatic heterocyclic compounds, the 6-position An indoloquinoxaline derivative having a corresponding substituent in which an aryl group is introduced can be synthesized. By bromination of this indoloquinoxaline derivative with N-bromosuccinimide or the like, an indoloquinoxaline derivative in which the 9-position is brominated can be synthesized. Here, bromo-substituted products having different substitution positions can be obtained by changing the bromination reagent and conditions. Cross-coupling reaction such as Suzuki coupling between this bromo-substituted product and a boronic acid or boronic acid ester having an anthracene ring structure synthesized by a known method (see, for example, Non-Patent Document 6) (see, for example, Non-Patent Document 7) ), A compound having an indoloquinoxaline ring structure can be synthesized.
本発明の一般式（１）で表されるインドロキノキサリン環構造を有する化合物の中で、好ましい化合物の具体例を以下に示すが、本発明は、これらの化合物に限定されるものではない。 Specific examples of preferable compounds among the compounds having an indoloquinoxaline ring structure represented by the general formula (1) of the present invention are shown below, but the present invention is not limited to these compounds.
これらの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、活性白土などによる吸着精製、溶媒による再結晶や晶析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るものであり、仕事関数は正孔阻止能力の指標となるものである。 These compounds were purified by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization or crystallization using a solvent, and the like. The compound was identified by NMR analysis. As physical property values, melting point, glass transition point (Tg) and work function were measured. The melting point is an index of vapor deposition, the glass transition point (Tg) is an index of stability in a thin film state, and the work function is an index of hole blocking ability.
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、ＤＳＣ３１００Ｓ）によって測定した。 Melting | fusing point and glass transition point (Tg) were measured with the high sensitivity differential scanning calorimeter (The Bruker AXS make, DSC3100S) using powder.
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型）を用いて測定した。 The work function was measured using an ionization potential measuring device (manufactured by Sumitomo Heavy Industries, Ltd., PYS-202 type) after forming a 100 nm thin film on the ITO substrate.
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、正孔輸送層、発光層、正孔阻止層、電子輸送層、陰極からなるもの、また、陽極と正孔輸送層の間に正孔注入層を有するもの、電子輸送層と陰極の間に電子注入層を有するもの、発光層と正孔輸送層の間に電子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することが可能であり、例えば基板上に順次に、陽極、正孔輸送層、発光層、電子輸送層、陰極を有する構成とすることもできる。 As the structure of the organic EL device of the present invention, an anode, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and a cathode are sequentially formed on the substrate, and the anode and the hole transport layer Examples include those having a hole injection layer between them, those having an electron injection layer between the electron transport layer and the cathode, and those having an electron blocking layer between the light emitting layer and the hole transport layer. In these multilayer structures, several organic layers can be omitted. For example, a structure having an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode sequentially on a substrate can be used. .
前記発光層、前記正孔輸送層、前記電子輸送層においては、それぞれが２層以上積層された構造であっても良い。 Each of the light emitting layer, the hole transport layer, and the electron transport layer may have a structure in which two or more layers are stacked.
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を３個以上、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トリフェニルアミン３量体および４量体、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 typified by copper phthalocyanine, a starburst type triphenylamine derivative, three or more triphenylamine structures in the molecule, single bond or heteroatom Use of triphenylamine trimers and tetramers such as arylamine compounds having a structure linked by a divalent group not containing an acceptor, acceptor heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials Can do. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a 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）、種々のトリフェニルアミン３量体および４量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、単独で成膜した層同士、混合して成膜した層同士、または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 a 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 , N′-di (α-naphthyl) -benzidine (hereinafter abbreviated as NPD), benzidine derivatives such as N, N, N ′, N′-tetrabiphenylylbenzidine, 1,1-bis [(di-4 -Tolylamino) phenyl] cyclohexane (hereinafter abbreviated as TAPC), various triphenylamine trimers and tetramers, and the like can be used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. Further, as a hole injection / transport layer, a coating type such as poly (3,4-ethylenedioxythiophene) (hereinafter abbreviated as PEDOT) / poly (styrene sulfonate) (hereinafter abbreviated as PSS) is used. These polymer materials can be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a 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などを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。 Further, in the hole injection layer or the hole transport layer, the material usually used for the layer is further P-doped with trisbromophenylamine hexachloroantimony or the structure of a benzidine derivative such as TPD. A high molecular compound having a 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、単独で成膜した層同士、混合して成膜した層同士、または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) A triphenylsilyl group represented by 9- [4- (carbazol-9-yl) phenyl] -9- [4- (triphenylsilyl) phenyl] -9H-fluorene, and the like. And a compound having an electron blocking action such as a compound having a triarylamine structure can be used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
本発明の有機ＥＬ素子の発光層として、本発明のインドロキノキサリン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良く、ホスト材料として前記発光材料に加え、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、単独で成膜した層同士、混合して成膜した層同士、または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。 As the light emitting layer of the organic EL device of the present invention, in addition to the compound having the indoloquinoxaline ring structure of the present invention, metal complexes of quinolinol derivatives such as Alq 3 , various metal complexes, anthracene derivatives, bisstyrylbenzene Derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, and the like can be used. In addition, the light-emitting layer may be composed of a host material and a dopant material. In addition to the light-emitting material, a thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative, or the like can be used as the host material. As the 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 alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used.
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る。
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 also possible to use a phosphorescent emitter as the light emitting material. As the phosphorescent emitter, a phosphorescent emitter of a metal complex such as iridium or platinum can be used. Green phosphorescent emitters such as Ir (ppy) 3 , blue phosphorescent emitters such as FIrpic and FIr6, red phosphorescent emitters such as Btp 2 Ir (acac), and the like are used as host materials. As the hole-injecting / transporting host material, 4,4′-di (N-carbazolyl) biphenyl (hereinafter abbreviated as CBP), carbazole derivatives such as TCTA, mCP, and the like can be used. As an electron transporting host material, p-bis (triphenylsilyl) benzene (hereinafter abbreviated as UGH2) and 2,2 ′, 2 ″-(1,3,5-phenylene) -tris (1-phenyl) -1H-benzimidazole) (hereinafter abbreviated as TPBI) or the like.
In order to avoid concentration quenching, the host material of the phosphorescent light emitting material is preferably doped by co-evaporation in the range of 1 to 30 weight percent with respect to the entire light emitting layer.
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） In addition, a material that emits delayed fluorescence such as CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN can be used as the light-emitting material. (For example, see Non-Patent Document 3)
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。 These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
本発明の有機ＥＬ素子の正孔阻止層として、本発明のインドロキノキサリン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、単独で成膜した層同士、混合して成膜した層同士、または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 a hole blocking layer of the organic EL device of the present invention, in addition to the compound having the indoloquinoxaline ring structure of the present invention, phenanthroline derivatives such as bathocuproin (hereinafter abbreviated as BCP) and metal complexes of quinolinol derivatives such as BAlq In addition to these, compounds having a hole blocking action such as various rare earth complexes, oxazole derivatives, triazole derivatives, and triazine derivatives can be used. These materials may also serve as the material for the electron transport layer. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
本発明の有機ＥＬ素子の電子輸送層として、本発明のインドロキノキサリン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、チアジアゾール誘導体、カルボジイミド誘導体、キノキサリン誘導体、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、単独で成膜した層同士、混合して成膜した層同士、または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 electron transport layer of the organic EL device of the present invention, in addition to the compound having an indoloquinoxaline ring structure of the present invention, metal complexes of quinolinol derivatives such as Alq 3 and BAlq, various metal complexes, triazole derivatives, triazines Derivatives, oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silole derivatives, and the like can be used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
本発明の有機ＥＬ素子の電子注入層として、本発明のインドロキノキサリン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、酸化アルミニウムなどの金属酸化物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 indoloquinoxaline ring structure of the present invention, alkali metal salts such as lithium fluoride and cesium fluoride, alkaline earth metal salts such as magnesium fluoride, A metal oxide such as aluminum oxide can be used, but this can be omitted in the preferred selection of the electron transport layer and the cathode.
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。 Further, in the electron injecting layer or the electron transporting layer, a material usually used for the layer and further doped with a metal such as cesium can be used.
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 the 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 the 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。 Embodiments of the present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
＜９−（９，１０−ジフェニル−アントラセン−２−イル）−６−フェニル−６Ｈ−インドロ［２，３−ｂ］キノキサリン（化合物１）の合成＞ <Synthesis of 9- (9,10-diphenyl-anthracen-2-yl) -6-phenyl-6H-indolo [2,3-b] quinoxaline (Compound 1)>
窒素置換した反応容器に、９−ブロモ−６−フェニル−６Ｈ−インドロ［２，３−ｂ］キノキサリン５．０ｇ、９，１０−ジフェニルアントラセン−２−イルボロン酸５．５ｇ、テトラキス（トリフェニルホスフィン）パラジウム０．８ｇ、２Ｍ炭酸カリウム水溶液２０ｍｌ、トルエン８０ｍｌ、エタノール２０ｍｌを加えて加熱し、攪拌しながら８時間還流した。室温まで冷却し、水２０ｍｌを加えた後に攪拌し、ろ過によって粗製物を得た。粗製物にトルエンを加えて加熱溶解し、ＮＨシリカゲルを加えて撹拌した後、ろ過によってろ液を採取し、濃縮した。得られた濃縮物をトルエン／メタノールの混合溶媒を用いた晶析精製を行うことによって、９−（９，１０−ジフェニル−アントラセン−２−イル）−６−フェニル−６Ｈ−インドロ［２，３−ｂ］キノキサリン（化合物１）の黄色粉体５．６ｇ（収率６７％）を得た。 In a reaction vessel purged with nitrogen, 5.0 g of 9-bromo-6-phenyl-6H-indolo [2,3-b] quinoxaline, 5.5 g of 9,10-diphenylanthracen-2-ylboronic acid, tetrakis (triphenylphosphine) ) 0.8 g of palladium, 20 ml of 2M aqueous potassium carbonate solution, 80 ml of toluene and 20 ml of ethanol were added and heated, and the mixture was refluxed for 8 hours with stirring. After cooling to room temperature, 20 ml of water was added and stirred, and a crude product was obtained by filtration. Toluene was added to the crude product and dissolved by heating. NH silica gel was added and stirred, and then the filtrate was collected by filtration and concentrated. The obtained concentrate was subjected to crystallization purification using a mixed solvent of toluene / methanol, whereby 9- (9,10-diphenyl-anthracen-2-yl) -6-phenyl-6H-indolo [2,3 -B] 5.6 g (yield 67%) of quinoxaline (compound 1) yellow powder was obtained.
得られた黄色粉体についてＮＭＲを使用して構造を同定した。１Ｈ−ＮＭＲ測定結果を図１に示した。 The structure of the obtained yellow powder was identified using NMR. The 1 H-NMR measurement results are shown in FIG.
１Ｈ−ＮＭＲ（ＴＨＦ−ｄ８）で以下の２９個の水素のシグナルを検出した。δ（ｐｐｍ）＝８．６９（１Ｈ）、８．２６（１Ｈ）、８．０４（１Ｈ）、８．０１（１Ｈ）、７．８８−７．８２（３Ｈ）、７．７８（２Ｈ）、７．７３−７．６３（１０Ｈ）、７．６１−７．５５（５Ｈ）、７．５４−７．４９（３Ｈ）、７．３５−７．３０（２Ｈ）。 The following 29 hydrogen signals were detected by 1 H-NMR (THF-d 8 ). δ (ppm) = 8.69 (1H), 8.26 (1H), 8.04 (1H), 8.01 (1H), 7.88-7.82 (3H), 7.78 (2H) 7.73-7.63 (10H), 7.61-7.55 (5H), 7.54-7.49 (3H), 7.35-7.30 (2H).
＜９−｛９，１０−ジ（ナフタレン−２−イル）アントラセン−２−イル｝−６−フェニル−６Ｈ−インドロ［２，３−ｂ］キノキサリン（化合物２）の合成＞
窒素置換した反応容器に、９−ブロモ−６−フェニル−６Ｈ−インドロ［２，３−ｂ］キノキサリン５．０ｇ、９，１０−ジ（ナフタレン−２−イル）アントラセン−２−イルボロン酸７．０ｇ、テトラキス（トリフェニルホスフィン）パラジウム０．８ｇ、２Ｍ炭酸カリウム水溶液２０ｍｌ、トルエン８０ｍｌ、エタノール２０ｍｌを加えて加熱し、攪拌しながら８時間還流した。室温まで冷却し、水２０ｍｌを加えた後に攪拌し、ろ過によって粗製物を得た。粗製物に１，２−ジクロロベンゼンを加えて加熱溶解し、ＮＨシリカゲルを加えて撹拌した後、ろ過によってろ液を採取し、濃縮した。得られた濃縮物を１，２−ジクロロベンゼン／メタノールの混合溶媒を用いた晶析精製を行うことによって、９−｛９，１０−ジ（ナフタレン−２−イル）アントラセン−２−イル｝−６−フェニル−６Ｈ−インドロ［２，３−ｂ］キノキサリン（化合物２）の黄色粉体５．６ｇ（収率５８％）を得た。
<Synthesis of 9- {9,10-di (naphthalen-2-yl) anthracen-2-yl} -6-phenyl-6H-indolo [2,3-b] quinoxaline (Compound 2)>
To a reaction vessel purged with nitrogen, 5.0 g of 9-bromo-6-phenyl-6H-indolo [2,3-b] quinoxaline, 9,10-di (naphthalen-2-yl) anthracen-2-ylboronic acid7. 0 g, tetrakis (triphenylphosphine) palladium 0.8 g, 2 M aqueous potassium carbonate solution 20 ml, toluene 80 ml, ethanol 20 ml were added and heated, and the mixture was refluxed for 8 hours with stirring. After cooling to room temperature, 20 ml of water was added and stirred, and a crude product was obtained by filtration. 1,2-Dichlorobenzene was added to the crude product and dissolved by heating. NH silica gel was added and stirred, and then the filtrate was collected by filtration and concentrated. 9- {9,10-di (naphthalen-2-yl) anthracen-2-yl}-is obtained by subjecting the obtained concentrate to crystallization purification using a mixed solvent of 1,2-dichlorobenzene / methanol. 5.6 g (yield 58%) of 6-phenyl-6H-indolo [2,3-b] quinoxaline (compound 2) yellow powder was obtained.
得られた黄色粉体についてＮＭＲを使用して構造を同定した。１Ｈ−ＮＭＲ測定結果を図２に示した。 The structure of the obtained yellow powder was identified using NMR. The results of 1 H-NMR measurement are shown in FIG.
１Ｈ−ＮＭＲ（ＴＨＦ−ｄ８）で以下の３３個の水素のシグナルを検出した。δ（ｐｐｍ）＝８．６７（１Ｈ）、８．２１（１Ｈ）、８．１７（２Ｈ）、８．１１（２Ｈ）、８．０８（２Ｈ）、８．０４（１Ｈ）、８．００−７．９６（３Ｈ）、７．９１（１Ｈ）、７．８５（１Ｈ）、７．７７（１Ｈ）、７．７６−７．６７（７Ｈ）、７．６５（１Ｈ）、７．６３−７．５５（６Ｈ）、７．５１（１Ｈ）、７．４７（１Ｈ）、７．３２（１Ｈ）、７．３０（１Ｈ）。 The following 33 hydrogen signals were detected by 1 H-NMR (THF-d 8 ). δ (ppm) = 8.67 (1H), 8.21 (1H), 8.17 (2H), 8.11 (2H), 8.08 (2H), 8.04 (1H), 8.00 -7.96 (3H), 7.91 (1H), 7.85 (1H), 7.77 (1H), 7.76-7.67 (7H), 7.65 (1H), 7.63 -7.55 (6H), 7.51 (1H), 7.47 (1H), 7.32 (1H), 7.30 (1H).
本発明の化合物について、高感度示差走査熱量計（ブルカー・エイエックスエス製、ＤＳＣ３１００Ｓ）によって融点とガラス転移点を求めた。
融点 ガラス転移点
本発明実施例１の化合物 ３４９℃ １６８℃
本発明実施例２の化合物 ３６０℃ １９７℃
About the compound of this invention, melting | fusing point and the glass transition point were calculated | required with the highly sensitive differential scanning calorimeter (The product made from Bruker AXS, DSC3100S).
Melting point Glass transition point
Inventive Example 1 Compound 349 ° C. 168 ° C.
Compound of Invention Example 2 360 ° C. 197 ° C.
本発明の化合物は１００℃以上のガラス転移点を有している。このことは、本発明の化合物において薄膜状態が安定であることを示すものである。 The compound of the present invention has a glass transition point of 100 ° C. or higher. This indicates that the thin film state is stable in the compound of the present invention.
本発明の化合物を用いて、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型）で仕事関数を測定した。
仕事関数
本発明実施例１の化合物 ５．９２ｅＶ
本発明実施例２の化合物 ５．９０ｅＶ
ＮＰＤ ５．５４ｅＶ
Using the compound of the present invention, a deposited film having a film thickness of 100 nm was prepared on an ITO substrate, and the work function was measured with an ionization potential measuring device (PYS-202 type, manufactured by Sumitomo Heavy Industries, Ltd.).
Work Function Compound of the Invention Example 1 5.92 eV
Inventive Example 2 compound 5.90 eV
NPD 5.54eV
このように本発明の化合物は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。 As described above, the compound of the present invention has a work function larger than 5.5 eV of a general hole transport material such as NPD or TPD, and has a large hole blocking ability.
有機ＥＬ素子は、図３に示すような、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. 3, the organic EL element has a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, and a hole blocking layer on a glass substrate 1 on which an ITO electrode is previously formed as a transparent anode 2. The layer 6, the electron transport layer 7, the electron injection layer 8, and the cathode (aluminum electrode) 9 were deposited in this order.
具体的には、膜厚１５０ｎｍのＩＴＯを成膜したガラス基板１を有機溶媒で洗浄した後に、酸素プラズマ処理にて表面を洗浄した。その後、このＩＴＯ電極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、下記構造式の化合物７０を蒸着速度６ｎｍ／ｍｉｎで膜厚２０ｎｍ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７１を蒸着速度６ｎｍ／ｍｉｎで膜厚４０ｎｍ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７２と下記構造式の化合物７３を、蒸着速度比が化合物７２：化合物７３＝５：９５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１）を蒸着速度６ｎｍ／ｍｉｎで膜厚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蒸着速度０．６ｎｍ／ｍｉｎで膜厚０．５ｎｍとなるように形成した。最後に、アルミニウムを膜厚１５０ｎｍとなるように蒸着して陰極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なった。 Specifically, the glass substrate 1 on which ITO having a thickness of 150 nm was formed was washed with an organic solvent, and then the surface was washed by oxygen plasma treatment. Then, this glass substrate with an ITO electrode was mounted in a vacuum vapor deposition machine and the pressure was reduced to 0.001 Pa or less. Subsequently, as a hole injection layer 3 so as to cover the transparent anode 2, a compound 70 having the following structural formula was formed at a deposition rate of 6 nm / min so as to have a film thickness of 20 nm. On the hole injection layer 3, a compound 71 having the following structural formula was formed as the hole transport layer 4 so as to have a film thickness of 40 nm at a deposition rate of 6 nm / min. On this hole transport layer 4, a compound 72 having the following structural formula and a compound 73 having the following structural formula are deposited as the light emitting layer 5 in a binary manner at a deposition rate such that the deposition rate ratio is compound 72: compound 73 = 5: 95. To form a film thickness of 30 nm. On this light emitting layer 5, the compound (Compound 1) of Example 1 of the present invention was formed as a hole blocking layer / electron transport layer 6 and 7 so as to have a film thickness of 30 nm at a deposition rate of 6 nm / min. On the hole blocking layer and electron transport layers 6 and 7, lithium fluoride was formed as the electron injection layer 8 so as to have a film thickness of 0.5 nm at a deposition rate of 0.6 nm / min. Finally, aluminum was deposited to a thickness of 150 nm to form the cathode 9. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere.
本発明の実施例１の化合物（化合物１）を使用して作製した有機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。 Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the organic EL device produced using the compound of Example 1 (Compound 1) of the present invention.
実施例５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１）に代えて本発明実施例２の化合物（化合物２）を膜厚３０ｎｍとなるように形成した以外は、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 5, instead of the compound of Example 1 of the present invention (Compound 1) as the material for the hole blocking layer / electron transport layers 6 and 7, the compound of Compound 2 of the present invention (Compound 2) has a thickness of 30 nm. An organic EL element was produced under the same conditions except that the above was formed. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere. Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the produced organic EL element.
［比較例１］
比較のために、実施例７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１）に代えて下記構造式の化合物７４（例えば、特許文献４参照）を膜厚３０ｎｍとなるように形成した以外は、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, in Example 7, instead of the compound of Example 1 of the present invention (Compound 1) as the material of the hole blocking layer / electron transport layers 6 and 7, Compound 74 of the following structural formula (for example, Patent Document 4) The organic EL element was produced under the same conditions except that the film was formed so as to have a film thickness of 30 nm. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere. Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the produced organic EL element.
表１に示す様に、電流密度１０ｍＡ／ｃｍ２時における駆動電圧は、前記構造式の化合物７４を用いた比較例１の５．９５Ｖに対して実施例５〜６では５．５１〜５．５６Ｖといずれも低電圧化し、さらに電流密度１０ｍＡ／ｃｍ２時における輝度、発光効率、電力効率のいずれも向上した。 As shown in Table 1, the driving voltage at a current density of 10 mA / cm 2 was 5.95 V in Comparative Example 1 using Compound 74 of the above structural formula, while 5.51 to 5.5 in Examples 5-6. The voltage was reduced to 56 V, and the luminance, luminous efficiency, and power efficiency were all improved at a current density of 10 mA / cm 2 .
上記と同一の有機ＥＬ素子を用いて発光開始電圧を測定した結果を以下に示した。
有機ＥＬ素子 化合物 発光開始電圧［Ｖ］
実施例５ 化合物１ ３．０
実施例６ 化合物２ ２．８
比較例１ 化合物７４ ３．１
その結果、前記構造式の化合物７４を使用した比較例１に対し、実施例５〜６では発光開始電圧を低電圧化していることが分かる。
The results of measuring the light emission starting voltage using the same organic EL element as described above are shown below.
Organic EL device Compound Luminescence start voltage [V]
Example 5 Compound 1 3.0
Example 6 Compound 2 2.8
Comparative Example 1 Compound 74 3.1
As a result, it can be seen that in Comparative Examples 1 using the compound 74 of the structural formula, the light emission starting voltage was lowered in Examples 5 to 6.
このように本発明の有機ＥＬ素子は、一般的な電子輸送材料として用いられている前記構造式の化合物７４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、さらに実用駆動電圧の顕著な低下が達成できることがわかった。 As described above, the organic EL device of the present invention is superior in light emission efficiency and power efficiency as compared with a device using the compound 74 of the structural formula used as a general electron transport material, and is further practically driven. It has been found that a significant drop in voltage can be achieved.
本発明のインドロキノキサリン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 an indoloquinoxaline 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 a stable thin film state. By producing an organic EL element using the compound, high efficiency can be obtained, driving voltage can be lowered, and durability can be improved. For example, it has become possible to develop home appliances and lighting.
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
DESCRIPTION OF SYMBOLS 1 Glass 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
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