JP2000344691A - Compound for organic electroluminescent element and organic electroluminescent element - Google Patents
Compound for organic electroluminescent element and organic electroluminescent elementInfo
- Publication number
- JP2000344691A JP2000344691A JP11157105A JP15710599A JP2000344691A JP 2000344691 A JP2000344691 A JP 2000344691A JP 11157105 A JP11157105 A JP 11157105A JP 15710599 A JP15710599 A JP 15710599A JP 2000344691 A JP2000344691 A JP 2000344691A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- organic
- layer
- aryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 126
- 125000003118 aryl group Chemical group 0.000 claims abstract description 52
- -1 mono(ortho-substituted phenyl) anthryl Chemical group 0.000 claims abstract description 41
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- 125000000732 arylene group Chemical group 0.000 claims abstract description 22
- BRSRUYVJULRMRQ-UHFFFAOYSA-N 1-phenylanthracene Chemical class C1=CC=CC=C1C1=CC=CC2=CC3=CC=CC=C3C=C12 BRSRUYVJULRMRQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000005647 linker group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 58
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 27
- 238000002347 injection Methods 0.000 claims description 23
- 239000007924 injection Substances 0.000 claims description 23
- 150000002894 organic compounds Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 125000006267 biphenyl group Chemical group 0.000 claims description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 9
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 8
- 230000005525 hole transport Effects 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000005504 styryl group Chemical group 0.000 claims description 5
- 125000001544 thienyl group Chemical group 0.000 claims description 5
- 230000001404 mediated effect Effects 0.000 claims description 4
- ZYVFZUPZEORVHB-UHFFFAOYSA-N 3-phenyl-2-thiophen-2-ylthiophene Chemical group C1=CSC(C2=C(C=CS2)C=2C=CC=CC=2)=C1 ZYVFZUPZEORVHB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 15
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 abstract description 6
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004912 1,5-cyclooctadiene Substances 0.000 abstract description 3
- 239000003086 colorant Substances 0.000 abstract description 2
- 150000008378 aryl ethers Chemical class 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 134
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 230000015572 biosynthetic process Effects 0.000 description 32
- 238000003786 synthesis reaction Methods 0.000 description 31
- 239000007787 solid Substances 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000007740 vapor deposition Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000010409 thin film Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000004949 mass spectrometry Methods 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000002019 doping agent Substances 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 230000006798 recombination Effects 0.000 description 7
- 238000005215 recombination Methods 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- 125000003944 tolyl group Chemical group 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006880 cross-coupling reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- MGRRGKWPEVFJSH-UHFFFAOYSA-N 10-(10-oxoanthracen-9-ylidene)anthracen-9-one Chemical compound C12=CC=CC=C2C(=O)C2=CC=CC=C2C1=C1C2=CC=CC=C2C(=O)C2=CC=CC=C21 MGRRGKWPEVFJSH-UHFFFAOYSA-N 0.000 description 2
- PLMFIWDPKYXMGE-UHFFFAOYSA-N 2-chloro-9,10-diphenylanthracene Chemical compound C=12C=CC=CC2=C(C=2C=CC=CC=2)C2=CC(Cl)=CC=C2C=1C1=CC=CC=C1 PLMFIWDPKYXMGE-UHFFFAOYSA-N 0.000 description 2
- OEYLQYLOSLLBTR-UHFFFAOYSA-N 9-(2-phenylphenyl)-10-[10-(2-phenylphenyl)anthracen-9-yl]anthracene Chemical group C1=CC=CC=C1C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1C1=CC=CC=C1 OEYLQYLOSLLBTR-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HLSPEMVMBBEBBJ-UHFFFAOYSA-N [Li]C1=CC=CC=C1C1=CC=CC=C1 Chemical group [Li]C1=CC=CC=C1C1=CC=CC=C1 HLSPEMVMBBEBBJ-UHFFFAOYSA-N 0.000 description 2
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000005336 allyloxy group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 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
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UGUHFDPGDQDVGX-UHFFFAOYSA-N 1,2,3-thiadiazole Chemical group C1=CSN=N1 UGUHFDPGDQDVGX-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 1
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- ZKSVYBRJSMBDMV-UHFFFAOYSA-N 1,3-diphenyl-2-benzofuran Chemical compound C1=CC=CC=C1C1=C2C=CC=CC2=C(C=2C=CC=CC=2)O1 ZKSVYBRJSMBDMV-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- OBZZEGPFTUQMCZ-UHFFFAOYSA-N 1-phenyl-10h-anthracen-9-one Chemical compound C=12C(=O)C3=CC=CC=C3CC2=CC=CC=1C1=CC=CC=C1 OBZZEGPFTUQMCZ-UHFFFAOYSA-N 0.000 description 1
- ZQXZUOJNJXNUEO-UHFFFAOYSA-N 10-(10-oxo-9h-anthracen-9-yl)-10h-anthracen-9-one Chemical compound C12=CC=CC=C2C(=O)C2=CC=CC=C2C1C1C2=CC=CC=C2C(=O)C2=CC=CC=C21 ZQXZUOJNJXNUEO-UHFFFAOYSA-N 0.000 description 1
- MVWPVABZQQJTPL-UHFFFAOYSA-N 2,3-diphenylcyclohexa-2,5-diene-1,4-dione Chemical class O=C1C=CC(=O)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 MVWPVABZQQJTPL-UHFFFAOYSA-N 0.000 description 1
- XZLJNFORBNAONR-UHFFFAOYSA-N 2-bromo-1,3-diphenylbenzene Chemical compound BrC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 XZLJNFORBNAONR-UHFFFAOYSA-N 0.000 description 1
- RPCYRQVOHKQOEC-UHFFFAOYSA-N 2-bromo-1,4-diphenylbenzene Chemical compound BrC1=CC(C=2C=CC=CC=2)=CC=C1C1=CC=CC=C1 RPCYRQVOHKQOEC-UHFFFAOYSA-N 0.000 description 1
- FPKCTSIVDAWGFA-UHFFFAOYSA-N 2-chloroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3C(=O)C2=C1 FPKCTSIVDAWGFA-UHFFFAOYSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- MZFPAWGWFDGCHP-UHFFFAOYSA-N 5-diphenylphosphanylpentyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 MZFPAWGWFDGCHP-UHFFFAOYSA-N 0.000 description 1
- ZYVKAGGQDPDPGW-UHFFFAOYSA-N 9-(2,6-dimethylphenyl)-10-[10-(2,6-dimethylphenyl)anthracen-9-yl]anthracene Chemical group CC1=CC=CC(C)=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=C(C)C=CC=C1C ZYVKAGGQDPDPGW-UHFFFAOYSA-N 0.000 description 1
- LBGSTYYIGHJJLH-UHFFFAOYSA-N 9-[2-(4-phenylphenyl)phenyl]-10-[10-[2-(4-phenylphenyl)phenyl]anthracen-9-yl]anthracene Chemical group C1=CC=CC=C1C1=CC=C(C=2C(=CC=CC=2)C=2C3=CC=CC=C3C(C=3C4=CC=CC=C4C(C=4C(=CC=CC=4)C=4C=CC(=CC=4)C=4C=CC=CC=4)=C4C=CC=CC4=3)=C3C=CC=CC3=2)C=C1 LBGSTYYIGHJJLH-UHFFFAOYSA-N 0.000 description 1
- SXGIRTCIFPJUEQ-UHFFFAOYSA-N 9-anthracen-9-ylanthracene Chemical group C1=CC=CC2=CC3=CC=CC=C3C(C=3C4=CC=CC=C4C=C4C=CC=CC4=3)=C21 SXGIRTCIFPJUEQ-UHFFFAOYSA-N 0.000 description 1
- BAFAFLNHBXDEJL-UHFFFAOYSA-N C1=CC=C(C=C1)C1=CC=CC(C2=CC=CC=C2)=C1C1=C2C=CC=CC2=C(C2=CC=CC=C12)C1=C2C=CC=CC2=C(C2=C1C=CC=C2)C1=C(C=CC=C1C1=CC=CC=C1)C1=CC=CC=C1 Chemical group C1=CC=C(C=C1)C1=CC=CC(C2=CC=CC=C2)=C1C1=C2C=CC=CC2=C(C2=CC=CC=C12)C1=C2C=CC=CC2=C(C2=C1C=CC=C2)C1=C(C=CC=C1C1=CC=CC=C1)C1=CC=CC=C1 BAFAFLNHBXDEJL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- AAXGWYDSLJUQLN-UHFFFAOYSA-N diphenyl(propyl)phosphane Chemical compound C=1C=CC=CC=1P(CCC)C1=CC=CC=C1 AAXGWYDSLJUQLN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 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
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有機ＥＬ（電界発
光）素子に用いられる化合物関し、詳しくは、フェニル
アントラセン誘導体である有機化合物、およびこの化合
物を有する積層構造薄膜に電界を印加して光を放出する
素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound used in an organic EL (electroluminescence) device, and more specifically to an organic compound which is a phenylanthracene derivative and a laminated structure thin film containing this compound, which is irradiated with an electric field to emit light. The element which emits.
【０００２】[0002]
【従来の技術】有機ＥＬ素子は、蛍光性有機化合物を含
む薄膜を、陰極と陽極とで挟んだ構成を有し、前記薄膜
に電子およびホールを注入して再結合させることにより
励起子（エキシトン）を生成させ、このエキシトンが失
活する際の光の放出（蛍光・燐光）を利用して発光する
素子である。2. Description of the Related Art An organic EL device has a structure in which a thin film containing a fluorescent organic compound is sandwiched between a cathode and an anode, and electrons and holes are injected into the thin film to recombine the excitons (exciton). ) Is generated, and light is emitted by utilizing light emission (fluorescence/phosphorescence) when the exciton is deactivated.
【０００３】有機ＥＬ素子の特徴は、１０V 程度の低電
圧で１００〜数千cd/m2 程度の高輝度の面発光が可能で
あり、また蛍光物質の種類を選択することにより青色か
ら赤色までの発光が可能なことであるが、発光寿命が短
く、保存耐久性に劣るという問題点を有しており、これ
らの問題点を解消するために現在様々な研究、開発が進
められている。The characteristic of the organic EL element is that it is capable of surface emission with a high brightness of 100 to several thousand cd/m 2 at a low voltage of about 10 V, and from blue to red by selecting the type of fluorescent material. However, it has a problem that the light emission life is short and the storage durability is inferior, and various researches and developments are currently underway in order to solve these problems.
【０００４】具体的には、高効率、長寿命化の手段とし
て、蛍光量子収率の大きい蛍光性色素を少量ドーピング
する方法（特開平05-198377号公報、特開平07-135077号
公報等）、また、発光層としてホール輸送性材料と電子
輸送性材料を混合したバイポーラ型発光層を用い、キャ
リアの再結合領域を拡大し、再結合確率を向上させて高
効率素子を得る方法（ WO 98/0836号、特開平03-114197
号公報等）等が報告されている。Specifically, as a means of achieving high efficiency and long life, a method of doping a small amount of a fluorescent dye having a high fluorescence quantum yield (JP-A-05-198377, JP-A-07-135077, etc.) Further, a method of obtaining a high efficiency device by using a bipolar type light emitting layer in which a hole transporting material and an electron transporting material are mixed as the light emitting layer to expand the recombination region of carriers and improve the recombination probability (WO 98 /0836, JP 03-114197
No. Gazette) etc. have been reported.
【０００５】しかしながら、ドーピング法を用いる場
合、ドーパントとなる蛍光性色素の多くは濃度消光性が
強く、素子を作成する際は重量比にして数パーセントの
レベルでのドーパント濃度の制御が必要となる。一般的
に低分子化合物を用いたＥＬ素子は真空蒸着法で作成さ
れることが多く、このような精密な濃度制御を行うこと
は容易ではなく、製造マージンを狭くする原因となって
いる。さらに、ドーピングにより青い発光を得るために
はエネルギーギャップの大きなドーパントを発光させる
ため、ホストとなり得る材料は限定され、ドーパントの
組み合わせの選定は困難となる。However, when the doping method is used, most of the fluorescent dyes serving as dopants have a strong concentration quenching property, and it is necessary to control the dopant concentration at a level of several percent in weight ratio when manufacturing a device. .. In general, EL devices using low molecular weight compounds are often manufactured by a vacuum deposition method, and it is not easy to perform such precise concentration control, which causes a manufacturing margin to be narrowed. Further, in order to obtain blue light emission by doping, since a dopant having a large energy gap is made to emit light, materials that can serve as a host are limited, and it is difficult to select a combination of dopants.
【０００６】また、バイポーラ型発光層を用いた場合で
も再結合確率は向上するものの、最終的にエネルギーを
光として取り出すためには高い蛍光量子収率を有するド
ーパントの使用が必要となる場合が多い。しかも、この
ようなバイポーラ型の混合発光層を用いると、駆動電圧
は比較的高くなってしまうという難点がある。Although the recombination probability is improved even when a bipolar type light emitting layer is used, it is often necessary to use a dopant having a high fluorescence quantum yield in order to finally extract energy as light. .. Moreover, when such a bipolar type mixed light emitting layer is used, the driving voltage becomes relatively high.
【０００７】一方、本発明者らは、特開平08-12600号公
報で、物理的変化、光化学的変化、電気化学的変化の少
ないフェニルアントラセン誘導体を用いた高輝度発光素
子を開示しているが、視感度の低い青色の領域に関して
は、十分な効率が得られておらず、また、発光寿命、耐
久性の面でも実用に向けてさらなる特性の向上が必要と
されている。On the other hand, the inventors of the present invention have disclosed in JP-A-08-12600 a high-brightness light emitting device using a phenylanthracene derivative with little physical change, photochemical change, or electrochemical change. In the blue region having low visibility, sufficient efficiency has not been obtained, and further improvement in characteristics is required for practical use in terms of light emission life and durability.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、物理
的変化や光化学的変化、電気化学的変化の少ない光・電
子機能材料として新規な有機ＥＬ素子用化合物を提供
し、この有機ＥＬ素子用化合物を用い、極めて高い信頼
性および発光効率を有する種々の発光色を持った有機Ｅ
Ｌ素子を実現することである。特に、分子量の大きな化
合物を蒸着法で形成した有機薄膜を用い、素子の駆動時
の駆動電圧上昇や輝度の低下、電流のリーク、部分的な
非発光部の出現・成長を抑えた高信頼性の高輝度発光素
子を実現することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel compound for an organic EL device as an optoelectronic functional material having little physical change, photochemical change, or electrochemical change, and this organic EL device. E with various emission colors having extremely high reliability and luminous efficiency
It is to realize an L element. In particular, using an organic thin film formed by vapor deposition of a compound with a large molecular weight, high reliability that suppresses the rise and decrease in driving voltage when driving the device, current leakage, and the appearance/growth of partial non-light emitting parts. It is to realize a high brightness light emitting device.
【０００９】[0009]
（２） 下記化１または化２で表される上記（１）の有
機ＥＬ素子用化合物。(2) The compound for organic EL device of the above (1) represented by the following chemical formula 1 or chemical formula 2.
【００１０】[0010]
【化３】 [Chemical 3]
【００１１】[0011]
【化４】 [Chemical 4]
【００１２】〔化１において、Ａｒ1 〜Ａｒ4 は、水素
原子、アリール基、複素環アリール基またはアリールエ
テニル基を表し、Ａｒ1 およびＡｒ2 、Ａｒ3 およびＡ
ｒ4 の少なくとも一方はアリール基、複素環アリール基
またはアリールエテニル基である。Ｒ1 およびＲ2 は、
各々アルキル基、アリール基、アリールエテニル基、ア
ルコキシ基、またはアミノ基を表し、これらは同一でも
異なるものであってもよい。ｒ１およびｒ２は、各々、
０または１〜３の整数を表し、ｒ１およびｒ２が、各
々、２以上の整数であるとき、Ｒ1 同士およびＲ2 同士
は各々同一でも異なるものであってもよい。Ｒ3 は、ア
ルキル基またはアリール基を表し、ｒ3は、各々、０ま
たは１〜３の整数を表す。ｒ3が、２以上の整数である
とき、Ｒ3 は各々同一でも異なるものであってもよい。
Ｌ1 は単結合またはアリーレン基を表し、アリーレン基
はアルキレン基、−Ｏ−、−Ｓ−または−ＮＲ−（ここ
で、Ｒはアルキル基またはアリール基を表す。）が介在
するものであってもよい。化２において、Ａｒ5 および
Ａｒ6 は、水素原子、アリール基、複素環アリール基ま
たはアリールエテニル基を表し、Ａｒ5 およびＡｒ6 の
少なくとも一方はアリール基、複素環アリール基または
アリールエテニル基である。Ｒ4 は、各々アルキル基、
アリール基、アリールエテニル基、アルコキシ基、また
はアミノ基を表し、これらは同一でも異なるものであっ
てもよい。ｒ４は、各々、０または１〜３の整数を表
し、ｒ４が、各々、２以上の整数であるとき、Ｒ4 同士
は各々同一でも異なるものであってもよい。Ｒ5 は、ア
ルキル基またはアリール基を表し、ｒ５は、各々、０ま
たは１〜４の整数を表す。ｒ５が、２以上の整数である
とき、Ｒ5 は各々同一でも異なるものであってもよい。
Ｌ2 は単結合またはアリーレン基を表し、アリーレン基
はアルキレン基、−Ｏ−、−Ｓ−または−ＮＲ−（ここ
で、Ｒはアルキル基またはアリール基を表す。）が介在
するものであってもよい。Ｌ2 は単結合またはアリーレ
ン基を表し、アリーレン基はアルキレン基、−Ｏ−、−
Ｓ−または−ＮＲ−（ここで、Ｒはアルキル基またはア
リール基を表す。）が介在するものであってもよい。〕 （３） 前記化１において、Ａｒ1 およびＡｒ2 、Ａｒ
3 およびＡｒ4 の少なくとも一方がフェニル基、ビフェ
ニル基、ターフェニル基、スチリル基、フェニルスチリ
ル基、ジフェニルスチリル基、チエニル基、メチルチエ
ニル基、フェニルチエニル基またはフェニルビチエニル
基である上記（２）の有機ＥＬ素子用化合物。 （４） 前記化２において、Ａｒ5 およびＡｒ6 、の少
なくとも一方がフェニル基、ビフェニル基、ターフェニ
ル基、スチリル基、フェニルスチリル基、ジフェニルス
チリル基、チエニル基、メチルチエニル基、フェニルチ
エニル基またはフェニルビチエニル基である上記（２）
のフェニルアントラセン誘導体。 （５） 前記化１において、Ａｒ1 およびＡｒ2 、Ａｒ
3 およびＡｒ4 の少なくとも一方がフェニル基、ビフェ
ニル基またはターフェニル基であり、Ｌ1 は単結合であ
る上記（２）の有機ＥＬ素子用化合物。 （６） 前記化２において、Ａｒ5 およびＡｒ6 、の少
なくとも一方がフェニル基、ビフェニル基またはターフ
ェニル基であり、Ｌ2 は単結合である上記（２）の有機
ＥＬ素子用化合物。 （７） 上記（１）の有機ＥＬ素子用化合物を含有する
少なくとも１層の有機化合物層を有する有機ＥＬ素子。 （８） 前記有機ＥＬ素子用化合物を含有する有機化合
物層が発光層である上記（７）の有機ＥＬ素子。 （９） さらに、少なくとも１層のホール注入層と、少
なくとも１層のホール輸送層と、少なくとも１層の電子
注入輸送層とを有する上記（８）の有機ＥＬ素子。 （１０） さらに、少なくとも１層のホール注入層と、
少なくとも１層のホール輸送層と、少なくとも１層の電
子輸送層と、少なくとも１層の電子注入層とを有する上
記（８）の有機ＥＬ素子。 （１１） 前記有機ＥＬ素子用化合物を含有する有機化
合物層が電子注入輸送層であり、さらに発光層を有する
上記（７）の有機ＥＬ素子。 （１２） 少なくとも１層の発光層を有し、この発光層
が電子注入輸送性化合物とホール注入輸送性化合物との
混合層であって、この混合層が前記有機ＥＬ素子用化合
物を含有する上記（７）の有機ＥＬ素子。 （１３） 前記電子注入輸送性化合物は、前記有機ＥＬ
素子用化合物であり、前記ホール注入輸送性化合物は、
アミン、またはスチリルアミン系化合物である上記（１
２）の有機ＥＬ素子。[In the formula 1 , Ar 1 to Ar 4 represent a hydrogen atom, an aryl group, a heterocyclic aryl group or an arylethenyl group, and are Ar 1 and Ar 2 , Ar 3 and A
At least one of r 4 is an aryl group, a heterocyclic aryl group, or an arylethenyl group. R 1 and R 2 are
Each represents an alkyl group, an aryl group, an arylethenyl group, an alkoxy group, or an amino group, which may be the same or different. r1 and r2 are each
When R1 and r2 are each an integer of 2 or more, R 1 s and R 2 s may be the same or different. R 3 represents an alkyl group or an aryl group, and r 3 represents 0 or an integer of 1 to 3, respectively. r3 is, when an integer of 2 or more, R 3 's may be the same or different in the same.
L 1 represents a single bond or an arylene group, and the arylene group is mediated by an alkylene group, —O—, —S— or —NR— (wherein R represents an alkyl group or an aryl group). Good. In Chemical formula 2, Ar 5 and Ar 6 represent a hydrogen atom, an aryl group, a heterocyclic aryl group or an arylethenyl group, and at least one of Ar 5 and Ar 6 is an aryl group, a heterocyclic aryl group or an arylethenyl group. Is. R 4 is an alkyl group,
It represents an aryl group, an arylethenyl group, an alkoxy group, or an amino group, which may be the same or different. Each r4 represents an integer of 0 or 1 to 3, and when r4 is an integer of 2 or more, R 4 s may be the same or different. R 5 represents an alkyl group or an aryl group, and r 5 represents 0 or an integer of 1 to 4, respectively. When r5 is an integer of 2 or more, R 5 may be the same or different.
L 2 represents a single bond or an arylene group, and the arylene group is mediated by an alkylene group, —O—, —S— or —NR— (wherein R represents an alkyl group or an aryl group). Good. L 2 represents a single bond or an arylene group, and the arylene group is an alkylene group, —O—, —
S- or -NR- (wherein R represents an alkyl group or an aryl group) may be present. (3) In the above chemical formula 1 , Ar 1 and Ar 2 , Ar
At least one of 3 and Ar 4 is a phenyl group, a biphenyl group, a terphenyl group, a styryl group, a phenylstyryl group, a diphenylstyryl group, a thienyl group, a methylthienyl group, a phenylthienyl group or a phenylbithienyl group (2). Compound for organic EL device of. (4) In the chemical formula 2, at least one of Ar 5 and Ar 6 is a phenyl group, a biphenyl group, a terphenyl group, a styryl group, a phenylstyryl group, a diphenylstyryl group, a thienyl group, a methylthienyl group, a phenylthienyl group or The above (2) which is a phenylbithienyl group
Phenylanthracene derivative of. (5) In the above chemical formula 1 , Ar 1 and Ar 2 , Ar
At least one of 3 and Ar 4 is a phenyl group, a biphenyl group or a terphenyl group, and L 1 is a single bond. (6) The compound for an organic EL device according to (2), wherein in the chemical formula 2, at least one of Ar 5 and Ar 6 is a phenyl group, a biphenyl group or a terphenyl group, and L 2 is a single bond. (7) An organic EL device having at least one organic compound layer containing the compound for organic EL device of (1) above. (8) The organic EL device according to (7), wherein the organic compound layer containing the compound for organic EL device is a light emitting layer. (9) The organic EL device according to (8), further including at least one hole injection layer, at least one hole transport layer, and at least one electron injection transport layer. (10) Further, at least one hole injection layer,
The organic EL device according to (8) above, which has at least one hole transport layer, at least one electron transport layer, and at least one electron injection layer. (11) The organic EL device according to (7), wherein the organic compound layer containing the compound for organic EL device is an electron injecting and transporting layer, and further has a light emitting layer. (12) A light emitting layer having at least one light emitting layer, wherein the light emitting layer is a mixed layer of an electron injecting and transporting compound and a hole injecting and transporting compound, and the mixed layer contains the compound for an organic EL device. (7) Organic EL device. (13) The electron injecting and transporting compound is the organic EL.
A device compound, wherein the hole injecting and transporting compound is
The above (1) which is an amine or styrylamine compound.
2) Organic EL device.
【００１３】[0013]
【作用】本発明の有機ＥＬ素子は上記式（Ｉ）、好まし
くは上記化３，化４に示される化合物を発光層に用いる
ため、１００００cd／m-2程度、あるいはそれ以上の高
輝度が安定して得られる。また、耐熱性・耐久性が高
く、素子電流密度も１０００mA／cm-2程度でも安定した
駆動が可能である。In the organic EL device of the present invention, the compound represented by the above formula (I), preferably the chemical formulas 3 and 4, is used for the light emitting layer, so that high brightness of about 10,000 cd/m -2 or more is stable. Obtained. Further, it has high heat resistance and durability, and stable driving is possible even when the device current density is about 1000 mA/cm -2 .
【００１４】特に、上記化合物は、フェニル基の２位ま
たは６位（アントラセン環への結合位置に対してオルト
位）に、アリール基、複素環アリールもしくはアリール
エテニル基を導入しているため、エキサイマーやエキサ
イプレックス等の分子間相互作用が殆どなく、色純度の
低下や効率の低下が極めて少ないため、信頼性及び発光
効率の高い有機ＥＬ素子を得ることができる。Particularly, in the above compound, an aryl group, a heterocyclic aryl or an arylethenyl group is introduced at the 2-position or 6-position of the phenyl group (ortho-position with respect to the bonding position to the anthracene ring). Since there is almost no intermolecular interaction such as an excimer or an exciplex, and a decrease in color purity and a decrease in efficiency are extremely small, it is possible to obtain an organic EL device having high reliability and light emission efficiency.
【００１５】また、オルト位の置換基が、本発明の化合
物のようなπ電子共役系として延びていると、キャリア
の輸送性を向上させ、素子の駆動電圧を低下させること
ができる。When the ortho-positioned substituent extends as a π-electron conjugated system like the compound of the present invention, carrier transportability can be improved and the device driving voltage can be lowered.
【００１６】上記化合物の蒸着膜は安定なアモルファス
状態なので、薄膜の膜物性が良好となりムラがなく均一
な発光が可能である。また、大気下で一年以上安定であ
り結晶化を起こさない。Since the vapor-deposited film of the above compound is in a stable amorphous state, the physical properties of the thin film are good and uniform light emission is possible without unevenness. Also, it is stable for more than a year in the atmosphere and does not cause crystallization.
【００１７】また、クロロホルム等へ溶解するスピンコ
ート等の湿式成膜プロセスにおいても安定なアモルファ
ス状態の薄膜を形成することが可能である。Further, it is possible to form a stable amorphous thin film even in a wet film forming process such as spin coating in which chloroform is dissolved.
【００１８】また、本発明の有機ＥＬ素子は、低駆動電
圧で効率よく発光する。Further, the organic EL device of the present invention efficiently emits light at a low driving voltage.
【００１９】なお、本発明の有機ＥＬ素子の発光極大波
長は、４００〜７００nm程度であり、特に４００〜５０
０nmの領域で効率よく発光する。The maximum emission wavelength of the organic EL device of the present invention is about 400 to 700 nm, and particularly 400 to 50 nm.
Emits light efficiently in the 0 nm region.
【００２０】[0020]
【発明の実施の形態】以下、本発明の具体的構成につい
て詳細に説明する。本発明のフェニルアントラセン誘導
体は式（Ｉ）で示されるものである。式（Ｉ）について
説明すると、Ａ1 およびＡ2 は、各々モノ（オルト置換
フェニル）アントリル基またはジ（オルト置換フェニ
ル）フェニルアントリル基を表し、これらは同一でも異
なるものであってもよい。BEST MODE FOR CARRYING OUT THE INVENTION The specific constitution of the present invention will be described in detail below. The phenylanthracene derivative of the present invention is represented by the formula (I). In the formula (I), A 1 and A 2 each represent a mono(ortho-substituted phenyl)anthryl group or a di(ortho-substituted phenyl)phenylanthryl group, and these may be the same or different.
【００２１】Ａ1 、Ａ2 で表されるモノ（オルト置換フ
ェニル）フェニルアントリル基またはジ（オルト置換フ
ェニル）フェニルアントリル基は、フェニル基の２位ま
たは６位（アントラセン環への結合位置に対してオルト
位）に、アリール基、複素環アリール基もしくはアリー
ルエテニル基を有するものである。また、オルト位以外
に置換基を有するものであってもよく、置換基を有する
場合の置換基としては、アルキル基、アリール基、アリ
ールエテニル基、アルコキシ基、アミノ基等が挙げら
れ、これらの置換基はさらに置換されていてもよい。こ
れらの置換基については後述する。The mono(ortho-substituted phenyl)phenyl anthryl group or di(ortho-substituted phenyl)phenyl anthryl group represented by A 1 or A 2 is a 2- or 6-position (bonding position to an anthracene ring) of a phenyl group. Ortho position) has an aryl group, a heterocyclic aryl group or an arylethenyl group. Further, it may have a substituent other than the ortho position, and in the case of having a substituent, the substituent includes an alkyl group, an aryl group, an arylethenyl group, an alkoxy group, an amino group, and the like. The substituent of may be further substituted. These substituents will be described later.
【００２２】また、アントラセン環におけるフェニル基
の結合位置はアントラセン環の９位、１０位であること
が好ましい。Further, the bonding position of the phenyl group in the anthracene ring is preferably 9-position and 10-position in the anthracene ring.
【００２３】式（Ｉ）において、Ｌは単結合または二価
の基を表すが、Ｌで表される二価の基としてはアルキレ
ン基等が介在してもよいアリーレン基が好ましい。この
ようなアリーレン基については後述する。In the formula (I), L represents a single bond or a divalent group, and the divalent group represented by L is preferably an arylene group in which an alkylene group or the like may be present. Such an arylene group will be described later.
【００２４】式（Ｉ）で示されるフェニルアントラセン
誘導体のなかでも、化３、化４で示されるものが好まし
い。化３について説明すると、化３において、Ar1〜Ar
3 は、水素原子、アリール基、複素環アリール基または
アリールエテニル基を表し、Ｒ1 およびＲ2 は、各々ア
ルキル基、アリール基、アリールエテニル基、アルコキ
シ基またはアミノ基を表し、Ｒ3 は、アルキル基または
アリール基を表す。Among the phenylanthracene derivatives represented by the formula (I), those represented by Chemical formulas 3 and 4 are preferable. Chemical formula 3 will be explained. In Chemical formula 3, Ar 1 to Ar
3 represents a hydrogen atom, an aryl group, a heterocyclic aryl group or an arylethenyl group, R 1 and R 2 each represent an alkyl group, an aryl group, an arylethenyl group, an alkoxy group or an amino group, and R 3 Represents an alkyl group or an aryl group.
【００２５】Ａｒ1 〜Ａｒ4 およびＲ1 〜Ｒ3 で表され
るアリール基としては、炭素数６〜２０のものが好まし
く、さらにはフェニル基、トリル基等の置換基を有する
ものであってもよい。具体的には、フェニル基、（ｏ
−，ｍ−，ｐ−）トリル基、ピレニル基、ナフチル基、
アントリル基、ビフェニル基、フェニルアントリル基、
トリルアントリル基等が挙げられる。The aryl group represented by Ar 1 to Ar 4 and R 1 to R 3 preferably has 6 to 20 carbon atoms and further has a substituent such as a phenyl group and a tolyl group. Good. Specifically, a phenyl group, (o
-, m-, p-) tolyl group, pyrenyl group, naphthyl group,
Anthryl group, biphenyl group, phenylanthryl group,
Examples include a tolyl anthryl group.
【００２６】Ａｒ1 〜Ａｒ4 で表される複素環アリール
基としては、フリル基、ベンゾフリル基、チエニル基、
ベンゾチエニル基、ピロリル基、N-アリルピロリル基、
インドリル基、ピリジル基、ビピリジル基、キノリル
基、キノキサリル基、オキサゾール基、ベンゾオキサゾ
ール基、オキサジアゾール基、チアゾール基、ベンゾチ
アゾール基、チアジアゾール基、イミダゾール基等が好
ましく、さらには、炭素数４２以下のアリール基、炭素
数１２以下のアルキル基、アルコキシ基、アリロキシ
基、アミノ基、シアノ基、ニトロ基等の置換基を有する
ものであってもよい。具体的には、具体的には、フェニ
ル基、（ｏ−，ｍ−，ｐ−）ビフェニル基、（１，２）
ナフチル基、メチル基、エチル基、プロピル基、ブチル
基、メトキシ基、エトキシ基、フェノキシ基、（ｏ−，
ｍ−，ｐ−）トリル基等が挙げられる。The heterocyclic aryl group represented by Ar 1 to Ar 4 includes a furyl group, a benzofuryl group, a thienyl group,
Benzothienyl group, pyrrolyl group, N-allylpyrrolyl group,
An indolyl group, a pyridyl group, a bipyridyl group, a quinolyl group, a quinoxalyl group, an oxazole group, a benzoxazole group, an oxadiazole group, a thiazole group, a benzothiazole group, a thiadiazole group, an imidazole group and the like are preferable, and a carbon number of 42 or less. May have a substituent such as an aryl group, an alkyl group having 12 or less carbon atoms, an alkoxy group, an allyloxy group, an amino group, a cyano group or a nitro group. Specifically, specifically, a phenyl group, (o-, m-, p-) biphenyl group, (1, 2)
Naphthyl group, methyl group, ethyl group, propyl group, butyl group, methoxy group, ethoxy group, phenoxy group, (o-,
and m-, p-) tolyl groups and the like.
【００２７】Ａｒ1 〜Ａｒ4 、Ｒ1 およびＲ2 で表され
るアリールエテニル基としては、２−フェニルエテニル
基、２，２−ジフェニルエテニル基等が好ましく、さら
にはアリール基、アルキル基、アルコキシ基、アリロキ
シ基、アミノ基、シアノ基、ニトロ基等の置換基を有す
るものであってもよい。具体的にはフェニル基、（ｏ
−，ｍ−，ｐ−）ビフェニル基、（１，２）ナフチル
基、メチル基、エチル基、プロピル基、ブチル基、メト
キシ基、エトキシ基、フェノキシ基、（ｏ−，ｍ−，ｐ
−）トリル基等が挙げられる。The arylethenyl group represented by Ar 1 to Ar 4 , R 1 and R 2 is preferably a 2-phenylethenyl group or a 2,2-diphenylethenyl group, and further, an aryl group or an alkyl group. It may have a substituent such as a group, an alkoxy group, an allyloxy group, an amino group, a cyano group and a nitro group. Specifically, a phenyl group, (o
-,M-,p-)biphenyl group, (1,2)naphthyl group, methyl group, ethyl group, propyl group, butyl group, methoxy group, ethoxy group, phenoxy group, (o-,m-,p
-) A tolyl group and the like can be mentioned.
【００２８】Ｒ1 〜Ｒ3 で表されるアルキル基として
は、直鎖状でも分岐を有するものであってもよく、炭素
数１〜１０、さらには１〜４の置換もしくは無置換のア
ルキル基が好ましい。特に、炭素数１〜４の無置換のア
ルキル基が好ましく、具体的にはメチル基、エチル基、
（ｎ−，ｉ−）プロピル基、（ｎ−，ｉ−，ｓ−，ｔ
−）ブチル基等が挙げられる。The alkyl group represented by R 1 to R 3 may be linear or branched and has 1 to 10 carbon atoms, more preferably 1 to 4 substituted or unsubstituted alkyl groups. Is preferred. In particular, an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and specifically, a methyl group, an ethyl group,
(N-,i-)propyl group, (n-,i-,s-,t
-) Butyl group and the like can be mentioned.
【００２９】Ｒ1 およびＲ2 で表されるアルコキシ基と
しては、アルキル基部分の炭素数が１〜６のものが好ま
しく、具体的にはメトキシ基、エトキシ基等が挙げられ
る。アルコキシ基は、さらに置換されていてもよい。The alkoxy group represented by R 1 and R 2 preferably has an alkyl group moiety having 1 to 6 carbon atoms, and specific examples thereof include a methoxy group and an ethoxy group. The alkoxy group may be further substituted.
【００３０】Ｒ1 およびＲ2 で表されるアミノ基は、無
置換でも置換基を有するものであってもよいが、置換基
を有することが好ましく、この場合の置換基としてはア
ルキル基（メチル基、エチル基等）、アリール基（フェ
ニル基等）などが挙げられる。具体的にはジエチルアミ
ノ基、ジフェニルアミノ基、ジ（ｍ−トリル）アミノ基
等が挙げられる。The amino group represented by R 1 and R 2 may be unsubstituted or may have a substituent, but preferably has a substituent. In this case, the substituent may be an alkyl group (methyl group). Group, ethyl group, etc.), aryl group (phenyl group, etc.) and the like. Specific examples thereof include a diethylamino group, a diphenylamino group and a di(m-tolyl)amino group.
【００３１】化３において、ｒ１およびｒ２は、各々、
０または１〜３の整数を表し、特に、０〜２であること
が好ましい。ｒ１およびｒ２が、各々、１〜３の整数、
特に１または２であるとき、Ｒ1 およびＲ2 は、各々、
メチル基、フェニル基であることが好ましい。In the chemical formula 3, r1 and r2 are respectively
It represents 0 or an integer of 1 to 3, particularly preferably 0 to 2. r1 and r2 are each an integer of 1 to 3,
Particularly when 1 or 2, R 1 and R 2 are each
It is preferably a methyl group or a phenyl group.
【００３２】化３において、ｒ3は、各々、０または１
〜３の整数を表し、特に、０〜２であることが好まし
い。ｒ３が、各々、１〜３の整数、特に１または２であ
るとき、Ｒ3 は、各々、メチル基、フェニル基であるこ
とが好ましい。In the chemical formula 3, r3 is 0 or 1 respectively.
It represents the integer of -3, and it is especially preferable that it is 0-2. When r3 is an integer of 1 to 3, particularly 1 or 2, R 3 is preferably a methyl group or a phenyl group, respectively.
【００３３】化３において、Ｒ1 〜Ｒ3 は同一でも異な
るものであってもよく、Ｒ1 、Ｒ2とＲ3 とが各々複数
存在するとき、Ｒ1 同士、Ｒ2 同士、Ｒ3 同士は各々同
一でも異なるものであってもよい。In the chemical formula 3 , R 1 to R 3 may be the same or different, and when there are a plurality of R 1 , R 2 and R 3 , each R 1 , R 2 , R 3 , R 3 May be the same or different.
【００３４】化３において、Ｌ1 は単結合またはアリー
レン基を表す。Ｌ1 で表されるアリーレン基としては、
無置換であることが好ましく、具体的にはフェニレン
基、ビフェニレン基、アントリレン基等の通常のアリー
レン基の他、２個ないしそれ以上のアリーレン基が直接
連結したものが挙げられる。Ｌ1 としては、単結合、ｐ
−フェニレン基、４，４′−ビフェニレン基等が好まし
い。In the chemical formula 3, L 1 represents a single bond or an arylene group. As the arylene group represented by L 1 ,
It is preferably unsubstituted, and specific examples thereof include ordinary arylene groups such as a phenylene group, a biphenylene group, and an anthrylene group, as well as those in which two or more arylene groups are directly linked. L 1 is a single bond, p
-Phenylene group, 4,4'-biphenylene group and the like are preferable.
【００３５】また、Ｌ1 で表されるアリーレン基は、２
個ないしそれ以上のアリーレン基がアルキレン基、−Ｏ
−、−Ｓ−または−ＮＲ−が介在して連結するものであ
ってもよい。ここで、Ｒはアルキル基またはアリール基
を表す。アルキル基としてはメチル基、エチル基等が挙
げられ、アリール基としてはフェニル基等が挙げられ
る。なかでも、アリール基が好ましく、上記のフェニル
基のほか、Ａ1 、Ａ2 であってもよく、さらにはフェニ
ル基にＡ1 またはＡ2 が置換したものであってもよい。The arylene group represented by L 1 is 2
One or more arylene groups are alkylene groups, -O
It may be linked via -, -S- or -NR-. Here, R represents an alkyl group or an aryl group. Examples of the alkyl group include a methyl group and an ethyl group, and examples of the aryl group include a phenyl group. Among them, the aryl group is preferred, other phenyl group of the above, A 1, may be A 2, further it may be those A 1 or A 2 is substituted in the phenyl group.
【００３６】また、アルキレン基としてはメチレン基、
エチレン基等が好ましい。このようなアリーレン基の具
体例を以下に示す。As the alkylene group, a methylene group,
Ethylene groups and the like are preferred. Specific examples of such an arylene group are shown below.
【００３７】[0037]
【化５】 [Chemical 5]
【００３８】次に、化４について説明すると、化４にお
いて、Ｒ4 は化３におけるＲ1 またはＲ2 と、またＲ5
は化３におけるＲ3 と、ｒ４は化３におけるｒ１または
ｒ２と、さらにＬ2 は化３におけるＬ１とそれぞれ同義
であり、好ましいものも同様である。Next, referring to Chemical formula 4, in Chemical formula 4, R 4 is R 1 or R 2 in Chemical formula 3, and R 5
R 3 has the same meaning as R 3 in Chemical Formula 3, r 4 has the same meaning as r 1 or r 2 in Chemical Formula 3, and L 2 has the same meaning as L 1 in Chemical Formula 3, and the preferred ones are also the same.
【００３９】また、化４において、ｒ５は、各々、０ま
たは１〜４の整数を表し、特に、０〜２であることが好
ましい。ｒ５が、各々、１〜３の整数、特に１または２
であるとき、Ｒ5 は、各々、メチル基、フェニル基であ
ることが好ましい。In the chemical formula 4, each r5 represents 0 or an integer of 1 to 4, preferably 0 to 2. r5 is an integer of 1 to 3, particularly 1 or 2
And R 5 is preferably a methyl group or a phenyl group, respectively.
【００４０】化４において、Ｒ4 とＲ5 とは同一でも異
なるものであってもよく、Ｒ4 とＲ 5 が各々複数存在す
るとき、Ｒ4 同士、Ｒ5 同士は、各々同一でも異なるも
のであってもよい。In the chemical formula 4, RFourAnd RFiveSame as but different from
May be RFourAnd R FiveThere are multiple
When RFourEach other, RFiveThey are the same or different
May be
【００４１】化３、化４で表される化合物を以下に例示
するが、本発明はこれらに限定されるものではない。な
お、表中の略号のうちＮ（Ｔｏｌｙ）2 は、Ｎ（トリ
ル）2を表す。The compounds represented by Chemical formulas 3 and 4 are exemplified below, but the present invention is not limited thereto. In the abbreviations in the table, N(Toly) 2 represents N(tolyl) 2 .
【００４２】[0042]
【表１】 [Table 1]
【００４３】[0043]
【表２】 [Table 2]
【００４４】[0044]
【表３】 [Table 3]
【００４５】[0045]
【表４】 [Table 4]
【００４６】[0046]
【表５】 [Table 5]
【００４７】[0047]
【表６】 [Table 6]
【００４８】[0048]
【表７】 [Table 7]
【００４９】[0049]
【表８】 [Table 8]
【００５０】[0050]
【表９】 [Table 9]
【００５１】[0051]
【表１０】 [Table 10]
【００５２】[0052]
【表１１】 [Table 11]
【００５３】[0053]
【表１２】 [Table 12]
【００５４】[0054]
【表１３】 [Table 13]
【００５５】[0055]
【表１４】 [Table 14]
【００５６】[0056]
【表１５】 [Table 15]
【００５７】[0057]
【表１６】 [Table 16]
【００５８】[0058]
【表１７】 [Table 17]
【００５９】[0059]
【表１８】 [Table 18]
【００６０】[0060]
【表１９】 [Table 19]
【００６１】[0061]
【表２０】 [Table 20]
【００６２】[0062]
【表２１】 [Table 21]
【００６３】[0063]
【表２２】 [Table 22]
【００６４】[0064]
【表２３】 [Table 23]
【００６５】[0065]
【表２４】 [Table 24]
【００６６】[0066]
【表２５】 [Table 25]
【００６７】[0067]
【表２６】 [Table 26]
【００６８】[0068]
【表２７】 [Table 27]
【００６９】[0069]
【表２８】 [Table 28]
【００７０】[0070]
【表２９】 [Table 29]
【００７１】[0071]
【表３０】 [Table 30]
【００７２】本発明のフェニルアントラセン誘導体であ
る有機ＥＬ素子用化合物（以下、「本発明の化合物」と
もいう。）は、（１）ハロゲン化アリールアントラセン
化合物を、Ｎｉ（ｃｏｄ）2 〔ｃｏｄ：１，５−シクロ
オクタジエン〕でカップリング、もしくはジハロゲン化
アリールをグリニャール化しＮｉＣｌ2 （ｄｐｐｅ）
［ｄｐｐｅ：ジフェニルフォスフィノエタン］、ＮｉＣ
ｌ2 （ｄｐｐｐ）〔ｄｐｐｐ：ジフェニルフォスフィノ
プロパン〕、などのＮｉ錯体などを用いてクロスカップ
リングする方法、（２）ボロン酸アリールとハロゲン化
アリールアントラセン化合物を、Ｐｄ錯体等を用いてク
ロスカプリングする方法、（３）アントラキノン、ベン
ゾキノン、フェニルアンスロンもしくはビアントロンと
グリニャール化したアリールもしくはリチオ化したアリ
ールとの反応および還元によりクロスカップリングする
方法、等により得られる。The compound for organic EL device which is the phenylanthracene derivative of the present invention (hereinafter, also referred to as "the compound of the present invention") is prepared by converting (1) a halogenated arylanthracene compound into Ni(cod) 2 [cod:1 , 5-Cyclooctadiene], or a dihalogenated aryl is Grignard-ized to form NiCl 2 (dppe)
[Dpppe: diphenylphosphinoethane], NiC
cross-coupling using a Ni complex such as l 2 (dppp) [dpppp: diphenylphosphinopropane], (2) cross-coupling of an aryl boronate and a halogenated aryl anthracene compound using a Pd complex or the like And (3) cross-coupling by the reaction and reduction of anthraquinone, benzoquinone, phenylanthrone or bianthrone with Grignard-ized aryl or lithiated aryl, and the like.
【００７３】このようにして得られた化合物は、元素分
析、質量分析、赤外吸収スペクトル、1Ｈまたは13Ｃ核
磁気共鳴吸収（ＮＭＲ）スペクトルなどによって同定す
ることができる。The compound thus obtained can be identified by elemental analysis, mass spectrometry, infrared absorption spectrum, 1 H or 13 C nuclear magnetic resonance absorption (NMR) spectrum and the like.
【００７４】本発明のフェニルアントラセン誘導体は、
４００〜２０００程度、さらには４００〜１０００程度
の分子量をもち、２００〜５００℃の高融点を有し、８
０〜２５０℃、さらには１００〜２５０℃、よりさらに
は１３０〜２５０℃、特に１５０〜２５０℃のガラス転
移温度（Ｔｇ）を示す。従って、通常の真空蒸着等によ
り透明で室温以上でも安定なアモルファス状態の平滑で
良好な膜を形成し、しかもその良好な膜の状態が長期間
に渡って維持される。The phenylanthracene derivative of the present invention is
It has a molecular weight of about 400 to 2000, further about 400 to 1000, a high melting point of 200 to 500° C., and 8
It exhibits a glass transition temperature (Tg) of 0-250°C, even 100-250°C, even more 130-250°C, especially 150-250°C. Therefore, a smooth and good film in an amorphous state, which is transparent and stable even at room temperature or more, is formed by ordinary vacuum vapor deposition and the good film state is maintained for a long period of time.
【００７５】本発明の有機ＥＬ素子（以下、「ＥＬ素
子」ともいう。）は、少なくとも１層の有機化合物層を
有し、少なくとも１層の有機化合物層が本発明の化合物
を含有する。本発明の有機ＥＬ素子の構成例を図１に示
す。同図に示される有機ＥＬ素子は、基板１上に、陽極
２、ホール注入輸送層３、発光層４、電子注入輸送層
５、陰極６を順次有する。The organic EL device of the present invention (hereinafter, also referred to as “EL device”) has at least one organic compound layer, and at least one organic compound layer contains the compound of the present invention. An example of the structure of the organic EL device of the present invention is shown in FIG. The organic EL device shown in the figure has an anode 2, a hole injecting and transporting layer 3, a light emitting layer 4, an electron injecting and transporting layer 5, and a cathode 6 on a substrate 1 in this order.
【００７６】発光層は、ホールおよび電子の注入機能、
それらの輸送機能、ホールと電子の再結合により励起子
を生成させる機能を有する。ホール注入輸送層は、陽極
からのホールの注入を容易にする機能、ホールを輸送す
る機能および電子の輸送を妨げる機能を有し、電子注入
輸送層は、陰極からの電子の注入を容易にする機能、電
子を輸送する機能およびホールの輸送を妨げる機能を有
するものであり、これらの層は、発光層へ注入されるホ
ールや電子を増大・閉じ込めさせ、再結合領域を最適化
させ、発光効率を改善する。電子注入輸送層およびホー
ル注入輸送層は、発光層に用いる化合物の電子注入、電
子輸送、ホール注入、ホール輸送の各機能の高さを考慮
し、必要に応じて設けられる。例えば、発光層に用いる
化合物のホール注入輸送機能または電子注入輸送機能が
高い場合には、ホール注入輸送層または電子注入輸送層
を設けずに、発光層がホール注入輸送層または電子注入
輸送層を兼ねる構成とすることができる。また、場合に
よってはホール注入輸送層および電子注入輸送層のいず
れも設けなくてよい。また、ホール注入輸送層および電
子注入輸送層は、それぞれにおいて、注入機能をもつ層
と輸送機能をもつ層とを別個に設けてもよい。The light emitting layer has a function of injecting holes and electrons,
It has a function of transporting them and a function of generating excitons by recombination of holes and electrons. The hole injecting and transporting layer has a function of facilitating injection of holes from the anode, a function of transporting holes and a function of hindering electron transport, and the electron injecting and transporting layer facilitates injection of electrons from the cathode. It has a function, a function of transporting electrons, and a function of hindering the transport of holes. These layers increase and confine holes and electrons injected into the light emitting layer, optimize the recombination region, and improve the luminous efficiency. To improve. The electron injecting and transporting layer and the hole injecting and transporting layer are provided as necessary in consideration of the electron injection, electron transport, hole injection, and hole transport functions of the compound used for the light emitting layer. For example, when the compound used for the light emitting layer has a high hole injecting/transporting function or an electron injecting/transporting function, the light emitting layer does not have the hole injecting/transporting layer or the electron injecting/transporting layer, and the light emitting layer does not have the hole injecting/transporting layer or the electron injecting/transporting layer. It is also possible to have a double-sided structure. In some cases, neither the hole injecting and transporting layer nor the electron injecting and transporting layer may be provided. Further, the hole injecting and transporting layer and the electron injecting and transporting layer may each be provided with a layer having an injection function and a layer having a transport function separately.
【００７７】本発明の化合物は、比較的ニュートラルな
化合物なので発光層に用いることが好ましいが、ホール
注入輸送層や電子注入輸送層にも適用可能である。Since the compound of the present invention is a relatively neutral compound, it is preferably used for the light emitting layer, but it is also applicable to the hole injecting and transporting layer and the electron injecting and transporting layer.
【００７８】また、組み合わせる発光層や電子注入輸送
層やホール注入輸送層のキャリア移動度やキャリア密度
（イオン化ポテンシャル・電子親和力により決まる）を
考慮しながら、膜厚をコントロールすることで、再結合
領域・発光領域を自由に設計することが可能であり、発
光色の設計や、両電極の干渉効果による発光輝度・発光
スペクトルの制御や、発光の空間分布の制御を可能にで
きる。The recombination region is controlled by controlling the film thickness while considering the carrier mobility and carrier density (determined by the ionization potential and electron affinity) of the light emitting layer, the electron injecting and transporting layer and the hole injecting and transporting layer to be combined. -It is possible to freely design the light emitting region, and it is possible to design the light emitting color, control the light emitting luminance and light emitting spectrum by the interference effect of both electrodes, and control the spatial distribution of light emission.
【００７９】本発明の化合物を発光層に用いる場合につ
いて説明する。発光層には本発明の化合物のほか、他の
蛍光性物質を用いてもよく、他の蛍光性物質としては、
例えば、特開昭６３−２６４６９２号公報に開示されて
いるような化合物、例えば、キナクリドン、スチリル系
色素、ルブレン等の芳香族炭化水素、ジフェニルイソベ
ンゾフラン等または３級アミン等の化合物から選択され
る少なくとも１種が挙げられる。このような蛍光性物質
の含有量は、本発明の化合物の１０モル％以下とするこ
とが好ましい。このような化合物を適宜選択して添加す
ることにより、発光光を長波長側にシフトすることがで
きる。The case where the compound of the present invention is used in the light emitting layer will be described. In addition to the compound of the present invention, other fluorescent substances may be used in the light emitting layer. As other fluorescent substances,
For example, it is selected from compounds such as those disclosed in JP-A-63-264692, for example, quinacridone, styryl dyes, aromatic hydrocarbons such as rubrene, compounds such as diphenylisobenzofuran and tertiary amines. At least 1 type is mentioned. The content of such a fluorescent substance is preferably 10 mol% or less of the compound of the present invention. The emission light can be shifted to the long wavelength side by appropriately selecting and adding such a compound.
【００８０】本発明の化合物を発光層に用いる場合、ホ
ール注入輸送層および電子注入輸送層には、通常の有機
ＥＬ素子に用いられている各種有機化合物、例えば、特
開昭６３−２９５６９５号公報、特開平２−１９１６９
４号公報、特開平３−７９２号公報等に記載されている
各種有機化合物を用いることができる。例えば、ホール
注入輸送層には、芳香族三級アミン、ヒドラゾン誘導
体、カルバゾール誘導体、トリアゾール誘導体、イミダ
ゾール誘導体等を用いることができ、また、電子注入輸
送層には、アルミキノリノールなどの有機金属錯体誘導
体、オキサジアゾール誘導体、ピリジン誘導体、ピリミ
ジン誘導体、キノリン誘導体、キノキサリン誘導体、ジ
フェニルキノン誘導体、ペリレン誘導体、フルオレン誘
導体等を用いることができる。When the compound of the present invention is used in the light emitting layer, the hole injecting and transporting layer and the electron injecting and transporting layer include various organic compounds used in ordinary organic EL devices, for example, JP-A-63-295695. JP-A-2-19169
Various organic compounds described in JP-A No. 4 and JP-A-3-792, etc. can be used. For example, an aromatic tertiary amine, a hydrazone derivative, a carbazole derivative, a triazole derivative, an imidazole derivative or the like can be used for the hole injecting and transporting layer, and an organometallic complex derivative such as aluminum quinolinol is used for the electron injecting and transporting layer. An oxadiazole derivative, a pyridine derivative, a pyrimidine derivative, a quinoline derivative, a quinoxaline derivative, a diphenylquinone derivative, a perylene derivative, a fluorene derivative, or the like can be used.
【００８１】ホール注入輸送層をホール注入層とホール
輸送層とに分けて設層する場合は、ホール注入輸送層用
の化合物のなかから好ましい組合せを選択して用いるこ
とができる。このとき、陽極（ＩＴＯ等）側からイオン
化ポテンシャルの小さい化合物の層の順に積層すること
が好ましい。また陽極表面には薄膜性の良好な化合物を
用いることが好ましい。このような積層順については、
ホール注入輸送層を２層以上設けるときも同様である。
このような積層順とすることによって、駆動電圧が低下
し、電流リークの発生やダークスポットの発生・成長を
防ぐことができる。また、素子化する場合、蒸着を用い
ているので１〜１０nm程度の薄い膜も、均一かつピンホ
ールフリーとすることができるため、ホール注入層にイ
オン化ポテンシャルが小さく、可視部に吸収をもつよう
な化合物を用いても、発光色の色調変化や再吸収による
効率の低下を防ぐことができる。When the hole injecting and transporting layer is separately formed into the hole injecting layer and the hole transporting layer, preferable combinations can be selected and used from the compounds for the hole injecting and transporting layer. At this time, it is preferable to stack layers of a compound having a small ionization potential in this order from the anode (ITO or the like) side. Further, it is preferable to use a compound having a good thin film property on the surface of the anode. For such a stacking order,
The same applies when two or more hole injecting and transporting layers are provided.
By adopting such a stacking order, the driving voltage is lowered, and it is possible to prevent the occurrence of current leakage and the generation/growth of dark spots. In addition, since vapor deposition is used for device formation, even thin films of about 1 to 10 nm can be made uniform and pinhole-free, so the hole injection layer has a low ionization potential and absorption in the visible region. Even if such a compound is used, it is possible to prevent a decrease in efficiency due to a change in the color tone of the emission color or reabsorption.
【００８２】電子注入輸送層を電子注入層と電子輸送層
とに分けて設層する場合は、電子注入輸送層用の化合物
のなかから好ましい組合せを選択して用いることができ
る。このとき、陰極側から電子親和力の値の大きい化合
物の層の順に積層することが好ましい。このような積層
順については電子注入輸送層を２層以上設けるときも同
様である。When the electron injecting and transporting layer is separately formed into the electron injecting layer and the electron transporting layer, preferred combinations can be selected and used from the compounds for the electron injecting and transporting layer. At this time, it is preferable to stack the layers of the compound having a large electron affinity value in this order from the cathode side. This stacking order is the same when two or more electron injecting and transporting layers are provided.
【００８３】なお、本発明では、発光層を電子注入輸送
性化合物とホール注入輸送性化合物との混合層とするこ
とも好ましい。そして、このような混合層に本発明の化
合物を含有させる。本発明の化合物は、通常、蛍光性物
質として含有されるため、より具体的には、本発明の化
合物が電子注入輸送性化合物であるとき、他のホール注
入輸送性化合物をさらに添加することが好ましく、本発
明の化合物がホール注入輸送性化合物であるときは、他
の電子注入輸送性化合物をさらに添加することが好まし
い。この場合、特に好ましい組み合わせとしては、電子
注入輸送性の化合物に本発明の化合物を用い、ホール注
入輸送性の化合物にアミン系、またはスチリルアミン系
の化合物を用いる。上記の混合層における電子注入輸送
性化合物とホール注入輸送性化合物との混合比は、用い
る材料のキャリア移動度とキャリア濃度に依存するが、
一般的には重量比で、電子注入輸送性化合物：ホール注
入輸送性化合物が５：９５〜９５：５であることが好ま
しく、特には１０：９０〜９０：１０であることが好ま
しい。また、さらには２０：８０〜２０：８０であるこ
とが好ましい。また、混合層の厚みは分子層１層から有
機化合物の膜厚未満とすることが好ましい。In the present invention, it is also preferable that the light emitting layer is a mixed layer of an electron injecting/transporting compound and a hole injecting/transporting compound. Then, the compound of the present invention is contained in such a mixed layer. Since the compound of the present invention is usually contained as a fluorescent substance, more specifically, when the compound of the present invention is an electron injecting and transporting compound, another hole injecting and transporting compound may be further added. Preferably, when the compound of the present invention is a hole injecting/transporting compound, another electron injecting/transporting compound is preferably added. In this case, as a particularly preferable combination, the compound of the present invention is used as the compound having an electron injecting and transporting property, and the amine compound or the styrylamine compound is used as the compound having a hole injecting and transporting property. The mixing ratio of the electron injecting and transporting compound and the hole injecting and transporting compound in the above mixed layer depends on the carrier mobility and carrier concentration of the material used,
Generally, the weight ratio of the electron injecting and transporting compound:hole injecting and transporting compound is preferably 5:95 to 95:5, and particularly preferably 10:90 to 90:10. Further, it is more preferably 20:80 to 20:80. In addition, the thickness of the mixed layer is preferably less than the thickness of one molecular layer to the thickness of the organic compound.
【００８４】この混合に供する電子注入輸送性化合物
は、上記の電子注入輸送層用の化合物のなかから、また
ホール注入輸送性化合物は、上記のホール注入輸送層用
の化合物のなかから選択して用いることができる。ま
た、場合によっては本発明の化合物から選択して用いて
もよい。さらに、混合層において、電子注入輸送性化合
物、ホール注入輸送性化合物は各々１種のみ用いても２
種以上を併用してもよい。また、混合層には発光強度を
高めるために、本発明の化合物や他の蛍光性物質をドー
プして用いてもよい。The electron injecting and transporting compound used for this mixing is selected from the above compounds for the electron injecting and transporting layer, and the hole injecting and transporting compound is selected from the above compounds for the hole injecting and transporting layer. Can be used. Moreover, you may select and use from the compound of this invention depending on the case. Furthermore, even if only one type of electron injecting/transporting compound and one type of hole injecting/transporting compound are used in the mixed layer, 2
You may use together 1 or more types. The mixed layer may be doped with the compound of the present invention or another fluorescent substance in order to increase the emission intensity.
【００８５】さらに、他の電子注入輸送性化合物および
他のホール注入輸送性化合物の混合層とし、このような
混合層に本発明の化合物をドープして用いてもよい。Further, a mixed layer of another electron injecting and transporting compound and another hole injecting and transporting compound may be formed, and such a mixed layer may be doped with the compound of the present invention.
【００８６】このような混合層をＥＬ素子に適用するこ
とによって、素子の安定性が向上する。By applying such a mixed layer to the EL device, the stability of the device is improved.
【００８７】本発明の化合物は電子注入輸送層に用いる
ことも好ましい。この場合、発光層に用いる蛍光性物質
は、本発明の化合物より長波長もしくは同程度の波長の
蛍光をもつものを用いることが好ましい。例えば、上記
した、発光層において本発明の化合物と併用できる蛍光
性物質のなかから選択して用いることができる。また、
本発明の化合物は、このような構成において、さらに発
光層にも用いることができる。また、本発明の化合物は
電子注入輸送層を兼ねた発光層にも用いることができ
る。また、電子注入輸送層とする場合、電子キャリア密
度を向上させるため、Ｌｉ，Ｎａ，Ｋ，Ｃｓ等の仕事関
数の小さな金属、金属ハロゲン化物もしくは金属酸化物
等を電極界面、もしくは界面近傍にドープしてもよい。The compounds of the present invention are also preferably used in the electron injecting and transporting layer. In this case, as the fluorescent substance used in the light emitting layer, it is preferable to use a substance having fluorescence having a wavelength longer than or about the same as the wavelength of the compound of the present invention. For example, it can be selected and used from the above-mentioned fluorescent substances that can be used in combination with the compound of the present invention in the light emitting layer. Also,
In such a constitution, the compound of the present invention can be further used in the light emitting layer. The compound of the present invention can also be used in a light emitting layer which also serves as an electron injecting and transporting layer. In the case of using an electron injecting and transporting layer, in order to improve the electron carrier density, a metal having a small work function such as Li, Na, K, Cs, a metal halide or a metal oxide is doped at the electrode interface or in the vicinity of the interface. You may.
【００８８】本発明の化合物はホール注入輸送層に用い
ることができる。The compound of the present invention can be used in the hole injecting and transporting layer.
【００８９】本発明の化合物をホール注入輸送層に用い
る場合、発光層に用いる蛍光性物質は、本発明の化合物
より長波長の蛍光をもつものから選択すればよく、例え
ば、上記した、発光層において本発明の化合物と併用さ
れる蛍光性物質の１種以上から適宜選択すればよい。こ
のような場合、発光層にも本発明の化合物を用いること
ができる。また、ホール注入輸送層とする場合、ホール
キャリア密度を向上させるために、４級アミン等のホー
ル発生ドーパントを電極界面、もしくは界面近傍にドー
プしてもよい。When the compound of the present invention is used in the hole injecting and transporting layer, the fluorescent substance used in the light emitting layer may be selected from those having fluorescence of a longer wavelength than that of the compound of the present invention. In, it may be appropriately selected from one or more fluorescent substances used in combination with the compound of the present invention. In such a case, the compound of the present invention can be used in the light emitting layer. In the case of forming a hole injecting and transporting layer, a hole generating dopant such as a quaternary amine may be doped at the electrode interface or in the vicinity of the interface in order to improve the hole carrier density.
【００９０】なお、上記において、他の蛍光性物質を主
に発光層に用いる場合、本発明の化合物を蛍光性物質と
して１０モル％以下添加して併用してもよい。In the above case, when another fluorescent substance is mainly used in the light emitting layer, the compound of the present invention may be added in an amount of 10 mol% or less as a fluorescent substance and used in combination.
【００９１】発光層の厚さ、ホール注入輸送層の厚さお
よび電子注入輸送層の厚さは特に限定されず、形成方法
によっても異なるが、通常、５〜１０００nm程度、特に
８〜２００nmとすることが好ましい。The thickness of the light emitting layer, the thickness of the hole injecting and transporting layer, and the thickness of the electron injecting and transporting layer are not particularly limited and may vary depending on the forming method, but are usually about 5 to 1000 nm, particularly 8 to 200 nm. Preferably.
【００９２】ホール注入輸送層の厚さおよび電子注入輸
送層の厚さは、再結合・発光領域の設計によるが、発光
層の厚さと同程度もしくは１／１０〜１０倍程度とすれ
ばよい。電子もしくはホールの、各々の注入層と輸送層
を分ける場合は、注入層は１nm以上、輸送層は２０nm以
上とするのが好ましい。このときの注入層、輸送層の厚
さの上限は、通常、注入層で１００nm程度、輸送層で１
０００nm程度である。The thickness of the hole injecting and transporting layer and the thickness of the electron injecting and transporting layer may be the same as the thickness of the light emitting layer or about 1/10 to 10 times, depending on the design of the recombination/light emitting region. When the electron injection layer and the hole injection layer are separated from the transport layer, it is preferable that the injection layer has a thickness of 1 nm or more and the transport layer has a thickness of 20 nm or more. At this time, the upper limit of the thickness of the injection layer and the transport layer is usually about 100 nm in the injection layer and 1 in the transport layer.
It is about 000 nm.
【００９３】陰極には、仕事関数の小さい材料、例え
ば、Ｌｉ、Ｎａ、Ｍｇ、Ａｌ、Ａｇ、Ｉｎあるいはこれ
らの１種以上を含む合金を用いることが好ましい。ま
た、陰極は結晶粒が細かいことが好ましく、特に、アモ
ルファス状態であることが好ましい。陰極の厚さは１０
〜１０００nm程度とすることが好ましい。For the cathode, it is preferable to use a material having a low work function, for example, Li, Na, Mg, Al, Ag, In or an alloy containing at least one of these. The cathode preferably has fine crystal grains, and particularly preferably is in an amorphous state. The thickness of the cathode is 10
It is preferably about 1000 nm.
【００９４】ＥＬ素子を面発光させるためには、少なく
とも一方の電極が透明ないし半透明である必要があり、
上記したように陰極の材料には制限があるので、好まし
くは発光光の透過率が８０％以上となるように陽極の材
料および厚さを決定することが好ましい。具体的には、
例えば、ＩＴＯ、ＳｎＯ2 、Ｎｉ、Ａｕ、Ｐｔ、Ｐｄ、
ドーパントをドープしたポリピロールなどを陽極に用い
ることが好ましい。また、陽極の厚さは１０〜５００nm
程度とすることが好ましい。また、素子の信頼性を向上
するために駆動電圧が低いことが必要であるが、好まし
いものとして１０〜３０Ω／□程度ないし１０Ω／□以
下（通常５〜１０Ω／□）のＩＴＯが挙げられる。At least one of the electrodes must be transparent or semi-transparent in order to allow the EL element to emit surface light.
Since the material of the cathode is limited as described above, it is preferable to determine the material and thickness of the anode so that the transmittance of emitted light is 80% or more. In particular,
For example, ITO, SnO 2 , Ni, Au, Pt, Pd,
It is preferable to use polypyrrole doped with a dopant for the anode. The thickness of the anode is 10-500nm
It is preferable to set it to a degree. Further, it is necessary that the driving voltage is low in order to improve the reliability of the device, but preferable examples include ITO having a resistance of about 10 to 30 Ω/□ to 10 Ω/□ or less (usually 5 to 10 Ω/□).
【００９５】基板材料に特に制限はないが、図示例では
基板側から発光光を取り出すため、ガラスや樹脂等の透
明ないし半透明材料を用いる。また、基板に色フィルタ
ー膜や誘電体反射膜を用いて発光色をコントロールして
もよい。The substrate material is not particularly limited, but in the illustrated example, a transparent or semitransparent material such as glass or resin is used in order to take out emitted light from the substrate side. In addition, the emission color may be controlled by using a color filter film or a dielectric reflection film on the substrate.
【００９６】なお、基板に不透明な材料を用いる場合に
は、図１に示される積層順序を逆にしてもよい。When an opaque material is used for the substrate, the stacking order shown in FIG. 1 may be reversed.
【００９７】次に、本発明の有機ＥＬ素子の製造方法を
説明する。陰極および陽極は、蒸着法やスパッタ法等の
気相成長法により形成することが好ましい。Next, a method for manufacturing the organic EL device of the present invention will be described. The cathode and the anode are preferably formed by vapor phase growth methods such as vapor deposition and sputtering.
【００９８】ホール注入輸送層、発光層および電子注入
輸送層の形成には、均質な薄膜が形成できることから真
空蒸着法を用いることが好ましい。真空蒸着法を用いた
場合、アモルファス状態または結晶粒径が０．２μm 以
下（通常０．０１μm 以上）の均質な薄膜が得られる。
結晶粒径が０．２μm を超えていると、不均一な発光と
なり、素子の駆動電圧を高くしなければならなくなり、
電荷の注入効率も著しく低下する。For forming the hole injecting and transporting layer, the light emitting layer and the electron injecting and transporting layer, it is preferable to use the vacuum deposition method because a uniform thin film can be formed. When the vacuum deposition method is used, a homogeneous thin film having an amorphous state or a crystal grain size of 0.2 μm or less (usually 0.01 μm or more) can be obtained.
If the crystal grain size exceeds 0.2 μm, non-uniform light emission occurs, and the drive voltage of the device must be increased,
The charge injection efficiency is also significantly reduced.
【００９９】真空蒸着の条件は特に限定されないが、１
０-5 Torr以下の真空度とし、蒸着速度は０．１〜１nm
／sec 程度とすることが好ましい。また、真空中で連続
して各層を形成することが好ましい。真空中で連続して
形成すれば、各層の界面に不純物が吸着することを防げ
るため、高特性が得られる。また、素子の駆動電圧を低
くすることができる。The conditions of vacuum vapor deposition are not particularly limited, but 1
The degree of vacuum is 0 -5 Torr or less, and the deposition rate is 0.1 to 1 nm.
/Sec is preferable. Moreover, it is preferable to form each layer continuously in a vacuum. If they are continuously formed in vacuum, impurities can be prevented from adsorbing to the interface of each layer, so that high characteristics can be obtained. Further, the driving voltage of the element can be lowered.
【０１００】これら各層の形成に真空蒸着法を用いる場
合において、１層に複数の化合物を含有させる場合、化
合物を入れた各ボートを個別に温度制御して水晶振動子
膜厚計でモニターしながら共蒸着することが好ましい。In the case where a vacuum vapor deposition method is used to form each of these layers, when a plurality of compounds are contained in one layer, the temperature of each boat containing the compounds is individually controlled while monitoring with a quartz oscillator film thickness meter. Co-deposition is preferred.
【０１０１】本発明のＥＬ素子は、通常、直流駆動型の
ＥＬ素子として用いられるが、交流駆動またはパルス駆
動することもできる。印加電圧は、通常、２〜２０V 程
度とされる。The EL element of the present invention is usually used as a DC drive type EL element, but it can also be AC driven or pulse driven. The applied voltage is usually about 2 to 20V.
【０１０２】[0102]
【実施例】以下、本発明の具体的実施例を比較例ととも
に示し、本発明をさらに詳細に説明する。 ＜合成例１＞ 化合物１（10,10’-ビス（2-ビフェニルイル）-9,9’-
ビアンスリル）の合成 ２−ブロモビフェニル７．８g、ジエチルエーテル５０m
lとトルエン５０mlを混合し、これに１．６Mブチルリチ
ウムのヘキサン溶液２０．４mlをゆっくり滴下しながら
１時間室温で攪拌し、２−リチオビフェニルを調整し
た。次に、トルエン１５０mlとビアンスロン４gの混合
物にこのリチオビフェニルをゆっくり滴下し、室温で一
昼夜攪拌した。次いで、これに蒸留水１００mlを加えさ
らに１時間攪拌した後、この溶液を濾過し、廬物をトル
エン、メタノールで洗浄した。得られた物をテトラヒド
ロフランとトルエンから再結晶した後、カラム精製し、
４．３g の白色固体としてジオール体を得た。EXAMPLES Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention together with comparative examples. <Synthesis Example 1> Compound 1 (10,10'-bis(2-biphenylyl)-9,9'-
Bianthryl) Synthesis 2-bromobiphenyl 7.8g, diethyl ether 50m
l and 50 ml of toluene were mixed, and 20.4 ml of a 1.6 M butyllithium hexane solution was slowly added dropwise thereto, and the mixture was stirred at room temperature for 1 hour to prepare 2-lithiobiphenyl. Next, this lithiobiphenyl was slowly added dropwise to a mixture of 150 ml of toluene and 4 g of Bianthlon, and the mixture was stirred at room temperature for 24 hours. Then, 100 ml of distilled water was added thereto, and the mixture was further stirred for 1 hour, then the solution was filtered, and the residue was washed with toluene and methanol. After recrystallizing the obtained product from tetrahydrofuran and toluene, column purification,
The diol was obtained as a white solid (4.3 g).
【０１０３】このジオール体４g とテトラヒドロフラン
４００mlをフラスコに入れ塩化すず２５g と塩酸２５ml
を混合した溶液をゆっくり滴下した。このフラスコを７
０度のオイルバスで２時間加熱した後冷却し、２００ml
のトルエンを加え、蒸留水及び炭酸水素ナトリウムで洗
浄した。硫酸マグネシウムで乾燥した後、カラム精製と
再沈を繰り返し、３．７g の淡黄白色固体を得た。この
淡黄白色固体３．０gを昇華精製し２．８g の黄白色固
体を得た。この目的物（10,10’-ビス（2-ビフェニルイ
ル）-9,9’-ビアンスリル）の構造を下記に示す。4 g of this diol and 400 ml of tetrahydrofuran were placed in a flask and 25 g of tin chloride and 25 ml of hydrochloric acid were added.
The mixed solution was slowly added dropwise. 7 this flask
Heat in an oil bath at 0 degrees for 2 hours, then cool to 200 ml
Of toluene was added, and the mixture was washed with distilled water and sodium hydrogen carbonate. After drying with magnesium sulfate, column purification and reprecipitation were repeated to obtain 3.7 g of a pale yellowish white solid. 3.0 g of this pale yellowish white solid was purified by sublimation to obtain 2.8 g of a yellowish white solid. The structure of this desired product (10,10′-bis(2-biphenylyl)-9,9′-bianthryl) is shown below.
【０１０４】[0104]
【化６】 [Chemical 6]
【０１０５】この黄白色個体の質量分析およびＮＭＲス
ペクトル、赤外吸収スペクトルの測定を行ったところ、
目的物と矛盾しないことを確認した。また、ガラス転移
温度を測定したところ、１４４度であった。Mass spectrometry and NMR spectrum and infrared absorption spectrum of this yellowish white solid were measured.
I confirmed that it does not conflict with the target. The glass transition temperature was measured and found to be 144 degrees.
【０１０６】＜合成例２＞ 化合物２（10,10’-ビス（2,6-ジフェニルフェニル）-
9,9’-ビアンスリル）の合成 合成例１の２−ブロモビフェニルの代わりに、1−ブロ
モ−２,６−ジフェニルベンゼン９．３g を用いて合成
を行い、４．０g の目的化合物を得た。この、目的物
（10,10’-ビス（2,6-ジフェニルフェニル）-9,9’-ビ
アンスリル）の構造を下記に示す。<Synthesis Example 2> Compound 2 (10,10'-bis(2,6-diphenylphenyl)-
Synthesis of 9,9'-bianthril) Instead of 2-bromobiphenyl of Synthesis Example 1, 9.3 g of 1-bromo-2,6-diphenylbenzene was used for synthesis to obtain 4.0 g of the target compound. .. The structure of this target compound (10,10′-bis(2,6-diphenylphenyl)-9,9′-bianthryl) is shown below.
【０１０７】[0107]
【化７】 [Chemical 7]
【０１０８】この化合物の質量分析およびＮＭＲスペク
トル、赤外吸収スペクトルの測定を行ったところ、目的
物と矛盾しないことを確認した。また、融点は３４０
℃、ガラス転移温度は、１６６度であった。1Ｈ−ＮＭ
Ｒスペクトルを図２に、13Ｃ−ＮＭＲスペクトルを図３
に、赤外線スペクトルを図４に示す。Mass spectrometry of this compound and measurement of its NMR spectrum and infrared absorption spectrum confirmed that it did not contradict the desired product. The melting point is 340.
The glass transition temperature was 166°C. 1 H-NM
FIG. 2 shows the R spectrum and FIG. 3 shows the 13 C-NMR spectrum.
The infrared spectrum is shown in FIG.
【０１０９】＜合成例３＞ 化合物３（１０，１０’−ビス−（２−ｐ−ターフェニ
ルイル）−９，９’−ビアンスリル）の合成 合成例１の２−ブロモビフェニルの代わりに、２−ブロ
モ−P−ターフェニル９．３g を用いて合成を行い、
４．０g の目的化合物を得た。この目的物（１０，１
０’−ビス−（２−ｐ−ターフェニルイル）−９，９’
−ビアンスリル）の構造式を下記に示す。<Synthesis Example 3> Synthesis of Compound 3 (10,10'-bis-(2-p-terphenylyl)-9,9'-bianthryl) Instead of 2-bromobiphenyl in Synthesis Example 1, 2 Synthesis was carried out using 9.3 g of -bromo-P-terphenyl,
4.0 g of the desired compound is obtained. This object (10,1
0'-bis-(2-p-terphenylyl)-9,9'
-Bianthril) structural formula is shown below.
【０１１０】[0110]
【化８】 [Chemical 8]
【０１１１】この化合物の質量分析およびＮＭＲスペク
トル、赤外吸収スペクトルの測定を行ったところ、目的
物と矛盾しないことを確認した。また、ガラス転移温度
を測定したところ、１５４度であった。1Ｈ−ＮＭＲス
ペクトルを図５に示す。Mass spectrometry of this compound and measurement of its NMR spectrum and infrared absorption spectrum confirmed that it did not contradict the desired product. The glass transition temperature was measured and found to be 154 degrees. The 1 H-NMR spectrum is shown in FIG.
【０１１２】＜合成例４＞ 化合物４（１０，１０’−ビス−（２，５−フェニルフ
ェニル）−９，９’−ビアンスリル）の合成 合成例１の２−ブロモビフェニルの代わりに、1−ブロ
モ−２,５−ジフェニルベンゼン９．３g を用いて合成
を行い、４．０g の目的化合物を得た。この目的物（１
０，１０’−ビス−（２，５−フェニルフェニル）−
９，９’−ビアンスリル）の構造式を下記に示す。<Synthesis Example 4> Synthesis of Compound 4 (10,10'-bis-(2,5-phenylphenyl)-9,9'-bianthril) Instead of 2-bromobiphenyl in Synthesis Example 1, 1- Synthesis was carried out using 9.3 g of bromo-2,5-diphenylbenzene to obtain 4.0 g of the target compound. This object (1
0,10'-bis-(2,5-phenylphenyl)-
The structural formula of 9,9′-bianthryl) is shown below.
【０１１３】[0113]
【化９】 [Chemical 9]
【０１１４】この化合物の質量分析およびＮＭＲスペク
トル、赤外吸収スペクトルの測定ヲ行ったところ、目的
物と矛盾しないことを確認した。また、ガラス転移温度
を測定したところ、１４５度であった。1Ｈ−ＮＭＲス
ペクトルを図６に、13Ｃ−ＮＭＲスペクトルを図７に、
赤外線スペクトルを図８に示す。Mass spectrometry of this compound and measurement of its NMR spectrum and infrared absorption spectrum confirmed that it did not contradict the desired product. The glass transition temperature was measured and found to be 145 degrees. 1 H-NMR spectrum is shown in FIG. 6, 13 C-NMR spectrum is shown in FIG.
The infrared spectrum is shown in FIG.
【０１１５】＜合成例５＞ 化合物５（10,10’-ビス[-2-(-5-フェニルチエニル-2-
イル）フェニル]-9,9’-ビアンスリル）の合成 合成例１の２−ブロモビフェニルの代わりに、2-(-5-フ
ェニルチエニル-2-イル）ブロモベンゼン３．５g を用
いて合成を行い、０．９g の目的化合物を得た。得られ
た目的物（10,10’-ビス[-2-(-5-フェニルチエニル-2-
イル）フェニル]-9,9’-ビアンスリル）の構造を下記に
示す。<Synthesis Example 5> Compound 5 (10,10'-bis[-2-(-5-phenylthienyl-2-
Synthesis of (yl)phenyl]-9,9′-bianthryl) Synthesis was carried out by using 3.5 g of 2-(-5-phenylthienyl-2-yl)bromobenzene instead of 2-bromobiphenyl in Synthesis Example 1. , 0.9 g of the desired compound was obtained. The obtained target product (10,10'-bis[-2-(-5-phenylthienyl-2-
The structure of (yl)phenyl]-9,9'-bianthryl) is shown below.
【０１１６】[0116]
【化１０】 [Chemical 10]
【０１１７】この黄白色個体の質量分析およびＮＭＲス
ペクトル、赤外吸収スペクトルの測定を行ったところ、
目的物と矛盾しないことを確認した。また、ガラス転移
温度を測定したところ、１４６度であった。1Ｈ−ＮＭ
Ｒスペクトルを図９に示す。Mass spectrometry of this yellowish white solid and measurement of its NMR spectrum and infrared absorption spectrum revealed that
I confirmed that it does not conflict with the target. The glass transition temperature was measured and found to be 146 degrees. 1 H-NM
The R spectrum is shown in FIG.
【０１１８】＜合成例６＞ 化合物・（９,９’,10,10’-テトラキス（-2-ビフェニ
ルイル）-2,2’-ビアンスリル）の合成 ２−ブロモビフェニル１１．４g、ジエチルエーテル５
０mlとトルエン５０m１を混合し、これに１．６Mブチル
リチウムのヘキサン溶液３０をゆっくり滴下しながら１
時間室温で攪拌し、２−リチオビフェニルを調整した。
次に、トルエン１５０m１と２−クロロアントラキノン
５．５gの混合物にこのリチオビフェニルをゆっくり滴
下し、室温で一昼夜攪拌した。次いで、これに蒸留水１
００mlを加えさらに１時間攪拌した後、この溶液を濾過
し、廬物をメタノールで洗浄した。得られた物を再結晶
した後、カラム精製し、９．８g の白色固体としてジオ
ール体を得た。<Synthesis Example 6> Synthesis of compound (9,9',10,10'-tetrakis(-2-biphenylyl)-2,2'-bianthryl) 2-bromobiphenyl 11.4 g, diethyl ether 5
0 ml and 50 ml of toluene were mixed, and 1.6M hexane solution of butyllithium 30 in 1.6M was slowly added dropwise to 1
After stirring at room temperature for 2 hours, 2-lithiobiphenyl was adjusted.
Next, this lithiobiphenyl was slowly added dropwise to a mixture of 150 ml of toluene and 5.5 g of 2-chloroanthraquinone, and the mixture was stirred at room temperature overnight. Then add distilled water 1
After adding 00 ml and stirring for further 1 hour, this solution was filtered and the residue was washed with methanol. The obtained product was recrystallized and purified by column to obtain 9.8 g of a diol as a white solid.
【０１１９】このジオール体９．６g とテトラヒドロフ
ラン４００mlを混合し、これに塩化すず２５gと塩酸２
５mlの混合液をゆっくり滴下した。さらに、これを７０
度のオイルバスで２時間加熱した後冷却し、２００mlの
トルエンを加え、蒸留水及び炭酸水素ナトリウムで洗浄
した。硫酸マグネシウムで乾燥した後、カラム精製と再
沈を繰り返し、純白色の２−クロロ−９,１０−ジフェ
ニルアントラセン７．１g を得た。9.6 g of this diol was mixed with 400 ml of tetrahydrofuran, and 25 g of tin chloride and 2 ml of hydrochloric acid were added to this mixture.
5 ml of the mixed solution was slowly added dropwise. In addition, 70
After heating for 2 hours in an oil bath, the mixture was cooled, 200 ml of toluene was added, and the mixture was washed with distilled water and sodium hydrogen carbonate. After drying over magnesium sulfate, column purification and reprecipitation were repeated to obtain 7.1 g of pure white 2-chloro-9,10-diphenylanthracene.
【０１２０】次に、２−クロロ−９,１０−ジフェニル
アントラセン４．５g、Ni(cod)2１．８g、DMF１００m
l、１,５−シクロオクタジエン３ml、２,２’−ビピリ
ジン１gを混合し、６０度で２０時間反応した後、これ
をメタノール２００m１に加え、さらに２時間攪拌し
た。この溶液を濾過し、廬物をメタノール、ヘキサン、
アセトンで洗浄した後、再結晶およびカラム精製を行
い、３g の白色固体を得た。これを昇華精製し、２．８
gの黄白色個体を得た。得られた目的物の構造を下記に
示す。Next, 4.5 g of 2-chloro-9,10-diphenylanthracene, Ni(cod)21.8 g and DMF 100 m
1, 1,5-Cyclooctadiene (3 ml) and 2,2'-bipyridine (1 g) were mixed and reacted at 60° C. for 20 hours, then, this was added to 200 ml of methanol and the mixture was further stirred for 2 hours. The solution was filtered and the residue was washed with methanol, hexane,
After washing with acetone, recrystallization and column purification were carried out to obtain 3 g of a white solid. This is sublimated and purified to 2.8.
g yellowish white solid was obtained. The structure of the obtained target product is shown below.
【０１２１】[0121]
【化１１】 [Chemical 11]
【０１２２】この黄白色個体の質量分析およびＮＭＲス
ペクトル、赤外吸収スペクトルの測定を行ったところ、
目的物と矛盾しないことを確認した。また、ガラス転移
温度を測定したところ、１６６度であった。Mass spectrometry of this yellowish white solid and measurement of its NMR spectrum and infrared absorption spectrum revealed that
I confirmed that it does not conflict with the target. The glass transition temperature was measured and found to be 166 degrees.
【０１２３】なお、ガラス上に蒸着して放置したところ
半年以上アモルファスの安定な膜を維持した。When vapor-deposited on glass and allowed to stand, a stable amorphous film was maintained for more than half a year.
【０１２４】＜合成例７＞ 化合物７（10,10’-ビス［2-(-5-フェニルチエニル-2-
イル）フェニル］-9,9’-ビアンスリル）の合成 乾燥した容器に、２−（５−フェニルチエニル−２−イ
ル）ブロモベンゼン３．５g と、トルエン５０mlとジエ
チルエーテル５０mlを加えた後、１．６Ｍのｎ−ブチル
リチウムのヘキサン溶液７．２mlをゆっくり加え１時間
室温で攪拌し、２−（５−フェニルチエニル−２−イ
ル）リチオベンゼンを得た。次に、乾燥した別の容器に
１０，１０’−ビアンスロン２g とトルエン１００mlを
加えよく撹拌した。この反応液の中に、先に調整した２
−（５−フェニルチエニル−２−イル）リチオベンゼン
をゆっくり滴下した。室温で２０時間攪拌した後、蒸留
水４０mlを加え、生じた沈殿物を濾別した。この沈殿物
を２回洗浄した後、カラム分離を２回行い、再結晶して
２．９g の白色固体としてジオール体を得た。<Synthesis Example 7> Compound 7 (10,10'-bis[2-(-5-phenylthienyl-2-
Synthesis of 2-(5-phenylthienyl-2-yl)bromobenzene (3.5 g), toluene (50 ml) and diethyl ether (50 ml) were added to a dry container. 7.2 ml of a hexane solution of n-butyllithium of 6M was slowly added and stirred for 1 hour at room temperature to obtain 2-(5-phenylthienyl-2-yl)lithiobenzene. Then, 10 g of 10,10'-Bianthrone and 100 ml of toluene were added to another dried container and stirred well. In this reaction solution,
-(5-Phenylthienyl-2-yl)lithiobenzene was slowly added dropwise. After stirring at room temperature for 20 hours, 40 ml of distilled water was added and the generated precipitate was separated by filtration. After washing this precipitate twice, column separation was performed twice and recrystallization to obtain 2.9 g of a diol as a white solid.
【０１２５】次に反応容器に、得られたジオール体２．
９g とテトラヒドロフラン４００mlに、塩化すず２５g
と塩酸４０mlを混合した溶液をゆっくり滴下した。この
反応容器を６０℃のオイルバスで２時間撹拌した。この
反応溶液に１００mlのトルエンを加え、有機層を分離し
た後、塩酸と蒸留水で洗浄した後、乾燥した。得られた
固体を、カラム精製２回（吸着剤：シリカゲル、展開溶
媒：トルエン）した後、トルエン／ヘキサン系溶液から
再沈し、黄白色の固体１．２g を得た。さらに、この黄
白色固体１．２g を昇華精製し０．９g の黄白色固体を
得た。得られた目的物（10,10’-ビス［2-(-5-フェニル
チエニル-2-イル）フェニル］-9,9’-ビアンスリル）の
構造式を下記に示す。Then, the obtained diol compound 2.
25 g of tin chloride in 9 g of tetrahydrofuran and 400 ml of tetrahydrofuran
A solution obtained by mixing 40 ml of hydrochloric acid with hydrochloric acid was slowly added dropwise. The reaction container was stirred in an oil bath at 60° C. for 2 hours. To this reaction solution was added 100 ml of toluene, the organic layer was separated, washed with hydrochloric acid and distilled water, and then dried. The obtained solid was subjected to column purification twice (adsorbent: silica gel, developing solvent: toluene) and then reprecipitated from a toluene/hexane system solution to obtain 1.2 g of a yellowish white solid. Further, 1.2 g of this yellowish white solid was purified by sublimation to obtain 0.9 g of a yellowish white solid. The structural formula of the obtained desired product (10,10′-bis[2-(-5-phenylthienyl-2-yl)phenyl]-9,9′-bianthril) is shown below.
【０１２６】[0126]
【化１２】 [Chemical formula 12]
【０１２７】この黄白色個体の質量分析およびＮＭＲス
ペクトル、赤外吸収スペクトルの測定を行ったところ、
目的物と矛盾しないことを確認した。Mass spectrometry of this yellowish white solid and measurement of its NMR spectrum and infrared absorption spectrum revealed that
I confirmed that it does not conflict with the target.
【０１２８】＜実施例１＞厚さ１００nmのＩＴＯ透明電
極（陽極）を有するガラス基板を、中性洗剤、アセト
ン、エタノールを用いて超音波洗浄し、煮沸エタノール
中から引き上げて乾燥した。透明電極表面をUV/O3 洗浄
した後、真空蒸着装置の基板ホルダーに固定して、チャ
ンバー内を１０-4 Pa以下の減圧状態とした。Example 1 A glass substrate having an ITO transparent electrode (anode) having a thickness of 100 nm was ultrasonically washed with a neutral detergent, acetone, and ethanol, pulled out from boiling ethanol and dried. After the surface of the transparent electrode was washed with UV/O 3, it was fixed to a substrate holder of a vacuum vapor deposition device, and the inside of the chamber was depressurized to 10 -4 Pa or less.
【０１２９】次に、ホール注入層として、減圧状態を保
ったまま、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス[N−
(４-メチルフェニル）− N−フェニル-（４-アミノフェ
ニル）]−１，１’−ビフェニル−４，４’−ジアミン
を蒸着速度０．１nm/secで８０nmの厚さに形成した。Next, as a hole injecting layer, N,N'-diphenyl-N,N'-bis[N-, while maintaining a reduced pressure state, was used.
(4-Methylphenyl)-N-phenyl-(4-aminophenyl)]-1,1′-biphenyl-4,4′-diamine was formed to a thickness of 80 nm at a deposition rate of 0.1 nm/sec.
【０１３０】次いで、減圧状態を保ったまま、ホール輸
送層として、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス
(１-ナフチル）−１，１’−ジフェニル−４，４’−ジ
アミンを蒸着速度０．１nm/secで１５nmの厚さに形成し
た。Next, with the reduced pressure maintained, N,N'-diphenyl-N,N'-bis was formed as a hole transport layer.
(1-Naphthyl)-1,1'-diphenyl-4,4'-diamine was formed to a thickness of 15 nm at a deposition rate of 0.1 nm/sec.
【０１３１】さらに、減圧状態を保ったまま、発光層と
して、化合物１を蒸着速度０．１nm/secで４０nmの厚さ
に形成した後、電子注入層として、トリス-8-キノリノ
ラトアルミニウムを蒸着速度０．１nm/secで１５nmの厚
さに形成した。Further, while maintaining a reduced pressure, Compound 1 was formed as a light emitting layer to a thickness of 40 nm at a vapor deposition rate of 0.1 nm/sec, and then tris-8-quinolinolato aluminum was used as an electron injection layer. It was formed to a thickness of 15 nm at a vapor deposition rate of 0.1 nm/sec.
【０１３２】次に、減圧状態を保ったまま、電子注入電
極としてＬｉ2Ｏを蒸着速度０．０１nm/secで１nmの厚
さに形成した後、配線電極として、Ａｌを蒸着速度２nm
/secで２００nmの厚さに形成したNext, while maintaining a reduced pressure, Li 2 O was formed as an electron injection electrode at a vapor deposition rate of 0.01 nm/sec to a thickness of 1 nm, and then Al was deposited as a wiring electrode at a vapor deposition rate of 2 nm.
/sec to 200nm thickness
【０１３３】この有機ＥＬ素子に電圧を印加して電流を
流したところ、６．０V 、１０mA/cm2 で２００cd/m2
の発光（発光極大波長λmax ＝４２０nm、色度座標（x,
y）=（０．１０,０．０８）が確認された。[0133] When a current flows by applying a voltage to the organic EL element, 6.0V, 10mA / cm 2 at 200 cd / m 2
Emission (maximum emission wavelength λ max =420 nm, chromaticity coordinates (x,
y)=(0.10,0.08) was confirmed.
【０１３４】また、この素子に、５０mA/cm2 の一定電
流を流し、連続発光させたところ、初期輝度８４０cd/m
2 初期駆動電圧は７．４V となり、１４０時間後に輝度
は半減した。このとき駆動電圧上昇は２．２Vであっ
た。When a constant current of 50 mA/cm 2 was passed through this element to cause continuous light emission, the initial luminance was 840 cd/m 2.
2 The initial drive voltage was 7.4V, and the brightness was halved after 140 hours. At this time, the driving voltage rise was 2.2V.
【０１３５】＜実施例２＞実施例１において、発光層と
して上記合成例の化合物１と下記化６で示す化合物を、
１００：３の重量比率で共蒸着する他は同様にして有機
ＥＬ素子を得た。<Example 2> In Example 1, the compound 1 of the above synthesis example and the compound represented by the following chemical formula 6 were used as the light emitting layer.
An organic EL device was obtained in the same manner except that co-evaporation was carried out at a weight ratio of 100:3.
【０１３６】[0136]
【化１３】 [Chemical 13]
【０１３７】この有機ＥＬ素子に電圧を印加して電流を
流したところ、５．９V 、１０mA/cm2 で１２００cd/m
2 の発光（発光極大波長λmax ＝４６０nm、色度座標
（x,y）=（０．１７,０．３２）が確認された。When a voltage was applied to this organic EL element to pass a current, it was 1200 cd/m 2 at 5.9 V and 10 mA/cm 2.
2 emission (maximum emission wavelength λ max =460 nm, chromaticity coordinates (x,y)=(0.17,0.32)) was confirmed.
【０１３８】また、この素子に、５０mA/cm2 の一定電
流を流し、連続発光させたところ、初期輝度６５００cd
/m2 初期駆動電圧は７．４V となり、４００時間後に輝
度は半減した。このとき駆動電圧上昇は２．２Vであっ
た。When a constant current of 50 mA/cm 2 was passed through this device to cause continuous light emission, the initial luminance was 6500 cd.
The initial drive voltage of /m 2 was 7.4 V, and the luminance was halved after 400 hours. At this time, the driving voltage rise was 2.2V.
【０１３９】＜実施例３＞実施例１において、発光層と
して上記合成例の化合物１と、下記化７で示す化合物を
１００：３の重量比率で共蒸着する他は同様にして有機
ＥＬ素子を得た。<Example 3> An organic EL device was prepared in the same manner as in Example 1, except that the compound 1 of the above-described Synthesis Example and the compound represented by the following Chemical formula 7 were co-deposited in a weight ratio of 100:3 as the light emitting layer. Obtained.
【０１４０】[0140]
【化１４】 [Chemical 14]
【０１４１】この有機ＥＬ素子に電圧を印加して電流を
流したところ、６．０V 、１０mA/cm2 で４００cd/m2
の発光（発光極大波長λmax ＝４２０nm、色度座標（x,
y）=（０．１０,０．１０）が確認された。[0141] When a current flows by applying a voltage to the organic EL element, 6.0V, 10mA / cm 2 at 400 cd / m 2
Emission (maximum emission wavelength λ max =420 nm, chromaticity coordinates (x,
y)=(0.10,0.10) was confirmed.
【０１４２】また、この素子に、５０mA/cm2 の一定電
流を流し、連続発光させたところ、初期輝度２１００cd
/m2 初期駆動電圧は７．６V となり、２５０時間後に輝
度は半減した。このとき駆動電圧上昇は２．２Vであっ
た。When a constant current of 50 mA/cm 2 was passed through this element to cause continuous light emission, the initial luminance was 2100 cd.
The initial drive voltage of /m 2 was 7.6 V, and the luminance was halved after 250 hours. At this time, the driving voltage rise was 2.2V.
【０１４３】＜比較例１＞実施例３において、発光層と
して化合物１の代わりに10,10’-ビス（2,6’-ジメチル
フェニル）-9,9’-ビアンスリルを用いる他は同様にし
て有機ＥＬ素子を得た。<Comparative Example 1> In the same manner as in Example 3, except that 10,10'-bis(2,6'-dimethylphenyl)-9,9'-bianthryl was used in place of the compound 1 in the light emitting layer. An organic EL device was obtained.
【０１４４】この有機ＥＬ素子に電圧を印加して電流を
流したところ、６．５V 、１０mA/cm2 で１４０cd/m2
の発光（発光極大波長λmax ＝４６０nm、色度座標（x,
y）=（０．１０,０．１０）が確認された。[0144] When a current flows by applying a voltage to the organic EL element, 6.5V, 10mA / cm 2 at 140 cd / m 2
Emission (maximum emission wavelength λ max =460 nm, chromaticity coordinates (x,
y)=(0.10,0.10) was confirmed.
【０１４５】また、この素子に、５０mA/cm2 の一定電
流を流し、連続発光させたところ、初期輝度６５０cd/m
2 初期駆動電圧は８．０V となり、２０時間後に輝度は
半減した。このとき駆動電圧上昇は３．０V であった。When a constant current of 50 mA/cm 2 was passed through this element to cause continuous light emission, the initial luminance was 650 cd/m 2.
2 The initial drive voltage was 8.0 V, and the brightness was halved after 20 hours. At this time, the driving voltage rise was 3.0V.
【０１４６】＜比較例２＞実施例４において、発光層と
して化合物１の代わりに10,10’-ビス（2,6’-ジメチル
フェニル）-9,9’-ビアンスリルを用いる他は同様にし
て有機ＥＬ素子を得た。<Comparative Example 2> In the same manner as in Example 4, except that 10,10'-bis(2,6'-dimethylphenyl)-9,9'-bianthril was used instead of the compound 1 in the light emitting layer. An organic EL device was obtained.
【０１４７】この有機ＥＬ素子に電圧を印加して電流を
流したところ、６．７V 、１０mA/cm2 で８６９cd/m2
の発光（発光極大波長λmax ＝４６０nm、色度座標（x,
y）=（０．１７,０．３２）が確認された。[0147] When a current flows by applying a voltage to the organic EL element, 6.7V, 10mA / cm 2 at 869cd / m 2
Emission (maximum emission wavelength λ max =460 nm, chromaticity coordinates (x,
y)=(0.17, 0.32) was confirmed.
【０１４８】また、この素子に、５０mA/cm2 の一定電
流を流し、連続発光させたところ、初期輝度４９００cd
/m2 初期駆動電圧は７．９V となり、５０時間後に輝度
は半減した。このとき駆動電圧上昇は３．２V であっ
た。When a constant current of 50 mA/cm 2 was passed through this element to cause continuous light emission, the initial luminance was 4900 cd.
The initial drive voltage of /m 2 was 7.9 V, and the brightness was halved after 50 hours. At this time, the driving voltage rise was 3.2V.
【０１４９】[0149]
【発明の効果】本発明の有機ＥＬ素子用化合物は、結晶
性が低く、アモルファス状態の良好な膜を形成すること
ができるので、有機ＥＬ素子用化合物、特に青色発光材
料や電子注入輸送材料として用いることができる。INDUSTRIAL APPLICABILITY The compound for organic EL element of the present invention has low crystallinity and can form a film in a good amorphous state. Therefore, it is used as a compound for organic EL element, especially as a blue light emitting material or an electron injecting and transporting material. Can be used.
【０１５０】また、本発明の有機ＥＬ素子用化合物を用
いた本発明の有機ＥＬ素子は電流リークがなく、非発光
部分（ダークスポット）の発生・成長がなく、膜中の結
晶化が抑制されるので連続発光の信頼性の高い素子とな
る。特に発光層に用いた場合１万cd/m2 以上の高輝度の
青色発光が可能となるだけでなく、十分な発光効率、長
寿命を有する。Further, the organic EL device of the present invention using the compound for organic EL device of the present invention has no current leakage, no generation/growth of non-light emitting portions (dark spots), and crystallization in the film is suppressed. Therefore, the device becomes a continuous light emitting device with high reliability. In particular, when it is used for a light emitting layer, it not only enables blue light emission with high brightness of 10,000 cd/m 2 or more, but also has sufficient light emission efficiency and long life.
【図１】本発明のＥＬ素子の構成例を示す側面図であ
る。FIG. 1 is a side view showing a configuration example of an EL element of the present invention.
【図２】本発明の合成例２の化合物の1Ｈ−ＮＭＲのス
ペクトルを示した図である。FIG. 2 is a diagram showing a 1 H-NMR spectrum of a compound of Synthesis Example 2 of the present invention.
【図３】本発明の合成例２の化合物の13Ｃ−ＮＭＲのス
ペクトルを示した図である。FIG. 3 is a diagram showing a 13 C-NMR spectrum of a compound of Synthesis Example 2 of the present invention.
【図４】本発明の合成例２の化合物の赤外線スペクトル
を示した図である。FIG. 4 is a diagram showing an infrared spectrum of the compound of Synthesis Example 2 of the present invention.
【図５】本発明の合成例３の化合物の1Ｈ−ＮＭＲのス
ペクトルを示した図である。FIG. 5 is a diagram showing a 1 H-NMR spectrum of a compound of Synthesis Example 3 of the present invention.
【図６】本発明の合成例４の化合物の1Ｈ−ＮＭＲのス
ペクトルを示した図である。FIG. 6 is a diagram showing a 1 H-NMR spectrum of a compound of Synthesis Example 4 of the present invention.
【図７】本発明の合成例４の化合物の13Ｃ−ＮＭＲのス
ペクトルを示した図である。FIG. 7 is a diagram showing a 13 C-NMR spectrum of a compound of Synthesis Example 4 of the present invention.
【図８】本発明の合成例４の化合物の赤外線スペクトル
を示した図である。FIG. 8 is a diagram showing an infrared spectrum of the compound of Synthesis Example 4 of the present invention.
【図９】本発明の合成例５の化合物の1Ｈ−ＮＭＲのス
ペクトルを示した図である。FIG. 9 is a diagram showing a 1 H-NMR spectrum of a compound of Synthesis Example 5 of the present invention.
１ 有機ＥＬ素子 ２ 基板 ３ 陽極 ４ ホール注入輸送層 ５ 発光層 ６ 電子注入輸送層 ７ 陰極 1 Organic EL Element 2 Substrate 3 Anode 4 Hole Injecting and Transporting Layer 5 Light Emitting Layer 6 Electron Injecting and Transporting Layer 7 Cathode
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０５Ｂ 33/14 Ｈ０５Ｂ 33/14 Ｂ 33/22 33/22 Ｂ (72)発明者 荒 健輔 東京都中央区日本橋一丁目13番１号 ティ ーディーケイ株式会社内 Ｆターム(参考） 3K007 AB00 AB02 AB03 AB04 AB06 AB11 AB14 BB06 CA01 CA05 DA00 DA01 DB03 EB00 FA01 FA03 4H006 AA01 AA03 AB92 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) H05B 33/14 H05B 33/14 B 33/22 33/22 B (72) Inventor Kensuke Ara Chuo-ku, Tokyo Nihonbashi 1-chome 13-1 FDC term in TDC Corporation (reference) 3K007 AB00 AB02 AB03 AB04 AB06 AB11 AB14 BB06 CA01 CA05 DA00 DA01 DB03 EB00 FA01 FA03 4H006 AA01 AA03 AB92
Claims (13)
ラセン誘導体である有機ＥＬ素子用化合物。 式（Ｉ） Ａ1 −Ｌ−Ａ2 〔式（Ｉ）において、Ａ1 およびＡ2 は、各々モノ（オ
ルト置換フェニル）アントリル基またはジ（オルト置換
フェニル）アントリル基を表し、これらは同一でも異な
るものであってもよい。Ｌは単結合または二価の連結基
を表す。〕1. A compound for an organic EL device, which is a phenylanthracene derivative represented by the following formula (I). Formula (I) A 1 -LA 2 [In Formula (I), A 1 and A 2 each represent a mono(ortho-substituted phenyl)anthryl group or a di(ortho-substituted phenyl)anthryl group, and these may be the same. It may be different. L represents a single bond or a divalent linking group. ]
の有機ＥＬ素子用化合物。 【化１】 【化２】 〔化１において、Ａｒ1 〜Ａｒ4 は、水素原子、アリー
ル基、複素環アリール基またはアリールエテニル基を表
し、Ａｒ1 およびＡｒ2 、Ａｒ3 およびＡｒ4 の少なく
とも一方はアリール基、複素環アリール基またはアリー
ルエテニル基である。Ｒ1 およびＲ2 は、各々アルキル
基、アリール基、アリールエテニル基、アルコキシ基、
またはアミノ基を表し、これらは同一でも異なるもので
あってもよい。ｒ１およびｒ２は、各々、０または１〜
３の整数を表し、ｒ１およびｒ２が、各々、２以上の整
数であるとき、Ｒ1 同士およびＲ2 同士は各々同一でも
異なるものであってもよい。Ｒ3 は、アルキル基または
アリール基を表し、ｒ3は、各々、０または１〜３の整
数を表す。ｒ3が、２以上の整数であるとき、Ｒ3 は各
々同一でも異なるものであってもよい。Ｌ1 は単結合ま
たはアリーレン基を表し、アリーレン基はアルキレン
基、−Ｏ−、−Ｓ−または−ＮＲ−（ここで、Ｒはアル
キル基またはアリール基を表す。）が介在するものであ
ってもよい。化２において、Ａｒ5 およびＡｒ6 は、水
素原子、アリール基、複素環アリール基またはアリール
エテニル基を表し、Ａｒ5 およびＡｒ6 の少なくとも一
方はアリール基、複素環アリール基またはアリールエテ
ニル基である。Ｒ4 は、各々アルキル基、アリール基、
アリールエテニル基、アルコキシ基、またはアミノ基を
表し、これらは同一でも異なるものであってもよい。ｒ
４は、各々、０または１〜３の整数を表し、ｒ４が、各
々、２以上の整数であるとき、Ｒ4 同士は各々同一でも
異なるものであってもよい。Ｒ5 は、アルキル基または
アリール基を表し、ｒ５は、各々、０または１〜４の整
数を表す。ｒ５が、２以上の整数であるとき、Ｒ5 は各
々同一でも異なるものであってもよい。Ｌ2 は単結合ま
たはアリーレン基を表し、アリーレン基はアルキレン
基、−Ｏ−、−Ｓ−または−ＮＲ−（ここで、Ｒはアル
キル基またはアリール基を表す。）が介在するものであ
ってもよい。Ｌ2 は単結合またはアリーレン基を表し、
アリーレン基はアルキレン基、−Ｏ−、−Ｓ−または−
ＮＲ−（ここで、Ｒはアルキル基またはアリール基を表
す。）が介在するものであってもよい。〕2. The method according to claim 1 or 2 below.
Compound for organic EL device of. [Chemical 1] [Chemical 2] [In Chemical Formula 1, Ar 1 to Ar 4 represent a hydrogen atom, an aryl group, a heterocyclic aryl group or an arylethenyl group, and at least one of Ar 1 and Ar 2 , Ar 3 and Ar 4 is an aryl group or a heterocyclic group. It is an aryl group or an arylethenyl group. R 1 and R 2 are each an alkyl group, an aryl group, an arylethenyl group, an alkoxy group,
Alternatively, it represents an amino group, which may be the same or different. r1 and r2 are each 0 or 1
When R1 and r2 are each an integer of 2 or more, R 1 s and R 2 s may be the same or different. R 3 represents an alkyl group or an aryl group, and r 3 represents 0 or an integer of 1 to 3, respectively. r3 is, when an integer of 2 or more, R 3 's may be the same or different in the same. L 1 represents a single bond or an arylene group, and the arylene group is mediated by an alkylene group, —O—, —S— or —NR— (wherein R represents an alkyl group or an aryl group). Good. In Chemical formula 2, Ar 5 and Ar 6 represent a hydrogen atom, an aryl group, a heterocyclic aryl group or an arylethenyl group, and at least one of Ar 5 and Ar 6 is an aryl group, a heterocyclic aryl group or an arylethenyl group. Is. R 4 is an alkyl group, an aryl group,
It represents an arylethenyl group, an alkoxy group, or an amino group, which may be the same or different. r
4 each represent an integer of 0 or 1 to 3, and when r4 is an integer of 2 or more, R 4 s may be the same or different. R 5 represents an alkyl group or an aryl group, and r 5 represents 0 or an integer of 1 to 4, respectively. When r5 is an integer of 2 or more, R 5 may be the same or different. L 2 represents a single bond or an arylene group, and the arylene group is mediated by an alkylene group, —O—, —S— or —NR— (wherein R represents an alkyl group or an aryl group). Good. L 2 represents a single bond or an arylene group,
The arylene group is an alkylene group, -O-, -S- or -.
NR- (wherein R represents an alkyl group or an aryl group) may be present. ]
ｒ2 、Ａｒ3 およびＡｒ 4 の少なくとも一方がフェニル
基、ビフェニル基、ターフェニル基、スチリル基、フェ
ニルスチリル基、ジフェニルスチリル基、チエニル基、
メチルチエニル基、フェニルチエニル基またはフェニル
ビチエニル基である請求項２の有機ＥＬ素子用化合物。3. In the chemical formula 1, Ar1And A
r2, Ar3And Ar FourAt least one of them is phenyl
Group, biphenyl group, terphenyl group, styryl group, phenyl group
Nylstyryl group, diphenylstyryl group, thienyl group,
Methylthienyl group, phenylthienyl group or phenyl
The compound for organic EL device according to claim 2, which is a bithienyl group.
ｒ6 、の少なくとも一方がフェニル基、ビフェニル基、
ターフェニル基、スチリル基、フェニルスチリル基、ジ
フェニルスチリル基、チエニル基、メチルチエニル基、
フェニルチエニル基またはフェニルビチエニル基である
請求項２のフェニルアントラセン誘導体。4. In the chemical formula 2, Ar 5 and A
at least one of r 6 is a phenyl group, a biphenyl group,
Terphenyl group, styryl group, phenylstyryl group, diphenylstyryl group, thienyl group, methylthienyl group,
The phenylanthracene derivative according to claim 2, which is a phenylthienyl group or a phenylbithienyl group.
ｒ2 、Ａｒ3 およびＡｒ 4 の少なくとも一方がフェニル
基、ビフェニル基またはターフェニル基であり、Ｌ1 は
単結合である請求項２の有機ＥＬ素子用化合物。5. In the chemical formula 1, Ar1And A
r2, Ar3And Ar FourAt least one of them is phenyl
Group, a biphenyl group or a terphenyl group, L1Is
The compound for an organic EL device according to claim 2, which is a single bond.
ｒ6 、の少なくとも一方がフェニル基、ビフェニル基ま
たはターフェニル基であり、Ｌ2 は単結合である請求項
２の有機ＥＬ素子用化合物。6. In the chemical formula 2, Ar 5 and A
The compound for an organic EL device according to claim 2, wherein at least one of r 6 is a phenyl group, a biphenyl group or a terphenyl group, and L 2 is a single bond.
する少なくとも１層の有機化合物層を有する有機ＥＬ素
子。7. An organic EL device having at least one organic compound layer containing the compound for organic EL device according to claim 1.
機化合物層が発光層である請求項７の有機ＥＬ素子。8. The organic EL device according to claim 7, wherein the organic compound layer containing the compound for an organic EL device is a light emitting layer.
と、少なくとも１層のホール輸送層と、少なくとも１層
の電子注入輸送層とを有する請求項８の有機ＥＬ素子。9. The organic EL device according to claim 8, further comprising at least one hole injection layer, at least one hole transport layer, and at least one electron injection transport layer.
層と、少なくとも１層のホール輸送層と、少なくとも１
層の電子輸送層と、少なくとも１層の電子注入層とを有
する請求項８の有機ＥＬ素子。10. Further, at least one hole injection layer, at least one hole transport layer, and at least one hole injection layer.
The organic EL device according to claim 8, which has a layer of an electron transport layer and at least one layer of an electron injection layer.
有機化合物層が電子注入輸送層であり、さらに発光層を
有する請求項７の有機ＥＬ素子。11. The organic EL device according to claim 7, wherein the organic compound layer containing the compound for organic EL device is an electron injecting and transporting layer, and further has a light emitting layer.
発光層が電子注入輸送性化合物とホール注入輸送性化合
物との混合層であって、この混合層が前記有機ＥＬ素子
用化合物を含有する請求項７の有機ＥＬ素子。12. A light emitting layer having at least one light emitting layer, the light emitting layer being a mixed layer of an electron injecting and transporting compound and a hole injecting and transporting compound, and the mixed layer containing the compound for an organic EL device. The organic EL device according to claim 7.
機ＥＬ素子用化合物であり、前記ホール注入輸送性化合
物は、アミン、またはスチリルアミン系化合物である請
求項１２の有機ＥＬ素子。13. The organic EL device according to claim 12, wherein the electron injecting and transporting compound is the compound for an organic EL device, and the hole injecting and transporting compound is an amine or a styrylamine compound.
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|---|---|---|---|
| JP15710599A JP3838816B2 (en) | 1999-06-03 | 1999-06-03 | Compound for organic EL device and organic EL device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15710599A JP3838816B2 (en) | 1999-06-03 | 1999-06-03 | Compound for organic EL device and organic EL device |
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|---|---|
| JP2000344691A true JP2000344691A (en) | 2000-12-12 |
| JP2000344691A5 JP2000344691A5 (en) | 2006-01-19 |
| JP3838816B2 JP3838816B2 (en) | 2006-10-25 |
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ID=15642350
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