WO2020241730A1 - Arylamine compound and use thereof - Google Patents
Arylamine compound and use thereof Download PDFInfo
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- WO2020241730A1 WO2020241730A1 PCT/JP2020/021058 JP2020021058W WO2020241730A1 WO 2020241730 A1 WO2020241730 A1 WO 2020241730A1 JP 2020021058 W JP2020021058 W JP 2020021058W WO 2020241730 A1 WO2020241730 A1 WO 2020241730A1
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- carbon atoms
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- -1 Arylamine compound Chemical class 0.000 title claims abstract description 331
- 239000002966 varnish Substances 0.000 claims abstract description 79
- 239000010409 thin film Substances 0.000 claims abstract description 71
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 60
- 125000003118 aryl group Chemical group 0.000 claims abstract description 57
- 125000005843 halogen group Chemical group 0.000 claims abstract description 46
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 28
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 28
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 214
- 150000001875 compounds Chemical class 0.000 claims description 147
- 125000000217 alkyl group Chemical group 0.000 claims description 87
- 239000000126 substance Substances 0.000 claims description 38
- 125000002521 alkyl halide group Chemical group 0.000 claims description 32
- 229910052760 oxygen Inorganic materials 0.000 claims description 30
- 229910052717 sulfur Inorganic materials 0.000 claims description 26
- 239000002019 doping agent Substances 0.000 claims description 24
- 125000003545 alkoxy group Chemical group 0.000 claims description 21
- 229910005965 SO 2 Inorganic materials 0.000 claims description 16
- 125000000732 arylene group Chemical group 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 7
- 238000002347 injection Methods 0.000 abstract description 53
- 239000007924 injection Substances 0.000 abstract description 53
- 230000003287 optical effect Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 2
- 125000005649 substituted arylene group Chemical group 0.000 abstract 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 abstract 1
- 125000003107 substituted aryl group Chemical group 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 138
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 96
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 95
- 239000002904 solvent Substances 0.000 description 87
- 238000006243 chemical reaction Methods 0.000 description 66
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 63
- 239000000243 solution Substances 0.000 description 62
- 238000004519 manufacturing process Methods 0.000 description 59
- 238000000034 method Methods 0.000 description 59
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 44
- 238000005259 measurement Methods 0.000 description 44
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 42
- 239000007787 solid Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 31
- 239000000203 mixture Substances 0.000 description 30
- 239000000758 substrate Substances 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 26
- 239000000463 material Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 238000001914 filtration Methods 0.000 description 23
- 230000005525 hole transport Effects 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- 0 C*c1c(*)c(*)c2-c3c(*)c(*)c(*)c(*)c3C3(c4c(*)c(C)c(*)c(*)c4-c4c(*)c(*)c(C)c(*)c34)c2c1* Chemical compound C*c1c(*)c(*)c2-c3c(*)c(*)c(*)c(*)c3C3(c4c(*)c(C)c(*)c(*)c4-c4c(*)c(*)c(C)c(*)c34)c2c1* 0.000 description 19
- 239000011148 porous material Substances 0.000 description 19
- 239000002994 raw material Substances 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 17
- 239000011541 reaction mixture Substances 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 16
- 239000010408 film Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- LYOIWHQTWCWWFK-UHFFFAOYSA-N 3-(7-bromo-9,9-dimethylfluoren-2-yl)-9-phenylcarbazole Chemical compound C1=C2C(C)(C)C3=CC(Br)=CC=C3C2=CC=C1C(C=C1C2=CC=CC=C22)=CC=C1N2C1=CC=CC=C1 LYOIWHQTWCWWFK-UHFFFAOYSA-N 0.000 description 15
- 125000001153 fluoro group Chemical group F* 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 14
- 125000003342 alkenyl group Chemical group 0.000 description 14
- 230000008033 biological extinction Effects 0.000 description 14
- 239000012141 concentrate Substances 0.000 description 14
- 229910052741 iridium Inorganic materials 0.000 description 14
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 12
- 125000006575 electron-withdrawing group Chemical group 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- 239000012528 membrane Substances 0.000 description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 12
- 238000007740 vapor deposition Methods 0.000 description 11
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 239000012046 mixed solvent Substances 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- JEYLGFCAZBGCMC-UHFFFAOYSA-N 3-(4-bromophenyl)-9-phenylcarbazole Chemical compound C1=CC(Br)=CC=C1C1=CC=C(N(C=2C=CC=CC=2)C=2C3=CC=CC=2)C3=C1 JEYLGFCAZBGCMC-UHFFFAOYSA-N 0.000 description 9
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 125000001624 naphthyl group Chemical group 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 230000002140 halogenating effect Effects 0.000 description 8
- 239000011964 heteropoly acid Substances 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 8
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 description 7
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- XJCVRTZCHMZPBD-UHFFFAOYSA-N 3-nitroaniline Chemical compound NC1=CC=CC([N+]([O-])=O)=C1 XJCVRTZCHMZPBD-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 235000011118 potassium hydroxide Nutrition 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 5
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- KUBSCXXKQGDPPD-UHFFFAOYSA-N 3-bromo-9-phenylcarbazole Chemical compound C12=CC=CC=C2C2=CC(Br)=CC=C2N1C1=CC=CC=C1 KUBSCXXKQGDPPD-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 5
- GYFSBCDGBBWMBE-UHFFFAOYSA-N [9-(4-methylphenyl)carbazol-3-yl]boronic acid Chemical compound C1=CC(C)=CC=C1N1C2=CC=C(B(O)O)C=C2C2=CC=CC=C21 GYFSBCDGBBWMBE-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 description 5
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 235000011181 potassium carbonates Nutrition 0.000 description 5
- 125000002577 pseudohalo group Chemical group 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 4
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 4
- LOXUVZPMEXKUEJ-UHFFFAOYSA-N 2-bromo-7-iodo-9,9-dimethylfluorene Chemical compound C1=C(I)C=C2C(C)(C)C3=CC(Br)=CC=C3C2=C1 LOXUVZPMEXKUEJ-UHFFFAOYSA-N 0.000 description 4
- RODQKGBYDIAMCF-UHFFFAOYSA-N 3-bromo-9-(4-methylphenyl)carbazole Chemical compound C1=CC(C)=CC=C1N1C2=CC=C(Br)C=C2C2=CC=CC=C21 RODQKGBYDIAMCF-UHFFFAOYSA-N 0.000 description 4
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 4
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
Definitions
- the present invention relates to arylamine compounds and their use.
- organic electroluminescence (hereinafter referred to as organic EL) elements are expected to be put into practical use in fields such as displays and lighting, and various developments related to materials and element structures are expected for the purpose of low voltage drive, high brightness, long life, etc. Has been made.
- a plurality of functional thin films are used in this organic EL element, and one of them, the hole injection layer, is responsible for the transfer of electric charge between the anode and the hole transport layer or the light emitting layer, and is low in the organic EL element. It plays an important role in achieving voltage drive and high brightness.
- the method for producing the hole injection layer is roughly classified into a dry process represented by a vapor deposition method and a wet process represented by a spin coating method. Comparing these processes, the wet process can efficiently produce a thin film with a large area and high flatness. For this reason, as the area of organic EL displays is being increased, a hole injection layer that can be formed by a wet process is desired.
- the present inventors have a charge transporting property that gives a thin film that can be applied to various wet processes and can realize excellent EL element characteristics when applied to a hole injection layer of an organic EL element.
- the charge-transporting thin film for organic EL elements has been in the visible region because the coloring of the charge-transporting thin film used for the organic EL element reduces the color purity and color reproducibility of the organic EL element. It is desired to have high transparency and high transparency (see Patent Document 6).
- the present invention has been made in view of such circumstances, and when a thin film having good solubility in an organic solvent and good optical characteristics is provided and this thin film is applied to a hole injection layer or the like. It is an object of the present invention to provide an arylamine compound capable of realizing an organic EL device having good properties.
- the present inventors have at least arylcarbazole at the center via a spacer having an aryldiamine skeleton and a predetermined arylene skeleton at the two amino groups.
- the compounds bonded one by one have good solubility in an organic solvent, and the varnish obtained by dissolving this in an organic solvent gives a thin film having excellent optical properties, and this thin film is applied to a hole injection layer or the like.
- the present invention has been completed by finding that an organic EL element having good characteristics can be obtained in some cases.
- Arylamine compounds represented by any of the following formulas (1) to (6) (excluding compounds represented by the following formulas (P1) to (P4)), wherein, Ar c each independently represent a group represented by the formula (Q), X represents an arylene group which may be independently substituted and may contain a heteroatom. Y represents a phenylene group which may be substituted independently of each other. g represents an integer of 1 to 10 independently of each other.
- R 1 is independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
- R 2 represents an aryl group that may be independently substituted and may contain a hetero atom
- Ar s represents an aryl group.
- R 3 is independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
- V 1 is an independent C (R 4 ) 2 (R 4 is an independent hydrogen atom and has 1 to 20 carbon atoms. It represents an alkyl group or an alkyl halide group having 1 to 20 carbon atoms), NR 5 (R 5 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. ), S, O, or SO 2 , V 2 stands for NR 5 (R 5 stands for the same meaning as above), S or O) 3.
- Ar s is represented by any of the following formulas (101A) to (118A).
- Ar s is 3 arylamine compound represented by any one of the following formulas (101A-1) ⁇ (118A -3), (In the formula, R 4 and R 5 have the same meanings as described above.) 5.
- X is an arylamine compound according to any one of 1 to 4 represented by any of the following formulas (201) to (207).
- R 6 is independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
- NR 8 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms), S, O, or SO 2.
- W 3 stands for NR 8 (R 8 stands for the same meaning as above), S or O.) 6. 5 arylamine compounds, wherein X is represented by any of the following formulas (201A) to (207A). (In the formula, R 6 , W 1 , W 2 and W 3 have the same meanings as described above.) 7. 6 arylamine compounds represented by any of the following formulas (201A-1) to (207A-1), wherein X is (In the formula, R 7 , R 8 and W 3 have the same meanings as described above.) 8. Wherein Ar c is one of arylamine compounds of 1-7 are the same group, 9. A charge-transporting varnish containing any of the arylamine compounds 1 to 8 and an organic solvent. 10. 9 charge-transporting varnishes containing dopant material, 11. Charge transport thin films made using 9 or 10 charge transport varnishes, 12. Provided is an electronic device including 11 charge transporting thin films.
- the arylamine compound of the present invention has good solubility in an organic solvent, and by using a charge-transporting varnish containing this arylamine compound, a charge-transporting thin film having high transparency and high refractive index can be obtained. be able to.
- This charge transporting thin film can be suitably used as a thin film for electronic devices such as organic EL devices, particularly as a thin film for electronic devices in which a thin film is laminated by a wet process on an upper layer, and the charge transporting property of the present invention can be used.
- a thin film to a hole injection layer or the like of an organic EL device, an device having good characteristics can be manufactured.
- FIG. 5 is a 1 H-NMR spectrum diagram of the compound obtained in Production Example 1-1. It is 1 H-NMR spectrum figure of the compound obtained in Production Example 1-2. It is 1 H-NMR spectrum figure of the compound obtained in Production Example 1-2. It is 1 H-NMR spectrum figure of the compound obtained in Production Example 1-2. 3 is a 1 H-NMR spectrum diagram of the compound obtained in Production Example 1-3. 3 is a 1 H-NMR spectrum diagram of the compound obtained in Production Example 1-3. It is 1 H-NMR spectrum figure of the compound obtained in the production example 1-4. It is 1 H-NMR spectrum figure of the compound obtained in the production example 1-4. It is 1 H-NMR spectrum figure of the compound obtained in Production Example 1-5.
- 6 is a 1 H-NMR spectrum diagram of the compound obtained in Production Example 1-6. 6 is a 1 H-NMR spectrum diagram of the compound obtained in Production Example 1-6. It is 1 H-NMR spectrum figure of the compound obtained in Production Example 1-7. It is 1 H-NMR spectrum figure of the compound obtained in Production Example 1-7. It is 1 H-NMR spectrum figure of the compound obtained in Production Example 1-8. It is 1 H-NMR spectrum figure of the compound obtained in Production Example 1-8. It is 1 H-NMR spectrum figure of the compound obtained in Production Example 1-9. It is 1 H-NMR spectrum figure of the compound obtained in Production Example 1-9.
- Example 1-2 It is 1 H-NMR spectrum figure of the compound obtained in Example 1-2. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-3. It is a 1 H-NMR spectrum of the compound obtained in Example 1-4. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-5. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-6. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-7. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-8. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-9. It is a 1 H-NMR spectrum of the compound obtained in Example 1-10. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-11.
- Example 1-12 It is 1 H-NMR spectrum figure of the compound obtained in Example 1-12. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-12. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-13. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-13. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-14. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-15. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-16. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-17. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-17. It is 1 H-NMR spectrum figure of the compound obtained in Example 1-18.
- the arylamine compound according to the present invention is characterized by being represented by any of the following formulas (1) to (6), and includes the compounds represented by the formulas (P1) to (P4) as described above. do not do.
- Ar c each independently represent a group represented by the following formula (Q), X is independently together may be substituted, a hetero atom Represents an arylene group which may contain, Y represents an independently and optionally substituted phenylene group, and g each independently represents an integer of 1 to 10, but preferably.
- Ar c each independently represent a group represented by the following formula (Q ') or (Q'').
- R 1 independently has a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and 1 carbon atom.
- Ar s represents an arylene group which may be independently substituted and may contain a heteroatom.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- the alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl.
- the alkyl group having 1 to 20 carbon atoms may have a linear, branched or cyclic alkyl group, and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy. , Isobutoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexyloxy, n-octyloxy, n-decyloxy, 2-methylhexyloxy, 2-ethylhexyloxy, 2-n-propylhexyloxy, 2- Examples thereof include n-butylhexyloxy, 2-ethyldecyloxy and 3-ethylhexyloxy groups.
- aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4- Examples include phenyl, 9-phenyl group and the like.
- the alkyl halide group having 1 to 20 carbon atoms is a group in which at least one hydrogen atom of the alkyl group having 1 to 20 carbon atoms is substituted with a halogen atom, and specific examples thereof include fluoromethyl, difluoromethyl, and tri.
- Fluoromethyl bromodifluoromethyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro-1, 1,2-Trifluoroethyl, pentafluoroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 1,1,1 , 3,3,3-Hexafluoropropane-2-yl, 3-bromo-2-methylpropyl, 4-bromobutyl, perfluoropentyl, 2- (perfluorohexyl) ethyl group and the like.
- R 1 is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and more preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. , All hydrogen atoms are even more preferred.
- the aryl group which may be substituted with R 2 in the above formulas (Q), (Q') and (Q ′′) and may contain a hetero atom contains a hetero atom as a constituent atom thereof. It is also a good arylene group, and may have a structure in which rings are condensed or a structure in which rings are linked.
- the number of carbon atoms is not particularly limited, but is usually 6 to 60, preferably 40 or less, and more preferably 30 or less.
- substituent of the aryl group which may be substituted with R 2 and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and a carbon number of carbon atoms.
- substituent of the aryl group which may be substituted with R 2 and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and a carbon number of carbon atoms.
- Examples thereof include an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms.
- alkenyl group having 2 to 20 carbon atoms include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-Methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, n- 1-Eicosenyl group and the like can be mentioned.
- alkynyl group having 2 to 20 carbon atoms examples include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n-3-butynyl, and 1-methyl-.
- an aryl group having 6 to 10 carbon atoms which may be substituted and may contain a hetero atom is preferable, and a phenyl group which may be substituted and a naphthyl group which may be substituted may be used. More preferably, both are more preferably a phenyl group or a naphthyl group, and both are even more preferably a phenyl group.
- groups suitable for R 2 will be given, but the present invention is not limited thereto.
- the arylene group which may be substituted with Ar s in the above formulas (Q), (Q') and (Q ′′) and may contain a hetero atom contains a hetero atom as a constituent atom thereof. It is also a good arylene group, and may have a structure in which rings are condensed or a structure in which rings are linked.
- the number of carbon atoms is not particularly limited, but is usually 6 to 60, preferably 40 or less, and more preferably 30 or less.
- substituent of the arylene group which may be substituted with Ar s and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and a carbon number of carbon atoms.
- substituent of the arylene group which may be substituted with Ar s and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and a carbon number of carbon atoms.
- examples thereof include an alkyl halide group having 1 to 20, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and the like, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a halogen having 1 to 20 carbon atoms.
- Ar s is a group represented by any one of the following formulas (101) to (118).
- R 3 independently contains a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.
- V 1 is an independent C (R 4 ) 2
- R 4 is an independent hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or (Represents an alkyl halide group having 1 to 20 carbon atoms)
- NR 5 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms
- S It represents O or SO 2 , where V 2 is NR 5 (R 5 has the same meaning as above), S or O.
- halogen atoms alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkyl halide groups having 1 to 20 carbon atoms in R 3 to R 5 are described above. The same can be mentioned.
- R 3 is preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkyl halide group having 1 to 10 carbon atoms, respectively, and has a hydrogen atom and a carbon number of carbon atoms.
- Alkyl groups of 1 to 5 and fluoroalkyl groups having 1 to 5 carbon atoms are more preferable, and hydrogen atoms, methyl groups and trifluoromethyl groups are even more preferable.
- At least one R 3 may be an electron-withdrawing group such as a halogen atom, a nitro group, a cyano group, or a fluoroalkyl group having 1 to 5 carbon atoms.
- a trifluoromethyl group is more preferable.
- R 4 preferably has an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group.
- R 5 is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, and a naphthyl group, and a hydrogen atom.
- Methyl group and phenyl group are even more preferable.
- V 1 is, S, O, SO 2
- V 2 is, S, O is preferred.
- V 2 is S or O
- an electron-withdrawing group may be present in R 3 .
- R 5 has the same meaning as above.
- R 5 has the same meaning as above.
- the arylene group which may be substituted with X in the above formulas (1) and (2) and may contain a hetero atom is not particularly limited, and even if the structure is a condensed ring, the ring is not particularly limited. May be a connected structure.
- the number of carbon atoms is not particularly limited, but is usually 6 to 60, preferably 40 or less, and more preferably 30 or less.
- Specific examples of the substituent of the arylene group which may be substituted with X and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and 1 carbon atom.
- Examples thereof include an alkyl group having 20 to 20, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and the like, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a halogenation having 1 to 20 carbon atoms.
- Examples of the alkyl group, the alkoxy group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms include the same as above.
- the arylene group which may be substituted with X in the above formulas (1) and (2) and may contain a heteroatom is the following formula (A divalent group represented by any one of 201) to (207) is preferable.
- R 6 independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and an alkyl halide group having 1 to 20 carbon atoms.
- W 1 is an independent single bond
- halogen atoms alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkyl halide groups having 1 to 20 carbon atoms in R 6 to R 8 are described above. The same can be mentioned.
- R 6 is preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkyl halide group having 1 to 10 carbon atoms, respectively, and has a hydrogen atom and a carbon number of carbon atoms.
- Alkyl groups of 1 to 5 and fluoroalkyl groups having 1 to 5 carbon atoms are more preferable, and hydrogen atoms, methyl groups and trifluoromethyl groups are even more preferable.
- At least one R 6 is preferably an electron-withdrawing group such as a halogen atom, a nitro group, a cyano group, or a fluoroalkyl group having 1 to 5 carbon atoms. Considering the point, a trifluoromethyl group is more preferable.
- R 7 preferably has an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group.
- R 8 is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, and a naphthyl group, and a hydrogen atom. , Methyl group and phenyl group are even more preferable.
- R 6 is not an electron withdrawing group
- W 1 is S, O, and SO 2
- an electron-withdrawing group may be present in R 6 .
- W 2 is, S, O, SO 2
- W 3 is, S, O is preferred.
- W 3 is S, O, SO 2
- an electron-withdrawing group may be present in R 6 .
- the bonding position of the amino group and the spacer W 1 on the aromatic ring is not particularly limited, but any of the following formulas (201A) to (207A).
- a divalent group represented by is preferable.
- R 6 ' are each independently a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms Represents an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
- Specific examples of the alkoxy group and the aryl group having 6 to 20 carbon atoms are the same as those described above.
- R 6' preferably an alkyl group having 1 to 10 carbon atoms and an alkyl halide group having 1 to 10 carbon atoms, and an alkyl group having 1 to 5 carbon atoms and a fluoroalkyl group having 1 to 5 carbon atoms. More preferably, a methyl group and a trifluoromethyl group are even more preferable.
- Examples of X suitable in the present invention include those represented by the following formulas, but are not limited thereto.
- Examples of the phenylene group in which Y may be substituted in the above formulas (3) to (6) include a 1,4-phenylene group, which may be substituted with a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, or the like. , 3-Phenylene group or 1,2-phenylene group, but may be substituted 1,4-phenylene group or 1,3-phenylene group in consideration of the balance of refractive index, transparency and electrical characteristics. Is preferable, and an unsubstituted 1,4-phenylene group or a 1,3-phenylene group is more preferable.
- g independently represents an integer of 1 to 10, but considering the solubility of the compound in an organic solvent and the transparency of the obtained thin film, 1 to 7 Is preferred, an integer of 1 to 5 is more preferred, an integer of 1 to 3 is even more preferred, 1 or 2 is even more preferred, and 1 is optimal considering the availability of the starting compound.
- Ar s is preferably a group represented by the formula (107), more preferably a group represented by any one of formulas (107A) ⁇ (107C), and even more preferably formula (107A-1) A group represented by any of (107C-5), more preferably a group represented by the formula (107B-1) or (107C-1).
- Arc is the same group in each of the formulas (1) to (6).
- Ar c is preferably a group (Ar C1) represented by the formula (Q-1), more preferably a group represented by the formula (Q-2) (Ar C2 ) or formula (Q-3 ) Is a group (Ar C3 ).
- the arylamine compound of the present invention is represented by any of the following formulas (1-1) to (6-1) in a preferred embodiment, and the following formulas (1-2) to (6-1) in a more preferred embodiment. It is represented by any of 6-2) and (1-3) to (6-3).
- the arylamine compound represented by the formula (1) or (2) of the present invention (hereinafter, also referred to as arylamine compound (1) or (2)) is an aryldiamine compound [I] as shown in the following scheme. ] And the aryl halide compound [II] can be produced by reacting in the presence of a catalyst.
- Z represents a halogen atom or a pseudohalogen group
- X, R 1 , R 2 and Ar s have the same meanings as above.
- Examples of the halogen atom include the same as above.
- Examples of the pseudohalogen group include (fluoro) alkylsulfonyloxy groups such as methanesulfonyloxy, trifluoromethanesulfonyloxy and nonafluorobutanesulfonyloxy groups; aromatic sulfonyloxy groups such as benzenesulfonyloxy and toluenesulfonyloxy groups. ..
- the charging ratio of the aryldiamine compound [I] to the halogenated aryl compound [II] depends on whether the compound to be synthesized is the arylamine compound (1) or (2), and the reaction of the raw material compound.
- the aryl halide compound is appropriately determined in the range of 1.2 to 0.6 equivalents with respect to the amount of all NH groups of the aryldiamine compound [I] in consideration of the properties and bulkiness.
- 1.0 equivalent or more of the aryl halide compound is preferable.
- Examples of the catalyst used in the above reaction include copper catalysts such as copper chloride, copper bromide and copper iodide; Pd (PPh 3 ) 4 (tetrax (triphenylphosphine) palladium), Pd (PPh 3 ) 2 Cl 2 (Bis (triphenylphosphine) dichloropalladium), Pd (dba) 2 (bis (dibenzylideneacetone) palladium), Pd 2 (dba) 3 (tris (dibenzylideneacetone) dipalladium), Pd (Pt-Bu) 3 ) Examples thereof include palladium catalysts such as 2 (bis (tri (t-butylphosphine)) palladium) and Pd (OAc) 2 (palladium acetate). These catalysts may be used alone or in combination of two or more. These catalysts may also be used with suitable known ligands.
- copper catalysts such as copper chloride, copper bromide and copper iodide
- ligands include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri-t-butylphosphine, di-t-butyl ( Phine) phosphine, di-t-butyl (4-dimethylaminophenyl) phosphine, 1,2-bis (diphenylphosphine) ethane, 1,3-bis (diphenylphosphine) propane, 1,4-bis (diphenylphos) Tertiary phosphine such as fino) butane, 1,1'-bis (diphenylphosphine) ferrocene, tertiary phosphine such as trimethylphosphine, triethylphosphine, triphenylphosphine, ter
- the amount of the catalyst used can be about 0.01 to 0.5 mol with respect to 1 mol of the aryl halide compound [II], but is preferably about 0.05 to 0.2 mol.
- the amount used can be 0.1 to 5 equivalents with respect to the metal complex to be used, but 1 to 2 equivalents are preferable.
- a base may be used in the above reaction.
- the base include lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, t-butoxysodium, t-butoxypotassium, sodium hydroxide, potassium hydroxide.
- Alkali metal alone such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, alkali metal hydride, alkali metal hydroxide, alkoxy alkali metal, alkali metal carbonate, alkali metal hydrogen carbonate; alkaline soil carbonate such as calcium carbonate Metals; n-butyl lithium, s-butyl lithium, t-butyl lithium, lithium diisopropylamide (LDA), lithium 2,2,6,6-tetramethylpiperidin (LiTMP), hexamethyldisilazane lithium (LHMDS), etc.
- LDA lithium 2,2,6,6-tetramethylpiperidin
- LiHMDS hexamethyldisilazane lithium
- Organic lithium examples thereof include amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, and pyridine.
- amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, and pyridine.
- the amount used can be 0.1 to 5 equivalents with respect to the aryl halide compound [II] to be used, but 1 to 2 equivalents are preferable.
- Each of the above reactions is carried out in a solvent when all the raw material compounds are solid or from the viewpoint of efficiently obtaining the target arylamine compound.
- a solvent the type is not particularly limited as long as it does not adversely affect the reaction.
- Specific examples include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), and aromatics.
- Group hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesityrene, etc.), halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, etc.) P-dichlorobenzene, etc.), ethers (diethyl ether, diisopropyl ether, t-butylmethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.), ketones (acetone, methylethylketone, etc.) Methylisobutylketone, di-n-butylketone, cyclohexanone, etc.), amides (N, N-dimethylformamide, N, N-dimethylacetamide
- the reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, but is particularly preferably about 0 to 200 ° C., more preferably 20 to 150 ° C.
- the reaction time is appropriately determined in consideration of the reaction temperature, the reactivity of the raw material compound, and the like, but is usually about 30 minutes to 50 hours.
- post-treatment can be carried out according to a conventional method to obtain the desired arylamine compound.
- arylamine compounds represented by the formulas (3) to (5) of the present invention are aryl as shown in the following scheme. It can be produced by reacting a diamine compound [I'] with an aryl halide compound [II] in the presence of a catalyst.
- the charging ratio of the aryldiamine compound [I'] to the aryl halide compound [II] is not particularly limited as long as the desired product can be obtained, but usually the compounds to be synthesized are the arylamine compounds (3) to Depending on which of (5) is used, and in consideration of the reactivity and bulkiness of the raw material compound, the amount of the aryl halide compound is 1 with respect to the total amount of NH groups of the aryldiamine compound [I']. .2 Equivalent or less is appropriately determined, and when synthesizing the arylamine compound (3), 1.0 equivalent or more of the aryl halide compound is preferable with respect to the amount of all NH groups of the aryldiamine compound [I'].
- the amount of the aryldiamine compound [I'] can be 2.0 equivalents or more of the aryl halide compound, but 2.0 to 2.4 equivalents.
- the amount of the aryl compound can be 4.0 equivalents or more with respect to the amount of the aryldiamine compound [I'], but 4.0 to 4.8 equivalents. Is preferable.
- various conditions and suitable conditions of the coupling reaction regarding the catalyst, the ligand, the base, the solvent, the temperature and time of the reaction, etc. are described with respect to the arylamine compound represented by the formula (1) or (2). Is the same as.
- arylamine compound represented by the formula (6) of the present invention (hereinafter, also referred to as arylamine compound (6)) can be produced by the following method. First, the dinitro compound [I "-1] is reacted with the aryl halide compound [II] to obtain the dinitro compound [I "-2].
- the charging ratio of the dinitro compound [I "-1] to the aryl halide compound [II] can be 1 equivalent or more of the aryl halide compound with respect to the amount of substance of the total NH groups of the dinitro compound. About 1 to 1.2 equivalents are preferable.
- the reaction conditions and suitable conditions regarding the catalyst, ligand, base, solvent, reaction temperature and time, etc. are the same as those described for the arylamine compound represented by the formula (1) or (2). Is.
- Hydrogenation includes a hydrogenation reaction using Pd / C or the like, and can be carried out by a known method.
- the amine compound [I "-3] can be reacted with the aryl halide compound [II] to obtain the arylamine compound (6).
- the charging ratio of the amine compound [I "-3] and the aryl halide compound [II] can be 2 equivalents or more of the aryl halide compound with respect to the amine compound, but is about 2 to 2.4 equivalents. Is preferable.
- the reaction conditions and suitable conditions regarding the catalyst, ligand, base, solvent, reaction temperature and time, etc. are the same as those described for the arylamine compound represented by the formula (1) or (2). Is.
- the aryl halide compound [II] which is a raw material used for producing the arylamine compound of the present invention, can be produced by reacting an arylcarbazole compound [III] with an aryldihalide compound [IV] in the presence of a catalyst.
- Z B independently represents a group represented by the following formula (E1) or (E2).
- Z' represents a halogen atom or a pseudohalogen group, and examples of the halogen atom and the pseudohalogen group include the same as above.
- Z and Z' may be the same, but from the viewpoint of efficiently obtaining the desired aryl halide compound [II], the reactivity of the atom (group) of Z'is Z. It is preferable that the reactivity of the atom (group) is higher than that of the atom (group).
- the Z B group in the arylcarbazole compound [III] reacts preferentially with the Z'atom (group) over the Z atom (group), and is efficient.
- the desired aryl halide compound [II] can be obtained.
- D 1 and D 2 independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
- D 3 is an alcandiyl group or carbon having 1 to 20 carbon atoms.
- alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms, which represent an arylene group having 6 to 20 carbon atoms are the same as those described above.
- the alcandiyl group having 1 to 20 carbon atoms includes methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, 2,2-dimethylpropane-1,3-diyl, and 2-ethyl-2.
- 1,2-phenylene, 1,2-naphthylene, 2,3-naphthylene, 1,8-naphthylene, 1,2-anthrylene, 2,3-anthrylene, 1,2 -Phenantrylene, 3,4-phenanthrylene, 9,10-phenanthrylene group and the like can be mentioned.
- the charging ratio of the arylcarbazole compound [III] to the dihalide aryl compound [IV] can be 1.0 or more with respect to the arylcarbazole compound [III] 1 in terms of molar ratio. However, it is preferably about 1.0 to 1.2.
- Each of the above reactions is carried out in a solvent when all the raw material compounds are solid or from the viewpoint of efficiently obtaining the target arylamine halide compound.
- a solvent the type is not particularly limited as long as it does not adversely affect the reaction.
- Specific examples include cyclic ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP).
- Ketones such as methylisobutylketone and cyclohexanone; halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene can be mentioned.
- halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene
- aromatic hydrocarbons such as benzene, toluene and xylene can be mentioned.
- These solvents can be used alone or in admixture of two or more. Of these, 1,4-dioxane, toluene, xylene and the like are particularly preferable.
- Examples of the catalyst used in the above reaction are [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride (PdCl 2 (dppf)) and tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ).
- the reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, but is particularly preferably about 0 to 200 ° C., more preferably 20 to 150 ° C.
- the reaction time is appropriately determined in consideration of the reaction temperature, the reactivity of the raw material compound, and the like, but is usually about 30 minutes to 50 hours.
- post-treatment can be carried out according to a conventional method to obtain the desired arylamine halide compound.
- the aryl halide compound [IV] can be obtained by reacting the compound represented by the formula [IV'] with a halogenating agent as shown in the scheme below.
- halogenating agent known ones can be used, and specific examples thereof include, but are not limited to, N-bromosuccinimide and the like.
- the amount of the halogenating agent is about 1 to 1.5 in terms of molar ratio with respect to the compound represented by the formula [IV'].
- the solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used in this type of reaction.
- the reaction temperature is usually appropriately determined from the range of 0 to 140 ° C., and the time is usually appropriately determined from the range of 0.1 to 100 hours.
- arylcarbazole compound [III] can be obtained by reacting a compound represented by the formula [III'] with a compound represented by the formula [V] as shown in the scheme below.
- the preparation of the compound represented by the formula [III'] and the compound represented by the formula [V] is represented by the formula [V] with respect to the compound 1 represented by the formula [III'] in terms of molar ratio.
- the solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used in this type of reaction.
- the temperature of the reaction is usually appropriately determined from the range of 0 to 140 ° C., and the time thereof is usually appropriately determined from the range of 0.1 to 100 hours.
- the compound represented by the formula [III'] is obtained after reacting the compound represented by the formula [III'-2] with an aryl halide compound (R 2 Z) as shown in the following scheme. , be accomplished by treatment with a halogenating agent, the compound represented by the formula [III'-2], after treatment with a halogenating agent, can be obtained by reacting a halogenated aryl compound (R 2 Z), The latter reaction is preferable from the viewpoint of avoiding halogenation of the N-position aryl group of the carbazole skeleton and obtaining the target product more efficiently.
- halogenating agent used in the above reaction a known halogenating agent can be used, and the amount of the halogenating agent is represented by the formula [III'-1-1] or [III'-2] in terms of molar ratio. It is about 1 to 1.5 with respect to the compound 1 to be produced.
- the solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used in this type of reaction.
- the temperature is usually appropriately determined from the range of 0 to 140 ° C., and the time is usually appropriately determined from the range of 0.1 to 100 hours.
- the compound represented by the formula [VI] having two alkyl groups at the 9-position of the fluorene ring which is a raw material of the spacer skeleton of Ar S , is prepared in the presence of a base as shown in the scheme below. It can be obtained by reacting a compound represented by the formula [VI'] with a compound represented by the formula [VII].
- R 4' are each independently an alkyl group or a halogenated alkyl group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms Represents.
- the preparation of the compound represented by the formula [VI'] and the compound represented by the formula [VII] is represented by the formula [VII] with respect to the compound 1 represented by the formula [VI'] in terms of molar ratio.
- Compounds 1 to 1.5 The bases that can be used in the above reaction are not particularly limited as long as they are the bases used in this type of reaction, and specific examples thereof include t-BuOK, t-BuONa, CsCO 3 , K 2 CO 3 , and Na.
- the solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used in this type of reaction.
- the temperature of the reaction is usually appropriately determined from the range of 0 to 140 ° C., and the time thereof is usually appropriately determined from the range of 0.1 to 100 hours.
- the amine compounds that can be used as raw materials for the arylamine compounds of the present invention are (A) amine compounds [I'''] or [I''''] and aryl compounds [VIII], as shown in the following scheme. ] And (B) the reduction reaction of the nitro group by hydrogenation. By repeating the reactions (A) and (B), the chain length (phenylene number) is extended. I can go.
- the amine compounds included in the amine compound [I'] are (A) m-phenylenediamine or 3-nitroaniline and 3-halonitrobenzene, as shown in the following scheme. It can be obtained by the coupling reaction of (B) and the reduction reaction of the nitro group by hydrogenation, and by repeating the reactions of (A) and (B), the chain length (m-phenylene number) is extended. I can go.
- An amine compound [I'] having a desired number of phenylene can be freely produced without using a method.
- the charging ratio of the raw material compounds in each reaction is 1 to 1 to the raw material compound having a nitro group (raw material compound containing a halogen atom (pseudohalogen group)) with respect to the raw material compound having an amino group.
- the charging ratio of the raw material compounds in each reaction is 1 to 1 to the raw material compound having a nitro group (raw material compound containing a halogen atom (pseudohalogen group)) with respect to the raw material compound having an amino group.
- a ligand can be used as the palladium catalyst used for the coupling reaction.
- a ligand in addition to those exemplified above, JohnPhos, CyjohnPhos, DavePhos, XPhos, SPhos, tBuXPhos, RuPhos, Me4tBuXPhos, sSPhos, tBuMePhos, MePhos, tBuDavePhos, PhDave, which are commercially available from Aldrich.
- -Biphenylphosphine compounds such as Dicyclohexylphosphino-2,4,6-trimethoxybiphenyl, BrettPhos, tBuBrettPhos, AdBrettPhos, Me 3 (OMe) tBuXPhos, (2-Biphenyl) di-1-adamantylphosphine, RockPhos, CPhos can be preferably used. ..
- Examples of the base used in the coupling reaction include lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, t-butoxysodium, t-butoxypotassium, and hydroxide.
- Alkali metal alone such as sodium, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, alkali metal hydride, alkali metal hydroxide, alkoxy alkali metal, alkali metal carbonate, alkali metal hydrogen carbonate; calcium carbonate Alkali carbonate earth metals such as n-butyllithium, s-butyllithium, t-butyllithium, lithium diisopropylamide (LDA), lithium 2,2,6,6-tetramethylpiperidine (LiTMP), hexamethyldisilazane.
- Organic lithium such as lithium (LHMDS); amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, pyridine and the like can be mentioned.
- H is a hydrogen atom
- Ph is a phenyl group
- Me is a methyl group
- n-Hex is an n-hexyl group
- p-Toly is a p-tolyl group
- 2-Thie is 2-thienyl.
- the groups, 1,3-Ph represents a 1,3-phenylene group
- 1,4-Ph represents a 1,4-phenylene group.
- the arylamine compounds of Nos. 1 and 865 are the following compounds, respectively. ..
- the above-mentioned arylamine compound of the present invention can be suitably used as a charge transporting substance.
- it can be used as a charge-transporting varnish containing the arylamine compound of the present invention and an organic solvent, and the charge-transporting varnish can be used to improve its charge-transporting ability depending on the use of the obtained thin film.
- It may contain a dopant substance for the purpose of.
- the arylamine compound of the present invention can be used in combination with other conventionally known charge-transporting substances such as an aniline derivative and a thiophene derivative, but the arylamine compound of the present invention alone can be used as a charge-transporting substance. preferable.
- charge transportability is synonymous with conductivity.
- the charge-transporting varnish may be one that has charge-transporting property by itself, and the solid film obtained thereby may have charge-transporting property.
- the dopant substance is not particularly limited as long as it is soluble in at least one solvent used for the varnish, and either an inorganic dopant substance or an organic dopant substance can be used. Further, the inorganic and organic dopant substances may be used alone or in combination of two or more. Furthermore, the dopant substance first exhibits its function as a dopant substance in the process of obtaining a charge-transporting thin film which is a solid film from the varnish, for example, when a part of the molecule is removed by an external stimulus such as heating during firing. Alternatively, it may be a substance that improves, for example, an aryl sulfonic acid ester compound protected by a group in which a sulfonic acid group is easily eliminated.
- a heteropolyacid is preferable as the inorganic dopant substance.
- the heteropolyacid has a structure in which a hetero atom is located at the center of a molecule, which is typically represented by a Keggin type represented by the formula (H1) or a Dawson type chemical structure represented by the formula (H2). It is a polyacid formed by condensing isopolyacid, which is an oxygen acid such as vanadium (V), molybdenum (Mo), and tungsten (W), and oxygen acid of a different element.
- Oxygen acids of such dissimilar elements mainly include oxygen acids of silicon (Si), phosphorus (P), and arsenic (As).
- heteropolyacid examples include phosphomolybdic acid, silicate molybdic acid, phosphotungstic acid, silicate tungstic acid, phosphotungstic acid, and the like, and these may be used alone or in combination of two or more. Good. These heteropolyacids are available as commercially available products, and can also be synthesized by a known method. In particular, when one kind of heteropolyacid is used, the one kind of heteropolyacid is preferably phosphotungstic acid or phosphomolybdic acid, and phosphotungstic acid is most suitable.
- one of the two or more kinds of heteropolyacids is preferably phosphotungstic acid or phosphomolybdic acid, and more preferably phosphotungstic acid.
- heteropolyacids in quantitative analysis such as elemental analysis, have a large number of elements or a small number of elements from the structure represented by the general formula, but the heteropolyacid is obtained as a commercially available product or a known synthesis. As long as it is properly synthesized according to the method, it can be used in the present invention.
- phosphotungsten acid is represented by chemical formulas H 3 (PW 12 O 40 ) and nH 2 O
- phosphomolydic acid is represented by chemical formulas H 3 (PMo 12 O 40 ) and nH 2 O, respectively.
- P (phosphorus), O (oxygen) or W (tungsten) or Mo (molybdenum) in this formula is large or small, it is obtained as a commercial product.
- it can be used in the present invention as long as it is appropriately synthesized according to a known synthesis method.
- the mass of the heteropolyacid defined in the present invention is not the mass of pure phosphotungstic acid (phosphotungstic acid content) in the synthetic product or the commercially available product, but the form available as the commercially available product and the known synthesis. In a form that can be isolated by the method, it means the total mass in a state containing hydrated water and other impurities.
- the amount of the heteropolyacid used can be about 0.001 to 50.0 with respect to the charge transporting substance 1 in terms of mass ratio, but is preferably about 0.01 to 20.0, more preferably 0. It is about 1 to 10.0.
- a tetracyanoquinodimethane derivative or a benzoquinone derivative can be particularly used as the organic dopant substance.
- the tetracyanoquinodimethane derivative include 7,7,8,8-tetracyanoquinodimethane (TCNQ) and halotetracyanoquinodimethane represented by the formula (H3).
- benzoquinone derivatives include tetrafluoro-1,4-benzoquinone (F4BQ), tetrachloro-1,4-benzoquinone (chloranil), tetrabromo-1,4-benzoquinone, 2,3-dichloro-5, and so on. 6-Dicyano-1,4-benzoquinone (DDQ) and the like can be mentioned.
- R 500 to R 503 each independently represent a hydrogen atom or a halogen atom, but at least one is a halogen atom, at least two are preferably halogen atoms, and at least three are halogen atoms. It is more preferable that all of them are halogen atoms.
- the halogen atom include the same as above, but a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.
- halotetracyanoquinodimethane examples include 2-fluoro-7,7,8,8-tetracyanoquinodimethane and 2-chloro-7,7,8,8-tetracyanoquinodimethane.
- 2,5-Difluoro-7,7,8,8-Tetracyanoquinodimethane 2,5-Dichloro-7,7,8,8-Tetracyanoquinodimethane, 2,3,5,6-Tetra
- the amount of the tetracyanoquinodimethane derivative and the benzoquinone derivative used is preferably 0.0001 to 100 equivalents, more preferably 0.01 to 50 equivalents, and even more preferably 1 to 20 equivalents, relative to the charge transporting substance. is there.
- the organic dopant substance is an electrically neutral onium composed of a monovalent or divalent anion represented by the following formula (a1) and a counter cation represented by the formulas (c1) to (c5). Borate salts can also be used.
- Ar represents an aryl group having 6 to 20 carbon atoms which may have a substituent or a heteroaryl group having 2 to 20 carbon atoms which may have a substituent, respectively, and L.
- the alkylene group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methylene, methylmethylene, dimethylmethylene, ethylene, trimethylene and propylene. , Tetramethylene, pentamethylene, hexamethylene group and the like. Examples of the aryl group and the heteroaryl group include the same as above.
- anion of the above formula (a1) include, but are not limited to, those represented by the formula (a2).
- the amount of the onium borate salt used can be about 0.1 to 10 with respect to the charge-transporting substance in terms of the amount of substance (molar).
- the onium borate salt can be synthesized by referring to, for example, a known method described in JP-A-2005-314682.
- an aryl sulfonic acid compound or an aryl sulfonic acid ester compound can also be preferably used.
- aryl sulfonic acid compound examples include benzene sulfonic acid, tosylic acid, p-styrene sulfonic acid, 2-naphthalene sulfonic acid, 4-hydroxybenzene sulfonic acid, 5-sulfosalicylic acid, p-dodecylbenzene sulfonic acid, and dihexyl benzene.
- aryl sulfonic acid compounds examples include aryl sulfonic acid compounds represented by the formula (H4) or (H5).
- a 1 represents O or S, with O being preferred.
- a 2 represents a naphthalene ring or an anthracene ring, but a naphthalene ring is preferable.
- a 3 represents a 2- to tetravalent perfluorobiphenyl group, p represents the number of bonds between A 1 and A 3, and is an integer satisfying 2 ⁇ p ⁇ 4, where A 3 is perfluorobiphenyldiyl.
- the group, preferably a perfluorobiphenyl-4,4'-diyl group, preferably has a p of 2.
- q represents the number of sulfonic acid groups bonded to A 2 , and is an integer satisfying 1 ⁇ q ⁇ 4, but 2 is optimal.
- a 4 to A 8 are independently hydrogen atom, halogen atom, cyano group, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms, or halogenation having 2 to 20 carbon atoms. Representing an alkenyl group, at least three of A 4 to A 8 are halogen atoms.
- Alkyl halide groups having 1 to 20 carbon atoms include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, and 3,3,3-trifluoropropyl. , 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4 , 4-Pentafluorobutyl, 2,2,3,3,4,5,4-heptafluorobutyl, 1,1,2,2,3,3,4,4,4-nonafluorobutyl group, etc. Be done.
- halogenated alkenyl group having 2 to 20 carbon atoms examples include perfluorovinyl, perfluoropropenyl (perfluoroallyl), perfluorobutenyl group and the like.
- Other examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms include the same as above, but the halogen atom is preferably a fluorine atom.
- a 4 to A 8 are hydrogen atoms, halogen atoms, cyano groups, alkyl groups having 1 to 10 carbon atoms, alkyl halide groups having 1 to 10 carbon atoms, or alkenyl halides having 2 to 10 carbon atoms.
- a 4 ⁇ a 8 is preferably a fluorine atom, a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, having 1 to 5 carbon atoms More preferably, it is an alkyl fluoride group or a fluorinated alkenyl group having 2 to 5 carbon atoms, and at least 3 of A 4 to A 8 are fluorine atoms, and hydrogen atom, fluorine atom, cyano group, and the like.
- the perfluoroalkyl group is a group in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms
- the perfluoroalkyl group is a group in which all the hydrogen atoms of the alkenyl group are substituted with fluorine atoms.
- R represents the number of sulfonic acid groups bonded to the naphthalene ring and is an integer satisfying 1 ⁇ r ⁇ 4, but 2 to 4 is preferable, and 2 is optimal.
- the molecular weight of the aryl sulfonic acid compound used as the dopant substance is not particularly limited, but is preferably 2000 or less, more preferably 2000 or less, considering the solubility in an organic solvent when used together with the arylamine compound of the present invention. It is 1500 or less.
- the amount of the aryl sulfonic acid compound used is preferably about 0.01 to 20.0, more preferably about 0.4 to 5.0, with respect to the charge transporting substance 1 in terms of the amount of substance (molar) ratio. ..
- Commercially available products may be used as the aryl sulfonic acid compound, but International Publication No. 2006/025342, International Publication No. 2009/096322, International Publication No. 2015/111654, International Publication No. 2015/0533320, International Publication No. 2015 It can also be synthesized by a known method described in / 115515 and the like.
- examples of the aryl sulfonic acid ester compound include an aryl sulfonic acid ester compound disclosed in International Publication No. 2017/217455, an aryl sulfonic acid ester compound disclosed in International Publication No. 2017/217457, and Japanese Patent Application No. 2017-243631 (Japanese Patent Application No. 2017-243631).
- Examples thereof include the aryl sulfonic acid ester compounds described in International Publication No. 2019/124412), and specifically, those represented by any of the following formulas (H6) to (H8) are preferable.
- n is an integer satisfying 1 ⁇ n ⁇ 4, but 2 is preferable.
- a 11 is an m-valent group derived from perfluorobiphenyl.
- a 12 is —O— or —S—, but —O— is preferred.
- a 13 is a (n + 1) -valent group derived from naphthalene or anthracene, but a group derived from naphthalene is preferable.
- R s1 to R s4 are each independently a hydrogen atom or a linear or branched chain alkyl group having 1 to 6 carbon atoms, and R s5 is an optionally substituted alkyl group having 2 to 20 carbon atoms. It is a monovalent hydrocarbon group of.
- linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl group and the like.
- An alkyl group having 1 to 3 carbon atoms is preferable.
- the monovalent hydrocarbon group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl.
- Alkyl groups such as groups; aryl groups such as phenyl, naphthyl and phenanthryl groups can be mentioned.
- R s1 to R s4 is a linear alkyl group having 1 to 3 carbon atoms, and the rest is a hydrogen atom, or R s1 is a linear alkyl group having 1 to 3 carbon atoms. It is preferable that R s2 to R s4 are hydrogen atoms. In this case, the methyl group is preferable as the linear alkyl group having 1 to 3 carbon atoms. Further, as R s5 , a linear alkyl group or a phenyl group having 2 to 4 carbon atoms is preferable.
- a 14 is an m-valent hydrocarbon group having 6 to 20 carbon atoms containing one or more aromatic rings which may be substituted, and the hydrocarbon group may be one or more. It is a group obtained by removing m hydrogen atoms from a hydrocarbon compound having 6 to 20 carbon atoms containing an aromatic ring. Examples of such a hydrocarbon compound include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, phenanthrene and the like.
- a part or all of the hydrogen atom may be further substituted with a substituent, and examples of such a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a nitro.
- Cyano hydroxy, amino, silanol, thiol, carboxy, sulfonic acid ester, phosphoric acid, phosphoric acid ester, ester, thioester, amide, organooxy, organoamino, organosilyl, organothio, acyl, sulfo, monovalent hydrocarbon group And so on.
- a 14 a group derived from benzene, biphenyl or the like is preferable.
- a 15 is —O— or —S—, but —O— is preferable.
- a 16 is a (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the aromatic hydrocarbon group is (n + 1) from the aromatic ring of the aromatic hydrocarbon compound having 6 to 20 carbon atoms. It is a group obtained by removing individual hydrogen atoms. Examples of such aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene and the like. Among them, as A 16 , a group derived from naphthalene or anthracene is preferable, and a group derived from naphthalene is more preferable.
- R s6 and R s7 are independently hydrogen atoms or linear or branched chain monovalent aliphatic hydrocarbon groups, and R s8 is a linear or branched chain monovalent aliphatic hydrocarbon. It is a hydrocarbon group. However, the total number of carbon atoms of R s6 , R s7 and R s8 is 6 or more. The upper limit of the total number of carbon atoms of R s6 , R s7 and R s8 is not particularly limited, but is preferably 20 or less, and more preferably 10 or less.
- linear or branched monovalent aliphatic hydrocarbon group examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, n-octyl, and the like.
- Alkyl groups having 1 to 20 carbon atoms such as 2-ethylhexyl and decyl groups; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as a hexenyl group.
- R s6 is preferably a hydrogen atom
- R s7 and R s8 are each independently preferably an alkyl group having 1 to 6 carbon atoms.
- R s9 to R s13 independently represent a hydrogen atom, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkyl halide group having 1 to 10 carbon atoms. Alternatively, it is an alkenyl halide group having 2 to 10 carbon atoms.
- the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and s-butyl.
- Examples thereof include t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl group and the like.
- the alkyl halide group having 1 to 10 carbon atoms is not particularly limited as long as it is a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms is substituted with a halogen atom.
- Specific examples include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3.
- the halogenated alkenyl group having 2 to 10 carbon atoms is not particularly limited as long as it is a group in which a part or all of hydrogen atoms of the alkenyl group having 2 to 10 carbon atoms is substituted with a halogen atom.
- Specific examples include perfluorovinyl, perfluoro-1-propenyl, perfluoro-2-propenyl, perfluoro-1-butenyl, perfluoro-2-butenyl, perfluoro-3-butenyl group and the like.
- R s9 a nitro group, a cyano group, an alkyl halide group having 1 to 10 carbon atoms, and an alkenyl halide group having 2 to 10 carbon atoms are preferable, and a nitro group, a cyano group, and 1 to 4 carbon atoms are preferable.
- the alkyl halide group and the alkenyl halide group having 2 to 4 carbon atoms are more preferable, and the nitro group, the cyano group, the trifluoromethyl group and the perfluoropropenyl group are even more preferable.
- R s10 to R s13 a halogen atom is preferable, and a fluorine atom is more preferable.
- a 17 is -O-, -S- or -NH-, but -O- is preferable.
- a 18 is a (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the aromatic hydrocarbon group is (n + 1) from the aromatic ring of the aromatic hydrocarbon compound having 6 to 20 carbon atoms. It is a group obtained by removing individual hydrogen atoms. Examples of such aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene and the like. Among these, as A 18 , a group derived from naphthalene or anthracene is preferable, and a group derived from naphthalene is more preferable.
- R s14 to R s17 are independently hydrogen atoms or linear or branched chain monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms.
- Specific examples of the monovalent aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl and n.
- -Alkyl groups having 1 to 20 carbon atoms such as heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl groups; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl
- alkenyl groups having 2 to 20 carbon atoms such as -2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl and hexenyl groups, but alkyl groups having 1 to 20 carbon atoms are preferable, and alkyl groups having 1 to 20 carbon atoms are preferable.
- An alkyl group of 10 is more preferable, and an alkyl group having 1 to 8 carbon atoms is even more preferable.
- R s18 is a linear or branched chain monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or OR s19 .
- R s19 is a monovalent hydrocarbon group having 2 to 20 carbon atoms which may be substituted. Examples of the linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms of R s18 include the same groups as described above.
- R s18 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. Even more preferable.
- Examples of the monovalent hydrocarbon group having 2 to 20 carbon atoms of R s19 include those other than the methyl group among the above-mentioned monovalent aliphatic hydrocarbon groups, and aryl groups such as phenyl, naphthyl, and phenanthryl groups. Among these, R s19 is preferably a linear alkyl group or a phenyl group having 2 to 4 carbon atoms. Examples of the substituent that the monovalent hydrocarbon group may have include a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group, and a cyano group.
- Suitable aryl sulfonic acid ester compounds include, but are not limited to, those shown below.
- the amount of the aryl sulfonic acid ester compound used is preferably about 0.01 to 20, more preferably about 0.05 to 10 with respect to the charge transporting substance 1 in terms of the amount of substance (molar) ratio.
- a commercially available product may be used as the aryl sulfonic acid ester compound, but it may also be synthesized by a known method described in International Publication No. 2017/217455, International Publication No. 2017/217457, International Publication No. 2019/124412 and the like. it can.
- aryl sulfonic acid compound or an aryl sulfonic acid ester compound as the dopant substance, and the solubility in a solvent is preferable.
- an aryl sulfonic acid ester compound in consideration of obtaining a thin film having a smaller extinction coefficient.
- the charge transport varnish is an organic silane compound for the purpose of improving the injection property into the hole transport layer and improving the life characteristics of the device. May include. Its content is usually about 1 to 30% by mass with respect to the total mass of the charge transporting substance and the dopant substance.
- a highly polar solvent capable of satisfactorily dissolving the arylamine compound of the present invention can be used as the organic solvent used when preparing the charge transporting varnish of the present invention.
- the arylamine compound of the present invention can be dissolved in a solvent regardless of the polarity of the solvent.
- a low-polarity solvent may be used because it is superior in process compatibility to a high-polarity solvent.
- a low-polarity solvent is defined as a solvent having a relative permittivity of less than 7 at a frequency of 100 kHz
- a high-polarity solvent is defined as a solvent having a relative permittivity of 7 or more at a frequency of 100 kHz.
- low polar solvents include, for example. Chlorine-based solvents such as chloroform and chlorobenzene; Aromatic hydrocarbon solvents such as toluene, xylene, tetralin, cyclohexylbenzene, decylbenzene; Aliphatic alcohol solvents such as 1-octanol, 1-nonanol, 1-decanol; Ether-based solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether; Esters such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis (2-ethylhexyl) phthalate, dibutyl male
- Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutyramide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone; Ketone solvents such as ethyl methyl ketone, isophorone, cyclohexanone; Cyan-based solvents such as acetonitrile and 3-methoxypropionitrile; Polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; Other than aliphatic alcohols such as diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenyl
- the viscosity of the charge-transporting varnish is appropriately determined depending on the thickness of the thin film to be produced and the solid content concentration, but is usually 1 to 50 mPa ⁇ s at 25 ° C.
- the solid content means a component other than the solvent contained in the charge transporting varnish of the present invention.
- the solid content concentration of the charge-transporting varnish is appropriately set in consideration of the viscosity and surface tension of the varnish, the thickness of the thin film to be produced, and the like, but is usually 0.1 to 20.0 mass. It is about%, preferably about 0.5 to 10.0% by mass, and more preferably about 1.0 to 5.0% by mass in consideration of improving the coatability of the varnish.
- the method for preparing the charge-transporting varnish is not particularly limited, but for example, a method of dissolving all solids such as a charge-transporting substance containing the arylamine compound of the present invention in an organic solvent at once, or a solid. Examples thereof include a method in which a part of the charge is dissolved in an organic solvent and then the remaining solid content is dissolved.
- a charge-transporting varnish when preparing a charge-transporting varnish, from the viewpoint of obtaining a thin film with higher flatness with good reproducibility, after dissolving a charge-transporting substance, a dopant substance, etc. in an organic solvent, a submicrometer-order filter or the like is used. It is desirable to use and filter.
- the charge transporting varnish described above can easily produce a charge transporting thin film by using the varnish, it can be suitably used when manufacturing an electronic device, particularly an organic EL device.
- the charge-transporting thin film can be formed by applying the above-mentioned charge-transporting varnish on a substrate and firing it.
- the varnish coating method is not particularly limited, and examples thereof include a dip method, a spin coating method, a transfer printing method, a roll coating method, a brush coating, an inkjet method, a spray method, and a slit coating method. It is preferable to adjust the viscosity and surface tension of the varnish accordingly.
- the firing atmosphere of the charge-transporting varnish after coating is not particularly limited, and a thin film having a uniform film-forming surface and high charge-transporting property not only in the air atmosphere but also in an inert gas such as nitrogen or in a vacuum can be obtained. Although it can be obtained, depending on the type of dopant substance used, a thin film having higher charge transportability may be obtained with good reproducibility by firing the varnish in an air atmosphere.
- the firing temperature is appropriately set within the range of about 100 to 260 ° C. in consideration of the intended use of the obtained thin film, the degree of charge transportability applied to the obtained thin film, the type of solvent, the boiling point, etc., and the obtained thin film is obtained.
- it is preferably about 140 to 250 ° C., more preferably about 145 to 240 ° C., but when the arylamine compound of the present invention is used as a charge transporting substance, it is as low as 200 ° C. or less. Even by firing, a thin film having good charge transportability can be formed.
- a temperature change of two or more steps may be applied for the purpose of exhibiting higher uniform film forming property or allowing the reaction to proceed on the substrate, and heating may be performed by, for example, a hot plate or the like. It may be carried out using an appropriate device such as an oven.
- the film thickness of the charge transporting thin film is not particularly limited, but is preferably 5 to 300 nm when used as a hole injection layer, a hole transport layer, or a hole transport layer of an organic EL element.
- a method of changing the film thickness there are methods such as changing the solid content concentration in the varnish and changing the amount of solution (varnish amount) on the substrate at the time of coating.
- the charge-transporting thin film of the present invention described above usually exhibits a refractive index (n) of 1.60 or more and an extinction coefficient (k) of 0.100 or less with an average value in the wavelength region of 400 to 800 nm. In some embodiments, it exhibits a refractive index of 1.65 or higher, in other embodiments it exhibits a refractive index of 1.70 or higher, and in some embodiments it has an extinction coefficient of 0.050 or lower. Shows an extinction coefficient of 0.010 or less.
- the above-mentioned charge-transporting thin film When the above-mentioned charge-transporting thin film is applied to an organic EL element, the above-mentioned charge-transporting thin film can be provided between a pair of electrodes constituting the organic EL element.
- Typical configurations of the organic EL element include, but are not limited to, the following (a) to (f).
- an electron block layer or the like may be provided between the light emitting layer and the anode, and a hole (hole) block layer or the like may be provided between the light emitting layer and the cathode.
- the hole injection layer, the hole transport layer or the hole injection transport layer may also have a function as an electron block layer or the like, and the electron injection layer, the electron transport layer or the electron injection transport layer is a hole (hole). It may also have a function as a block layer or the like. Further, if necessary, an arbitrary functional layer can be provided between the layers.
- A Electron / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode
- b anode / hole injection layer / hole transport layer / light emitting layer / electron injection transport layer / Cathode
- c anode / hole injection transport layer / light emitting layer / electron transport layer / electron injection layer / cathode
- d anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode
- e anode / positive Hole injection layer / hole transport layer / light emitting layer / cathode
- f anode / hole injection transport layer / light emitting layer / cathode
- the "hole injection layer”, “hole transport layer” and “hole injection transport layer” are layers formed between the light emitting layer and the anode, and transport holes from the anode to the light emitting layer.
- it has a function and only one layer of hole transporting material is provided between the light emitting layer and the anode, it is a "hole injection transport layer", and between the light emitting layer and the anode,
- the layer close to the anode is the “hole injection layer” and the other layers are the “hole transport layer”.
- the hole injection (transport) layer a thin film having excellent not only hole acceptability from the anode but also hole injection property into the hole transport (emission) layer is used.
- the "electron injection layer”, “electron transport layer” and “electron transport layer” are layers formed between the light emitting layer and the cathode and have a function of transporting electrons from the cathode to the light emitting layer.
- an “electron injection transporting layer” When only one layer of electron transporting material is provided between the light emitting layer and the cathode, it is an “electron injection transporting layer”, and a layer of electron transporting material is provided between the light emitting layer and the cathode.
- the layer close to the cathode is the “electron injection layer”
- the other layers are the “electron transport layer”.
- the "light emitting layer” is an organic layer having a light emitting function, and includes a host material and a dopant material when a doping system is adopted.
- the host material mainly has a function of promoting the recombination of electrons and holes and confining excitons in the light emitting layer, and the dopant material efficiently emits excitons obtained by recombination.
- the host material mainly has a function of confining excitons generated by the dopant in the light emitting layer.
- the charge-transporting thin film produced from the charge-transporting varnish of the present invention is a functional layer such as a hole injection layer, a hole transport layer, and a hole injection transport layer provided between the anode and the light emitting layer of the organic EL element.
- a functional layer such as a hole injection layer, a hole transport layer, and a hole injection transport layer provided between the anode and the light emitting layer of the organic EL element.
- it is usually suitable as a hole injection layer on which an upper layer is formed by a coating method.
- Examples of materials and methods for producing an organic EL device using the charge-transporting varnish of the present invention include, but are not limited to, the following.
- An example of a method for manufacturing an OLED device having a hole injection layer made of a thin film obtained from the charge transporting varnish is as follows. It is preferable that the electrode is preliminarily subjected to surface treatment such as cleaning with alcohol, pure water or the like, UV ozone treatment, oxygen-plasma treatment or the like within a range that does not adversely affect the electrode.
- a hole injection layer is formed on the anode substrate by the above method using the above charge transporting varnish.
- a hole transport layer, a light emitting layer, an electron transport layer / hole block layer, an electron injection layer, and a cathode metal are sequentially vapor-deposited.
- a composition for forming a hole transport layer containing a hole transport polymer and a composition for forming a light emitting layer containing a light emitting polymer are used. These layers are formed by a wet process using. If necessary, an electron block layer may be provided between the light emitting layer and the hole transport layer.
- anode material examples include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), metals typified by aluminum, and metal anodes composed of alloys thereof. Those that have been flattened are preferable. Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used. Examples of other metals constituting the metal anode include, but are not limited to, gold, silver, copper, indium, and alloys thereof.
- Materials for forming the hole transport layer include (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spirodimer, N, N'-bis (naphthalen-1-yl) -N, N'-bis.
- Examples of the material forming the light emitting layer include a metal complex such as an aluminum complex of 8-hydroxyquinoline, a metal complex of 10-hydroxybenzo [h] quinoline, a bisstyrylbenzene derivative, a bisstyrylarylene derivative, and (2-hydroxyphenyl) benzo.
- a metal complex such as an aluminum complex of 8-hydroxyquinoline, a metal complex of 10-hydroxybenzo [h] quinoline, a bisstyrylbenzene derivative, a bisstyrylarylene derivative, and (2-hydroxyphenyl) benzo.
- Low molecular weight luminescent materials such as thiazole metal complexes and silol derivatives; poly (p-phenylene vinylene), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene], poly (3-alkyl Examples thereof include, but are not limited to, a system in which a light emitting material and an electron transfer material are mixed with a polymer compound such as thiophene) and polyvinylcarbazole.
- the light emitting layer When the light emitting layer is formed by vapor deposition, it may be co-deposited with a light emitting dopant, and the light emitting dopant is a metal complex such as tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3 ). , A naphthacene derivative such as rubrene, a quinacridone derivative, a condensed polycyclic aromatic ring such as perylene, and the like, but are not limited thereto.
- Examples of the material for forming the electron transport layer / whole block layer include, but are not limited to, an oxydiazole derivative, a triazole derivative, a phenanthroline derivative, a phenylquinoxaline derivative, a benzimidazole derivative, and a pyrimidine derivative.
- Materials for forming the electron injection layer include metal oxides such as lithium oxide (Li 2 O), magnesium oxide (Mg O), and alumina (Al 2 O 3 ), lithium fluoride (LiF), and sodium fluoride (NaF). Examples include, but are not limited to, metal fluorides such as.
- Examples of the cathode material include, but are not limited to, aluminum, magnesium-silver alloy, aluminum-lithium alloy, and the like.
- Examples of the material for forming the electron block layer include, but are not limited to, tris (phenylpyrazole) iridium and the like.
- hole-transporting polymer examples include poly [(9,9-dihexylfluorenyl-2,7-diyl) -co- (N, N'-bis ⁇ p-butylphenyl ⁇ -1,4-diaminophenylene).
- the luminescent polymer examples include polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), and poly (2-methoxy-5- (2'-ethylhexoxy) -1,4-phenylene vinylene) (MEH-).
- polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF)
- MEH- poly (2-methoxy-5- (2'-ethylhexoxy) -1,4-phenylene vinylene)
- PVCz polyvinylcarbazole
- the charge-transporting thin film obtained from the charge-transporting varnish of the present invention serves as a functional layer such as a hole injection layer, a hole transport layer, and a hole injection transport layer provided between the anode and the light emitting layer of the organic EL element.
- organic photoelectric conversion elements organic thin film solar cells, organic perovskite photoelectric conversion elements, organic integrated circuits, organic field effect transistors, organic thin films, organic light emitting transistors, organic optical testers, organic photoreceivers, organic It can also be used as a charge transporting thin film in electronic devices such as electric field extinguishing devices, light emitting electronic chemical batteries, quantum dot light emitting diodes, quantum lasers, organic laser diodes and organic Plasmon light emitting devices.
- electronic devices such as electric field extinguishing devices, light emitting electronic chemical batteries, quantum dot light emitting diodes, quantum lasers, organic laser diodes and organic Plasmon light emitting devices.
- Fine shape measuring machine Surfcoder ET-4000 Manufacture of element: Multi-function vapor deposition equipment system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd. (7) Measurement of element current density and brightness: Multi-channel IVL measuring device manufactured by EHC Co., Ltd. (8) Life measurement of EL element (brightness half-life measurement): Organic EL brightness life manufactured by EHC Co., Ltd. Evaluation system PEL-105S (9) Measurement of refractive index (n) and extinction coefficient (k): Multi-incident angle spectroscopic ellipsometer VASE manufactured by JA Woolam Japan
- Lithium Hexamethyldi Shirajide (LHMDS) 1.3 mol / L tetrahydrofuran solution 2-Bromo-7-iodofluorene manufactured by Tokyo Kasei Kogyo Co., Ltd. benzyltriethylammonium chloride manufactured by Tokyo Kasei Kogyo Co., Ltd. 3-Nitroaniline manufactured by Tokyo Kasei Kogyo Co., Ltd. Tokyo 1-Bromo-3-nitrobenzene manufactured by Kasei Kogyo Co., Ltd. Hydrogen chloride (approx. 1 mL / L ethyl acetate solution) manufactured by Tokyo Kasei Kogyo Co., Ltd.
- the dried solid was dissolved in 20 mL of tetrahydrofuran, the obtained solution was added to 200 mL of n-hexane, the precipitated solid was filtered off by a membrane filter, and the filtered solid was dried under reduced pressure at 60 ° C.
- the dried solid was dissolved in 20 mL of tetrahydrofuran, the obtained solution was added to 200 mL of a mixed solvent of methanol and water (3/1 (v / v)), and the precipitated solid was filtered off by a membrane filter. The obtained solid was dried under reduced pressure at 60 ° C.
- the aqueous layer was removed.
- the obtained organic layer was added dropwise to a mixed solvent of methanol and water (3/1 (v / v)), the precipitated solid was filtered off with a membrane filter, and the filtered solid was dried under reduced pressure at 60 ° C. Further, the dried solid was dissolved in 20 mL of tetrahydrofuran, the obtained solution was added to 200 mL of n-hexane, the precipitated solid was filtered off by a membrane filter, and the filtered solid was dried under reduced pressure at 60 ° C.
- the reaction mixture was cooled to room temperature, filtered through a filter filled with 200 g of silica gel N60, the obtained filtrate was concentrated to a weight of 100 g, the concentrate was added dropwise to 1000 mL of toluene, and the resulting solid was filtered off. .. The obtained solid was dried to obtain 24.1 g of bis (3-nitrophenyl) amine (yield 93.1%).
- Example 1-1 except that 0.5 mmol (123.2 mg) of N, N'-bis (4-aminophenyl) terephthalamide was used instead of 3,3', 5,5'-tetramethylbenzidine. The operation was carried out in the same manner to obtain 0.43 g (70.9%) of the arylamine compound D2d.
- the 1 H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.
- Example 1-1 Same as in Example 1-1 except that 0.5 mmol (160.12 mg) of 2,2'-bis (trifluoromethyl) benzidine was used instead of 3,3', 5,5'-tetramethylbenzidine. The procedure was carried out to obtain 0.46 g (44.8%) of arylamine compound A3d.
- the 1 H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.
- the arylamine compound was operated in the same manner as in Example 1-1 except that 0.5 mmol (106.1 mg) of m-trizine was used instead of 3,3', 5,5'-tetramethylbenzidine. 0.17 g (17.5%) of G3d was obtained.
- the 1 H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.
- Example 2-1 A solution obtained by adding arylamine compound A3b (0.028 g) and aryl sulfonic acid ester A (0.022 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared having a pore size of 0.2 ⁇ m. The mixture was filtered through a syringe filter to obtain a charge-transporting varnish A3b-1.
- Example 2-2 The solution obtained by adding arylamine compound A3c (0.030 g) and aryl sulfonic acid ester A (0.020 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 ⁇ m. Filtering with a filter gave a charge-transporting varnish A3c-1.
- Example 2-3 The solution obtained by adding arylamine compound A3d (0.031 g) and aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 ⁇ m. Filtering with a filter gave a charge-transporting varnish A3d-1.
- Example 2-4 The solution obtained by adding arylamine compound A3e (0.031 g) and aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 ⁇ m. Filtering with a filter gave a charge-transporting varnish A3e-1.
- Example 2-5 The solution obtained by adding arylamine compound A3f (0.032 g) and aryl sulfonic acid ester A (0.018 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 ⁇ m. The mixture was filtered through a filter to obtain a charge-transporting varnish A3f-1.
- Example 2-6 The solution obtained by adding 3 g (0.031 g) of the arylamine compound A (0.031 g) and the aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 ⁇ m. Filtering with a filter gave a charge-transporting varnish A3g-1.
- Example 2-7 The solution obtained by adding arylamine compound A3h (0.031 g) and aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 ⁇ m. The mixture was filtered through a filter to obtain a charge-transporting varnish A3h-1.
- Example 2-8 The solution obtained by adding arylamine compound B3b (0.029 g) and aryl sulfonic acid ester A (0.021 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 ⁇ m. Filtering with a filter gave a charge-transporting varnish B3b-1.
- Example 2-9 The solution obtained by adding arylamine compound B3c (0.030 g) and aryl sulfonic acid ester A (0.020 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 ⁇ m. Filtering with a filter gave a charge-transporting varnish B3c-1.
- Example 2-10 The solution obtained by adding arylamine compound B3d (0.031 g) and aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 ⁇ m. Filtering with a filter gave a charge-transporting varnish B3d-1.
- Example 2-11 The solution obtained by adding arylamine compound B2b (0.022 g) and aryl sulfonic acid ester A (0.028 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 ⁇ m. Filtering with a filter gave a charge-transporting varnish B2b-1.
- Example 2-12 The solution obtained by adding arylamine compound B2c (0.024 g) and aryl sulfonic acid ester A (0.026 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 ⁇ m. Filtering with a filter gave a charge-transporting varnish B2c-1.
- Example 2-13 The solution obtained by adding arylamine compound B2d (0.025 g) and aryl sulfonic acid ester A (0.025 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 ⁇ m. Filtering with a filter gave a charge-transporting varnish B2d-1.
- Example 2-14 The solution obtained by adding arylamine compound H3d (0.033 g) and aryl sulfonic acid ester A (0.017 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 ⁇ m. Filtering with a filter gave a charge-transporting varnish H3d-1.
- Example 2-15 The solution obtained by adding arylamine compound I3d (0.033 g) and aryl sulfonic acid ester A (0.017 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 ⁇ m. Filtering with a filter gave a charge-transporting varnish I3d-1.
- Examples 3-1 to 3-11 In the same manner as in Comparative Example 3-1 except that the arylamine compounds A3b, A3c, A3d, A3e, A3f, A3g, A3h, B3d, B2d, H3d, or I3d were used instead of the arylamine compound A3a. Obtains charge-transporting varnishes A3b-2, A3c-2, A3d-2, A3e-2, A3f-2, A3g-2, A3h-2, B3d-2, B2d-2, H3d-2, or I3d-2. It was.
- the thin film obtained from the charge-transporting varnish of the present invention has the same or higher refractive index than the thin film obtained from the charge-transporting varnish of Comparative Example 4-1 and is equivalent. Or it can be seen that it has a low extinction coefficient.
- the charge-transporting varnish A3a-2 was applied onto the hole injection layer using a spin coater, and then fired at 130 ° C. for 10 minutes in an air atmosphere to form a hole transport layer (film thickness: 40 nm). Formed.
- a hole-only element (HOD) was obtained by forming an aluminum thin film of 80 nm at 0.2 nm / sec using a vapor deposition apparatus (vacuum degree 1.0 ⁇ 10 -5 Pa).
- the composition for forming a hole injection layer was prepared by the following procedure. 0.137 g of the aniline derivative represented by the formula (3) synthesized according to the method described in WO2013 / 084664 and the aryl represented by the formula (4) synthesized according to the method described in WO 2006/025432.
- 0.271 g of sulfonic acid was dissolved in 6.7 g of 1,3-dimethyl-2-imidazolidinone under a nitrogen atmosphere.
- 10 g of cyclohexanol and 3.3 g of propylene glycol were sequentially added and stirred to obtain a composition for forming a hole injection layer (the same applies hereinafter).
- Example 5-1 to 5-11 instead of the charge-transporting varnish A3a-2, the charge-transporting varnish A3b-2, A3c-2, A3d-2, A3e-2, A3f-2, A3g-2, A3h-2, B3d-2, B2d-2 , H3d-2, or I3d-2 were used, respectively, and HOD was prepared in the same manner as in Example 5-1.
- the thin film prepared from the charge transporting varnish of the present invention exhibits better charge transporting property than the thin film prepared from the charge transporting varnish of the comparative example. This improvement in charge transportability is considered to be associated with an increase in the effective conjugation length of the conductive site in the arylamine compound of the present invention.
- Example 7-1 to 7-12, Comparative Example 7-2 instead of the charge-transporting varnish A3a-1, the charge-transporting varnishes A3b-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3h-1, B3b-1, B3d-, respectively.
- HOD was prepared in the same manner as in Comparative Example 7-1 except that 1, B2d-1, H3d-1, I3d-1, or B3a-1 was used.
- the device using the hole injection layer made from the charge-transporting varnish of the present invention has a higher relative strength of the HOD current density with respect to the SLD current density than the device made in the comparative example. I understand.
- a 10 nm film was formed on the electronic block material HTEB-01 manufactured by Kanto Chemical Co., Inc.
- the light emitting layer host material NS60 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and the light emitting layer dopant material Ir (ppy) 3 were co-deposited.
- the vapor deposition rate was controlled so that the concentration of Ir (ppy) 3 was 6%, and 40 nm was laminated.
- thin films of Alq 3 , lithium fluoride and aluminum were sequentially laminated to obtain an organic EL device.
- the vapor deposition rate was 0.2 nm / sec for Alq 3 and aluminum, and 0.02 nm / sec for lithium fluoride, respectively, and the film thicknesses were 20 nm, 0.5 nm, and 80 nm, respectively.
- the organic EL element was sealed with a sealing substrate and then the characteristics were evaluated. Sealing was performed by the following procedure.
- an organic EL element is placed between the sealing substrates, and the sealing substrate is an adhesive (Matsumura Oil Research Corp., Moresco Moisture Cut WB90US (P)). It was pasted together.
- a water catching agent (HD-071010W-40 manufactured by Dynic Co., Ltd.) was housed in the sealing substrate together with the organic EL element.
- the bonded substrate was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ / cm 2 ) and then annealed at 80 ° C. for 1 hour to cure the adhesive.
- Example 8-1 to 8-12 instead of the charge-transporting varnish A3a-1, the charge-transporting varnishes A3b-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3h-1, B3b-1, B3d-, respectively.
- An organic EL device was produced in the same manner as in Comparative Example 8-1 except that 1, B2d-1, H3d-1, or I3d-1 was used.
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Abstract
Description
この有機EL素子では複数の機能性薄膜が用いられるが、その中の1つである正孔注入層は、陽極と正孔輸送層または発光層との電荷の授受を担い、有機EL素子の低電圧駆動および高輝度を達成するために重要な役割を果たす。 Organic electroluminescence (hereinafter referred to as organic EL) elements are expected to be put into practical use in fields such as displays and lighting, and various developments related to materials and element structures are expected for the purpose of low voltage drive, high brightness, long life, etc. Has been made.
A plurality of functional thin films are used in this organic EL element, and one of them, the hole injection layer, is responsible for the transfer of electric charge between the anode and the hole transport layer or the light emitting layer, and is low in the organic EL element. It plays an important role in achieving voltage drive and high brightness.
このため、有機ELディスプレイの大面積化が進められている現在、ウェットプロセスで形成可能な正孔注入層が望まれている。 The method for producing the hole injection layer is roughly classified into a dry process represented by a vapor deposition method and a wet process represented by a spin coating method. Comparing these processes, the wet process can efficiently produce a thin film with a large area and high flatness.
For this reason, as the area of organic EL displays is being increased, a hole injection layer that can be formed by a wet process is desired.
このように、屈折率は有機EL素子の設計上重要な要素であり、有機EL素子用材料では、屈折率も考慮すべき重要な物性値と考えられている。 On the other hand, various efforts have been made to improve the performance of organic EL devices, but efforts have been made to adjust the refractive index of the functional thin film used for the purpose of improving the light extraction efficiency. There is. Specifically, by using a hole injection layer or a hole transport layer having a relatively high or low refractive index in consideration of the overall configuration of the device and the refractive index of other adjacent members, the efficiency of the device is high. Attempts have been made to achieve this (see Patent Documents 4 and 5).
As described above, the refractive index is an important factor in the design of the organic EL element, and in the material for the organic EL element, the refractive index is also considered to be an important physical property value to be considered.
1. 下記式(1)~(6)のいずれかで表されることを特徴とするアリールアミン化合物(ただし、下記式(P1)~(P4)で表される化合物を除く。)、
Xは、それぞれ独立して、置換されていてもよいとともに、ヘテロ原子を含んでいてもよいアリーレン基を表し、
Yは、それぞれ独立して、置換されていてもよいフェニレン基を表し、
gは、それぞれ独立して、1~10の整数を表す。
3. 前記Arsが、下記式(101A)~(118A)のいずれかで表される1のアリールアミン化合物、
4. 前記Arsが、下記式(101A-1)~(118A-3)のいずれかで表される3のアリールアミン化合物、
5. 前記Xが、下記式(201)~(207)のいずれかで表される1~4のいずれかのアリールアミン化合物、
6. 前記Xが、下記式(201A)~(207A)のいずれかで表される5のアリールアミン化合物、
7. 前記Xが、下記式(201A-1)~(207A-1)のいずれかで表される6のアリールアミン化合物、
8. 前記Arcが、同一の基である1~7のいずれかのアリールアミン化合物、
9. 1~8のいずれかのアリールアミン化合物と、有機溶媒とを含む電荷輸送性ワニス、
10. ドーパント物質を含む9の電荷輸送性ワニス、
11. 9または10の電荷輸送性ワニスを用いて作製される電荷輸送性薄膜、
12. 11の電荷輸送性薄膜を備える電子素子
を提供する。 That is, the present invention
1. 1. Arylamine compounds represented by any of the following formulas (1) to (6) (excluding compounds represented by the following formulas (P1) to (P4)),
X represents an arylene group which may be independently substituted and may contain a heteroatom.
Y represents a phenylene group which may be substituted independently of each other.
g represents an integer of 1 to 10 independently of each other.
3. 3. 1 arylamine compound, wherein Ar s is represented by any of the following formulas (101A) to (118A).
4. Wherein Ar s is 3 arylamine compound represented by any one of the following formulas (101A-1) ~ (118A -3),
5. X is an arylamine compound according to any one of 1 to 4 represented by any of the following formulas (201) to (207).
6. 5 arylamine compounds, wherein X is represented by any of the following formulas (201A) to (207A).
7. 6 arylamine compounds represented by any of the following formulas (201A-1) to (207A-1), wherein X is
8. Wherein Ar c is one of arylamine compounds of 1-7 are the same group,
9. A charge-transporting varnish containing any of the arylamine compounds 1 to 8 and an organic solvent.
10. 9 charge-transporting varnishes containing dopant material,
11. Charge transport thin films made using 9 or 10 charge transport varnishes,
12. Provided is an electronic device including 11 charge transporting thin films.
この電荷輸送性薄膜は、有機EL素子をはじめとした電子素子用薄膜として、特に、上層にウェットプロセスで薄膜が積層される電子素子用薄膜として好適に用いることができ、本発明の電荷輸送性薄膜を有機EL素子の正孔注入層等に適用することで、良好な特性を有する素子を作製することができる。 The arylamine compound of the present invention has good solubility in an organic solvent, and by using a charge-transporting varnish containing this arylamine compound, a charge-transporting thin film having high transparency and high refractive index can be obtained. be able to.
This charge transporting thin film can be suitably used as a thin film for electronic devices such as organic EL devices, particularly as a thin film for electronic devices in which a thin film is laminated by a wet process on an upper layer, and the charge transporting property of the present invention can be used. By applying a thin film to a hole injection layer or the like of an organic EL device, an device having good characteristics can be manufactured.
本発明に係るアリールアミン化合物は、下記式(1)~(6)のいずれかで表されることを特徴とするが、上記のとおり式(P1)~(P4)で表される化合物を包含しない。 Hereinafter, the present invention will be described in more detail.
The arylamine compound according to the present invention is characterized by being represented by any of the following formulas (1) to (6), and includes the compounds represented by the formulas (P1) to (P4) as described above. do not do.
炭素数1~20のアルキル基としては、直鎖状、分岐鎖状、環状のいずれでもよく、例えば、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、s-ブチル、t-ブチル、n-ペンチル、n-ヘキシル、n-ヘプチル、n-オクチル、n-ノニル、n-デシル基等の炭素数1~20の直鎖または分岐鎖状アルキル基;シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシル、ビシクロブチル、ビシクロペンチル、ビシクロヘキシル、ビシクロヘプチル、ビシクロオクチル、ビシクロノニル、ビシクロデシル基等の炭素数3~20の環状アルキル基などが挙げられる。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl. , N-Pentyl, n-Hexyl, n-Heptyl, n-octyl, n-Nonyl, n-decyl group and other linear or branched alkyl groups having 1 to 20 carbon atoms; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. , Cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl group and other cyclic alkyl groups having 3 to 20 carbon atoms.
R2の置換されていてもよいとともに、ヘテロ原子を含んでいてもよいアリール基の置換基の具体例としては、ハロゲン原子、ニトロ基、シアノ基、炭素数1~20のアルキル基、炭素数2~20のアルケニル基、炭素数2~20のアルキニル基、炭素数1~20のハロゲン化アルキル基、炭素数1~20のアルコキシ基および炭素数6~20のアリール基等が挙げられ、ハロゲン原子、炭素数1~20のアルキル基および炭素数1~20のハロゲン化アルキル基、炭素数1~20のアルコキシ基および炭素数6~20のアリール基の具体例としては上記と同様のものが挙げられる。 The aryl group which may be substituted with R 2 in the above formulas (Q), (Q') and (Q ″) and may contain a hetero atom contains a hetero atom as a constituent atom thereof. It is also a good arylene group, and may have a structure in which rings are condensed or a structure in which rings are linked. The number of carbon atoms is not particularly limited, but is usually 6 to 60, preferably 40 or less, and more preferably 30 or less.
Specific examples of the substituent of the aryl group which may be substituted with R 2 and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and a carbon number of carbon atoms. Examples thereof include an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms. Specific examples of the atom, the alkyl group having 1 to 20 carbon atoms, the alkyl halide group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms are the same as above. Can be mentioned.
以下、R2として好適な基の具体例を挙げるが、これらに限定されない。 As R 2 , an aryl group having 6 to 10 carbon atoms which may be substituted and may contain a hetero atom is preferable, and a phenyl group which may be substituted and a naphthyl group which may be substituted may be used. More preferably, both are more preferably a phenyl group or a naphthyl group, and both are even more preferably a phenyl group.
Hereinafter, specific examples of groups suitable for R 2 will be given, but the present invention is not limited thereto.
Arsの置換されていてもよいとともに、ヘテロ原子を含んでいてもよいアリーレン基の置換基の具体例としては、ハロゲン原子、ニトロ基、シアノ基、炭素数1~20のアルキル基、炭素数1~20のハロゲン化アルキル基、炭素数1~20のアルコキシ基および炭素数6~20のアリール基等が挙げられ、ハロゲン原子、炭素数1~20のアルキル基、炭素数1~20のハロゲン化アルキル基、炭素数1~20のアルコキシ基および炭素数6~20のアリール基としては上記と同様のものが挙げられる。
好ましい一態様では、Arsが、下記式(101)~(118)のいずれかで表される基である。 The arylene group which may be substituted with Ar s in the above formulas (Q), (Q') and (Q ″) and may contain a hetero atom contains a hetero atom as a constituent atom thereof. It is also a good arylene group, and may have a structure in which rings are condensed or a structure in which rings are linked. The number of carbon atoms is not particularly limited, but is usually 6 to 60, preferably 40 or less, and more preferably 30 or less.
Specific examples of the substituent of the arylene group which may be substituted with Ar s and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and a carbon number of carbon atoms. Examples thereof include an alkyl halide group having 1 to 20, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and the like, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a halogen having 1 to 20 carbon atoms. Examples of the alkylated alkyl group, the alkoxy group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms are the same as those described above.
In one preferred embodiment, Ar s is a group represented by any one of the following formulas (101) to (118).
R3~R5における、ハロゲン原子、炭素数1~20のアルキル基、炭素数1~20のアルコキシ基、炭素数6~20のアリール基、炭素数1~20のハロゲン化アルキル基としては上記と同様のものが挙げられる。 R 3 independently contains a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. Alternatively, it represents an aryl group having 6 to 20 carbon atoms, where V 1 is an independent C (R 4 ) 2 (R 4 is an independent hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or (Represents an alkyl halide group having 1 to 20 carbon atoms), NR 5 (R 5 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms), S, It represents O or SO 2 , where V 2 is NR 5 (R 5 has the same meaning as above), S or O.
The halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkyl halide groups having 1 to 20 carbon atoms in R 3 to R 5 are described above. The same can be mentioned.
R4は、それぞれ独立して、炭素数1~10のアルキル基が好ましく、炭素数1~5のアルキル基がより好ましく、いずれもメチル基がより一層好ましい。
R5は、水素原子、炭素数1~10のアルキル基、炭素数6~10のアリール基が好ましく、水素原子、炭素数1~5のアルキル基、フェニル基、ナフチル基がより好ましく、水素原子、メチル基、フェニル基がより一層好ましい。 In particular, R 3 is preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkyl halide group having 1 to 10 carbon atoms, respectively, and has a hydrogen atom and a carbon number of carbon atoms. Alkyl groups of 1 to 5 and fluoroalkyl groups having 1 to 5 carbon atoms are more preferable, and hydrogen atoms, methyl groups and trifluoromethyl groups are even more preferable. From the viewpoint of lowering the extinction coefficient of the obtained thin film, at least one R 3 may be an electron-withdrawing group such as a halogen atom, a nitro group, a cyano group, or a fluoroalkyl group having 1 to 5 carbon atoms. Preferably, in consideration of this point, a trifluoromethyl group is more preferable.
Independently, R 4 preferably has an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group.
R 5 is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, and a naphthyl group, and a hydrogen atom. , Methyl group and phenyl group are even more preferable.
さらに、全てのR3が電子吸引基ではない場合、得られる薄膜の消衰係数を低下させるという点から、V2は、S、Oが好ましい。なお、V2が、S、Oの場合に、R3中に電子吸引基が存在してもよい。 Also, if all R 3 is not an electron withdrawing group, the extinction coefficient of the thin film from the viewpoint of reducing the resulting, V 1 is, S, O, SO 2 are preferred. When V 1 is S, O, SO 2 , an electron-withdrawing group may be present in R 3 .
Furthermore, if all R 3 is not an electron withdrawing group, from the viewpoint of lowering the extinction coefficient of the thin film obtained, V 2 is, S, O is preferred. When V 2 is S or O, an electron-withdrawing group may be present in R 3 .
Xの置換されていてもよいとともに、ヘテロ原子を含んでいてもよいアリーレン基の置換基の具体例としては、ハロゲン原子、ニトロ基、シアノ基、炭素数1~20のアルキル基、炭素数1~20のハロゲン化アルキル基、炭素数1~20のアルコキシ基および炭素数6~20のアリール基等が挙げられ、ハロゲン原子、炭素数1~20のアルキル基、炭素数1~20のハロゲン化アルキル基、炭素数1~20のアルコキシ基および炭素数6~20のアリール基としては上記と同様のものが挙げられる。 The arylene group which may be substituted with X in the above formulas (1) and (2) and may contain a hetero atom is not particularly limited, and even if the structure is a condensed ring, the ring is not particularly limited. May be a connected structure. The number of carbon atoms is not particularly limited, but is usually 6 to 60, preferably 40 or less, and more preferably 30 or less.
Specific examples of the substituent of the arylene group which may be substituted with X and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, and 1 carbon atom. Examples thereof include an alkyl group having 20 to 20, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and the like, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a halogenation having 1 to 20 carbon atoms. Examples of the alkyl group, the alkoxy group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms include the same as above.
R7は、それぞれ独立して、炭素数1~10のアルキル基が好ましく、炭素数1~5のアルキル基がより好ましく、いずれもメチル基がより一層好ましい。
R8は、水素原子、炭素数1~10のアルキル基、炭素数6~10のアリール基が好ましく、水素原子、炭素数1~5のアルキル基、フェニル基、ナフチル基がより好ましく、水素原子、メチル基、フェニル基がより一層好ましい。 In particular, R 6 is preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkyl halide group having 1 to 10 carbon atoms, respectively, and has a hydrogen atom and a carbon number of carbon atoms. Alkyl groups of 1 to 5 and fluoroalkyl groups having 1 to 5 carbon atoms are more preferable, and hydrogen atoms, methyl groups and trifluoromethyl groups are even more preferable. From the viewpoint of lowering the extinction coefficient of the obtained thin film, at least one R 6 is preferably an electron-withdrawing group such as a halogen atom, a nitro group, a cyano group, or a fluoroalkyl group having 1 to 5 carbon atoms. Considering the point, a trifluoromethyl group is more preferable.
Independently, R 7 preferably has an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group.
R 8 is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, and a naphthyl group, and a hydrogen atom. , Methyl group and phenyl group are even more preferable.
さらに、全てのR6が電子吸引基ではない場合、得られる薄膜の消衰係数を低下させるという点から、W3は、S、Oが好ましい。なお、W3が、S、O、SO2の場合に、R6中に電子吸引基が存在してもよい。 Also, if all R 6 is not an electron withdrawing group, the extinction coefficient of the thin film from the viewpoint of reducing the obtained, W 2 is, S, O, SO 2 are preferred. When W 2 is S, O, SO 2 , an electron-withdrawing group may be present in R 6 .
Furthermore, if all R 6 is not an electron withdrawing group, from the viewpoint of lowering the extinction coefficient of the resulting thin film, W 3 is, S, O is preferred. When W 3 is S, O, SO 2 , an electron-withdrawing group may be present in R 6 .
これらの中でも、R6’は、炭素数1~10のアルキル基、炭素数1~10のハロゲン化アルキル基が好ましく、炭素数1~5のアルキル基、炭素数1~5のフルオロアルキル基がより好ましく、メチル基、トリフルオロメチル基がより一層好ましい。 In the formula (201A ') ~ (207A' ), R 6 ' are each independently a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms Represents an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Specific examples of the alkoxy group and the aryl group having 6 to 20 carbon atoms are the same as those described above.
Among these, R 6'preferably an alkyl group having 1 to 10 carbon atoms and an alkyl halide group having 1 to 10 carbon atoms, and an alkyl group having 1 to 5 carbon atoms and a fluoroalkyl group having 1 to 5 carbon atoms. More preferably, a methyl group and a trifluoromethyl group are even more preferable.
特に、Arcは、好ましくは式(Q-1)で表される基(ArC1)であり、より好ましくは式(Q-2)で表される基(ArC2)または式(Q-3)で表される基(ArC3)である。 In the present invention, from the viewpoint of ease of synthesis, it is preferable that Arc is the same group in each of the formulas (1) to (6).
In particular, Ar c is preferably a group (Ar C1) represented by the formula (Q-1), more preferably a group represented by the formula (Q-2) (Ar C2 ) or formula (Q-3 ) Is a group (Ar C3 ).
擬ハロゲン基としては、メタンスルホニルオキシ、トリフルオロメタンスルホニルオキシ、ノナフルオロブタンスルホニルオキシ基等の(フルオロ)アルキルスルホニルオキシ基;ベンゼンスルホニルオキシ、トルエンスルホニルオキシ基等の芳香族スルホニルオキシ基などが挙げられる。 Examples of the halogen atom include the same as above.
Examples of the pseudohalogen group include (fluoro) alkylsulfonyloxy groups such as methanesulfonyloxy, trifluoromethanesulfonyloxy and nonafluorobutanesulfonyloxy groups; aromatic sulfonyloxy groups such as benzenesulfonyloxy and toluenesulfonyloxy groups. ..
また、配位子を用いる場合、その使用量は、使用する金属錯体に対し0.1~5当量とすることができるが、1~2当量が好適である。 The amount of the catalyst used can be about 0.01 to 0.5 mol with respect to 1 mol of the aryl halide compound [II], but is preferably about 0.05 to 0.2 mol.
When a ligand is used, the amount used can be 0.1 to 5 equivalents with respect to the metal complex to be used, but 1 to 2 equivalents are preferable.
塩基を用いる場合、その使用量は、使用するハロゲン化アリール化合物[II]に対し0.1~5当量とすることができるが、1~2当量が好適である。 In addition, a base may be used in the above reaction. Examples of the base include lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, t-butoxysodium, t-butoxypotassium, sodium hydroxide, potassium hydroxide. , Alkali metal alone such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, alkali metal hydride, alkali metal hydroxide, alkoxy alkali metal, alkali metal carbonate, alkali metal hydrogen carbonate; alkaline soil carbonate such as calcium carbonate Metals; n-butyl lithium, s-butyl lithium, t-butyl lithium, lithium diisopropylamide (LDA),
When a base is used, the amount used can be 0.1 to 5 equivalents with respect to the aryl halide compound [II] to be used, but 1 to 2 equivalents are preferable.
反応終了後は、常法にしたがって後処理をし、目的とするアリールアミン化合物を得ることができる。 The reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, but is particularly preferably about 0 to 200 ° C., more preferably 20 to 150 ° C. The reaction time is appropriately determined in consideration of the reaction temperature, the reactivity of the raw material compound, and the like, but is usually about 30 minutes to 50 hours.
After completion of the reaction, post-treatment can be carried out according to a conventional method to obtain the desired arylamine compound.
その他、触媒、配位子、塩基、溶媒、反応の温度および時間等に関するカップリング反応の諸条件および好適な条件は、式(1)または(2)で表されるアリールアミン化合物に関して説明したものと同じである。 The charging ratio of the aryldiamine compound [I'] to the aryl halide compound [II] is not particularly limited as long as the desired product can be obtained, but usually the compounds to be synthesized are the arylamine compounds (3) to Depending on which of (5) is used, and in consideration of the reactivity and bulkiness of the raw material compound, the amount of the aryl halide compound is 1 with respect to the total amount of NH groups of the aryldiamine compound [I']. .2 Equivalent or less is appropriately determined, and when synthesizing the arylamine compound (3), 1.0 equivalent or more of the aryl halide compound is preferable with respect to the amount of all NH groups of the aryldiamine compound [I']. , In the case of synthesizing the arylamine compound (4), the amount of the aryldiamine compound [I'] can be 2.0 equivalents or more of the aryl halide compound, but 2.0 to 2.4 equivalents. Preferably, when synthesizing the arylamine halide compound (5), the amount of the aryl compound can be 4.0 equivalents or more with respect to the amount of the aryldiamine compound [I'], but 4.0 to 4.8 equivalents. Is preferable.
In addition, various conditions and suitable conditions of the coupling reaction regarding the catalyst, the ligand, the base, the solvent, the temperature and time of the reaction, etc. are described with respect to the arylamine compound represented by the formula (1) or (2). Is the same as.
まず、ジニトロ化合物[I”-1]とハロゲン化アリール化合物[II]とを反応させて、ジニトロ化合物[I”-2]を得る。 The arylamine compound represented by the formula (6) of the present invention (hereinafter, also referred to as arylamine compound (6)) can be produced by the following method.
First, the dinitro compound [I "-1] is reacted with the aryl halide compound [II] to obtain the dinitro compound [I "-2].
その他、触媒、配位子、塩基、溶媒、反応の温度および時間等に関する反応の諸条件および好適な条件は、式(1)または(2)で表されるアリールアミン化合物に関して説明したものと同じである。 The charging ratio of the dinitro compound [I "-1] to the aryl halide compound [II] can be 1 equivalent or more of the aryl halide compound with respect to the amount of substance of the total NH groups of the dinitro compound. About 1 to 1.2 equivalents are preferable.
In addition, the reaction conditions and suitable conditions regarding the catalyst, ligand, base, solvent, reaction temperature and time, etc. are the same as those described for the arylamine compound represented by the formula (1) or (2). Is.
その他、触媒、配位子、塩基、溶媒、反応の温度および時間等に関する反応の諸条件および好適な条件は、式(1)または(2)で表されるアリールアミン化合物に関して説明したものと同じである。 The charging ratio of the amine compound [I "-3] and the aryl halide compound [II] can be 2 equivalents or more of the aryl halide compound with respect to the amine compound, but is about 2 to 2.4 equivalents. Is preferable.
In addition, the reaction conditions and suitable conditions regarding the catalyst, ligand, base, solvent, reaction temperature and time, etc. are the same as those described for the arylamine compound represented by the formula (1) or (2). Is.
ここで、ZおよびZ’は、いずれも同じものであってもよいが、効率的に所望のハロゲン化アリール化合物[II]を得る観点から、Z’の原子(基)の反応性は、Zの原子(基)の反応性よりも高いほうが好ましい。このような反応性の差を設けることで、アリールカルバゾール化合物[III]におけるZBの基は、Zの原子(基)よりも、Z’の原子(基)と優先的に反応し、効率的に所望のハロゲン化アリール化合物[II]を得ることができる。 Z'represents a halogen atom or a pseudohalogen group, and examples of the halogen atom and the pseudohalogen group include the same as above.
Here, Z and Z'may be the same, but from the viewpoint of efficiently obtaining the desired aryl halide compound [II], the reactivity of the atom (group) of Z'is Z. It is preferable that the reactivity of the atom (group) is higher than that of the atom (group). By providing such a difference in reactivity, the Z B group in the arylcarbazole compound [III] reacts preferentially with the Z'atom (group) over the Z atom (group), and is efficient. The desired aryl halide compound [II] can be obtained.
反応終了後は、常法にしたがって後処理をし、目的とするハロゲン化アリールアミン化合物を得ることができる。 The reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, but is particularly preferably about 0 to 200 ° C., more preferably 20 to 150 ° C. The reaction time is appropriately determined in consideration of the reaction temperature, the reactivity of the raw material compound, and the like, but is usually about 30 minutes to 50 hours.
After completion of the reaction, post-treatment can be carried out according to a conventional method to obtain the desired arylamine halide compound.
上記反応で用い得る溶媒は、この種の反応に用いられる溶媒であれば特に限定されるものではない。
反応温度は、通常0~140℃の範囲から適宜決定され、その時間は、通常、0.1~100時間の範囲から適宜決定される。 As the halogenating agent, known ones can be used, and specific examples thereof include, but are not limited to, N-bromosuccinimide and the like. The amount of the halogenating agent is about 1 to 1.5 in terms of molar ratio with respect to the compound represented by the formula [IV'].
The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used in this type of reaction.
The reaction temperature is usually appropriately determined from the range of 0 to 140 ° C., and the time is usually appropriately determined from the range of 0.1 to 100 hours.
上記反応で用い得る溶媒は、この種の反応に用いられる溶媒であれば特に限定されるものではない。
上記反応の温度は、通常0~140℃の範囲から適宜決定され、その時間は、通常、0.1~100時間の範囲から適宜決定される。 The preparation of the compound represented by the formula [III'] and the compound represented by the formula [V] is represented by the formula [V] with respect to the compound 1 represented by the formula [III'] in terms of molar ratio. Compounds 1 to 3.
The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used in this type of reaction.
The temperature of the reaction is usually appropriately determined from the range of 0 to 140 ° C., and the time thereof is usually appropriately determined from the range of 0.1 to 100 hours.
上記反応で用い得る溶媒は、この種の反応に用いられる溶媒であれば特に限定されるものではない。
上記温度は、通常0~140℃の範囲から適宜決定され、その時間は、通常、0.1~100時間の範囲から適宜決定される。 As the halogenating agent used in the above reaction, a known halogenating agent can be used, and the amount of the halogenating agent is represented by the formula [III'-1-1] or [III'-2] in terms of molar ratio. It is about 1 to 1.5 with respect to the compound 1 to be produced.
The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used in this type of reaction.
The temperature is usually appropriately determined from the range of 0 to 140 ° C., and the time is usually appropriately determined from the range of 0.1 to 100 hours.
上記反応で用い得る塩基は、この種の反応に用いられる塩基であれば特に限定されるものではなく、その具体例としては、t-BuOK、t-BuONa、CsCO3、K2CO3、Na2CO3、n-BuLi、t-BuLi、s-BuLi、NaOH、KOH、LiOH等が挙げられるが、t-BuOK、t-BuONa、n-BuLi、t-BuLi、s-BuLi、NaOH、KOHが好ましい。
上記反応で用い得る溶媒は、この種の反応に用いられる溶媒であれば特に限定されるものではない。
上記反応の温度は、通常0~140℃の範囲から適宜決定され、その時間は、通常、0.1~100時間の範囲から適宜決定される。 The preparation of the compound represented by the formula [VI'] and the compound represented by the formula [VII] is represented by the formula [VII] with respect to the compound 1 represented by the formula [VI'] in terms of molar ratio. Compounds 1 to 1.5.
The bases that can be used in the above reaction are not particularly limited as long as they are the bases used in this type of reaction, and specific examples thereof include t-BuOK, t-BuONa, CsCO 3 , K 2 CO 3 , and Na. 2 CO 3 , n-BuLi, t-BuLi, s-BuLi, NaOH, KOH, LiOH, etc., but t-BuOK, t-BuONa, n-BuLi, t-BuLi, s-BuLi, NaOH, KOH Is preferable.
The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used in this type of reaction.
The temperature of the reaction is usually appropriately determined from the range of 0 to 140 ° C., and the time thereof is usually appropriately determined from the range of 0.1 to 100 hours.
また、Pd/Cを用いた水素添加反応は、公知の手法によって行うことができる。
なお、メタフェニレン基の代わりにパラフェニレン基またはオルトフェニレンを導入する場合は、3-ハロニトロベンゼンの代わりに4-ハロニトロベンゼンまたは2-ハロニトロベンゼンを用いればよい。 In addition, various conditions and suitable conditions of the coupling reaction regarding the catalyst, solvent, temperature and time of the reaction, etc. are the same as those described for the arylamine compound represented by the formula (1) or (2).
Further, the hydrogenation reaction using Pd / C can be carried out by a known method.
When a paraphenylene group or orthophenylene is introduced instead of the metaphenylene group, 4-halonitrobenzene or 2-halonitrobenzene may be used instead of 3-halonitrobenzene.
なお、表中、Hは水素原子を、Phはフェニル基を、Meはメチル基を、n-Hexはn-ヘキシル基を、p-Tolyはp-トリル基を、2-Thieは2-チエニル基を、1,3-Phは1,3-フェニレン基を、1,4-Phは1,4-フェニレン基をそれぞれ表し、例えば番号1および865のアリールアミン化合物は、それぞれ下記の化合物である。 Hereinafter, specific examples of the arylamine compound of the present invention will be given, but the present invention is not limited thereto.
In the table, H is a hydrogen atom, Ph is a phenyl group, Me is a methyl group, n-Hex is an n-hexyl group, p-Toly is a p-tolyl group, and 2-Thie is 2-thienyl. The groups, 1,3-Ph represents a 1,3-phenylene group, and 1,4-Ph represents a 1,4-phenylene group. For example, the arylamine compounds of Nos. 1 and 865 are the following compounds, respectively. ..
なお、本発明において、電荷輸送性とは導電性と同義である。電荷輸送性ワニスとは、それ自体に電荷輸送性があるものでもよく、それにより得られる固形膜が電荷輸送性を有するものでもよい。 The above-mentioned arylamine compound of the present invention can be suitably used as a charge transporting substance. In this case, it can be used as a charge-transporting varnish containing the arylamine compound of the present invention and an organic solvent, and the charge-transporting varnish can be used to improve its charge-transporting ability depending on the use of the obtained thin film. It may contain a dopant substance for the purpose of. Further, the arylamine compound of the present invention can be used in combination with other conventionally known charge-transporting substances such as an aniline derivative and a thiophene derivative, but the arylamine compound of the present invention alone can be used as a charge-transporting substance. preferable.
In the present invention, charge transportability is synonymous with conductivity. The charge-transporting varnish may be one that has charge-transporting property by itself, and the solid film obtained thereby may have charge-transporting property.
また、無機系および有機系のドーパント物質は、1種類単独で用いてもよく、2種類以上組み合わせて用いてもよい。
さらにドーパント物質は、ワニスから固体膜である電荷輸送性薄膜を得る過程で、例えば焼成時の加熱といった外部からの刺激によって、例えば分子内の一部が外れることによってドーパント物質としての機能が初めて発現または向上するようになる物質、例えばスルホン酸基が脱離しやすい基で保護されたアリールスルホン酸エステル化合物であってもよい。 The dopant substance is not particularly limited as long as it is soluble in at least one solvent used for the varnish, and either an inorganic dopant substance or an organic dopant substance can be used.
Further, the inorganic and organic dopant substances may be used alone or in combination of two or more.
Furthermore, the dopant substance first exhibits its function as a dopant substance in the process of obtaining a charge-transporting thin film which is a solid film from the varnish, for example, when a part of the molecule is removed by an external stimulus such as heating during firing. Alternatively, it may be a substance that improves, for example, an aryl sulfonic acid ester compound protected by a group in which a sulfonic acid group is easily eliminated.
ヘテロポリ酸とは、代表的に式(H1)で表されるKeggin型あるいは式(H2)で表されるDawson型の化学構造で示される、ヘテロ原子が分子の中心に位置する構造を有し、バナジウム(V)、モリブデン(Mo)、タングステン(W)等の酸素酸であるイソポリ酸と、異種元素の酸素酸とが縮合してなるポリ酸である。このような異種元素の酸素酸としては、主にケイ素(Si)、リン(P)、ヒ素(As)の酸素酸が挙げられる。 In particular, in the present invention, a heteropolyacid is preferable as the inorganic dopant substance.
The heteropolyacid has a structure in which a hetero atom is located at the center of a molecule, which is typically represented by a Keggin type represented by the formula (H1) or a Dawson type chemical structure represented by the formula (H2). It is a polyacid formed by condensing isopolyacid, which is an oxygen acid such as vanadium (V), molybdenum (Mo), and tungsten (W), and oxygen acid of a different element. Oxygen acids of such dissimilar elements mainly include oxygen acids of silicon (Si), phosphorus (P), and arsenic (As).
特に、1種類のヘテロポリ酸を用いる場合、その1種類のヘテロポリ酸は、リンタングステン酸またはリンモリブデン酸が好ましく、リンタングステン酸が最適である。また、2種類以上のヘテロポリ酸を用いる場合、その2種類以上のヘテロポリ酸の1つは、リンタングステン酸またはリンモリブデン酸が好ましく、リンタングステン酸がより好ましい。
なお、ヘテロポリ酸は、元素分析等の定量分析において、一般式で示される構造から元素の数が多いもの、または少ないものであっても、それが市販品として入手したもの、あるいは、公知の合成方法にしたがって適切に合成したものである限り、本発明において用いることができる。
すなわち、例えば、一般的には、リンタングステン酸は化学式H3(PW12O40)・nH2Oで、リンモリブデン酸は化学式H3(PMo12O40)・nH2Oでそれぞれ示されるが、定量分析において、この式中のP(リン)、O(酸素)またはW(タングステン)もしくはMo(モリブデン)の数が多いもの、または少ないものであっても、それが市販品として入手したもの、あるいは、公知の合成方法にしたがって適切に合成したものである限り、本発明において用いることができる。この場合、本発明に規定されるヘテロポリ酸の質量とは、合成物や市販品中における純粋なリンタングステン酸の質量(リンタングステン酸含量)ではなく、市販品として入手可能な形態および公知の合成法にて単離可能な形態において、水和水やその他の不純物等を含んだ状態での全質量を意味する。 Specific examples of the heteropolyacid include phosphomolybdic acid, silicate molybdic acid, phosphotungstic acid, silicate tungstic acid, phosphotungstic acid, and the like, and these may be used alone or in combination of two or more. Good. These heteropolyacids are available as commercially available products, and can also be synthesized by a known method.
In particular, when one kind of heteropolyacid is used, the one kind of heteropolyacid is preferably phosphotungstic acid or phosphomolybdic acid, and phosphotungstic acid is most suitable. When two or more kinds of heteropolyacids are used, one of the two or more kinds of heteropolyacids is preferably phosphotungstic acid or phosphomolybdic acid, and more preferably phosphotungstic acid.
In addition, in quantitative analysis such as elemental analysis, heteropolyacids have a large number of elements or a small number of elements from the structure represented by the general formula, but the heteropolyacid is obtained as a commercially available product or a known synthesis. As long as it is properly synthesized according to the method, it can be used in the present invention.
That is, for example, in general, phosphotungsten acid is represented by chemical formulas H 3 (PW 12 O 40 ) and nH 2 O, and phosphomolydic acid is represented by chemical formulas H 3 (PMo 12 O 40 ) and nH 2 O, respectively. , In quantitative analysis, even if the number of P (phosphorus), O (oxygen) or W (tungsten) or Mo (molybdenum) in this formula is large or small, it is obtained as a commercial product. Alternatively, it can be used in the present invention as long as it is appropriately synthesized according to a known synthesis method. In this case, the mass of the heteropolyacid defined in the present invention is not the mass of pure phosphotungstic acid (phosphotungstic acid content) in the synthetic product or the commercially available product, but the form available as the commercially available product and the known synthesis. In a form that can be isolated by the method, it means the total mass in a state containing hydrated water and other impurities.
テトラシアノキノジメタン誘導体の具体例としては、7,7,8,8-テトラシアノキノジメタン(TCNQ)や、式(H3)で表されるハロテトラシアノキノジメタンなどが挙げられる。
また、ベンゾキノン誘導体の具体例としては、テトラフルオロ-1,4-ベンゾキノン(F4BQ)、テトラクロロ-1,4-ベンゾキノン(クロラニル)、テトラブロモ-1,4-ベンゾキノン、2,3-ジクロロ-5,6-ジシアノ-1,4-ベンゾキノン(DDQ)などが挙げられる。 On the other hand, as the organic dopant substance, a tetracyanoquinodimethane derivative or a benzoquinone derivative can be particularly used.
Specific examples of the tetracyanoquinodimethane derivative include 7,7,8,8-tetracyanoquinodimethane (TCNQ) and halotetracyanoquinodimethane represented by the formula (H3).
Specific examples of benzoquinone derivatives include tetrafluoro-1,4-benzoquinone (F4BQ), tetrachloro-1,4-benzoquinone (chloranil), tetrabromo-1,4-benzoquinone, 2,3-dichloro-5, and so on. 6-Dicyano-1,4-benzoquinone (DDQ) and the like can be mentioned.
ハロゲン原子としては上記と同じものが挙げられるが、フッ素原子または塩素原子が好ましく、フッ素原子がより好ましい。 In the formula, R 500 to R 503 each independently represent a hydrogen atom or a halogen atom, but at least one is a halogen atom, at least two are preferably halogen atoms, and at least three are halogen atoms. It is more preferable that all of them are halogen atoms.
Examples of the halogen atom include the same as above, but a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.
なお、上記オニウムボレート塩は、例えば、特開2005-314682号公報等に記載された公知の方法を参考に合成することができる。 The amount of the onium borate salt used can be about 0.1 to 10 with respect to the charge-transporting substance in terms of the amount of substance (molar).
The onium borate salt can be synthesized by referring to, for example, a known method described in JP-A-2005-314682.
A2は、ナフタレン環またはアントラセン環を表すが、ナフタレン環が好ましい。
A3は、2~4価のパーフルオロビフェニル基を表し、pは、A1とA3との結合数を示し、2≦p≦4を満たす整数であるが、A3がパーフルオロビフェニルジイル基、好ましくはパーフルオロビフェニル-4,4’-ジイル基であり、かつ、pが2であることが好ましい。
qは、A2に結合するスルホン酸基数を表し、1≦q≦4を満たす整数であるが、2が最適である。 A 1 represents O or S, with O being preferred.
A 2 represents a naphthalene ring or an anthracene ring, but a naphthalene ring is preferable.
A 3 represents a 2- to tetravalent perfluorobiphenyl group, p represents the number of bonds between A 1 and A 3, and is an integer satisfying 2 ≦ p ≦ 4, where A 3 is perfluorobiphenyldiyl. The group, preferably a perfluorobiphenyl-4,4'-diyl group, preferably has a p of 2.
q represents the number of sulfonic acid groups bonded to A 2 , and is an integer satisfying 1 ≦ q ≦ 4, but 2 is optimal.
その他、ハロゲン原子、炭素数1~20のアルキル基の例としては上記と同様のものが挙げられるが、ハロゲン原子としては、フッ素原子が好ましい。 Examples of the halogenated alkenyl group having 2 to 20 carbon atoms include perfluorovinyl, perfluoropropenyl (perfluoroallyl), perfluorobutenyl group and the like.
Other examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms include the same as above, but the halogen atom is preferably a fluorine atom.
なお、パーフルオロアルキル基とは、アルキル基の水素原子全てがフッ素原子に置換された基であり、パーフルオロアルケニル基とは、アルケニル基の水素原子全てがフッ素原子に置換された基である。 Among these, A 4 to A 8 are hydrogen atoms, halogen atoms, cyano groups, alkyl groups having 1 to 10 carbon atoms, alkyl halide groups having 1 to 10 carbon atoms, or alkenyl halides having 2 to 10 carbon atoms. a group, and at least 3 of the a 4 ~ a 8 is preferably a fluorine atom, a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, having 1 to 5 carbon atoms More preferably, it is an alkyl fluoride group or a fluorinated alkenyl group having 2 to 5 carbon atoms, and at least 3 of A 4 to A 8 are fluorine atoms, and hydrogen atom, fluorine atom, cyano group, and the like. It is even more preferable that it is a perfluoroalkyl group having 1 to 5 carbon atoms or a perfluoroalkenyl group having 1 to 5 carbon atoms, and that A 4 , A 5 and A 8 are fluorine atoms.
The perfluoroalkyl group is a group in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and the perfluoroalkyl group is a group in which all the hydrogen atoms of the alkenyl group are substituted with fluorine atoms.
アリールスルホン酸化合物は市販品を用いてもよいが、国際公開第2006/025342号、国際公開第2009/096352号、国際公開第2015/111654号、国際公開第2015/053320号、国際公開第2015/115515号等に記載の公知の方法で合成することもできる。 The amount of the aryl sulfonic acid compound used is preferably about 0.01 to 20.0, more preferably about 0.4 to 5.0, with respect to the charge transporting substance 1 in terms of the amount of substance (molar) ratio. ..
Commercially available products may be used as the aryl sulfonic acid compound, but International Publication No. 2006/025342, International Publication No. 2009/096322, International Publication No. 2015/111654, International Publication No. 2015/0533320, International Publication No. 2015 It can also be synthesized by a known method described in / 115515 and the like.
A12は、-O-または-S-であるが、-O-が好ましい。
A13は、ナフタレンまたはアントラセンから誘導される(n+1)価の基であるが、ナフタレンから誘導される基が好ましい。
Rs1~Rs4は、それぞれ独立して、水素原子、または直鎖状もしくは分岐鎖状の炭素数1~6のアルキル基であり、Rs5は、置換されていてもよい炭素数2~20の1価炭化水素基である。 In formula (H6), A 11 is an m-valent group derived from perfluorobiphenyl.
A 12 is —O— or —S—, but —O— is preferred.
A 13 is a (n + 1) -valent group derived from naphthalene or anthracene, but a group derived from naphthalene is preferable.
R s1 to R s4 are each independently a hydrogen atom or a linear or branched chain alkyl group having 1 to 6 carbon atoms, and R s5 is an optionally substituted alkyl group having 2 to 20 carbon atoms. It is a monovalent hydrocarbon group of.
炭素数2~20の1価炭化水素基は、直鎖状、分岐鎖状、環状のいずれでもよく、その具体例としては、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、t-ブチル基等のアルキル基;フェニル、ナフチル、フェナントリル基等のアリール基などが挙げられる。 Specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl group and the like. , An alkyl group having 1 to 3 carbon atoms is preferable.
The monovalent hydrocarbon group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl. Alkyl groups such as groups; aryl groups such as phenyl, naphthyl and phenanthryl groups can be mentioned.
また、Rs5としては、炭素数2~4の直鎖アルキル基またはフェニル基が好ましい。 In particular, among R s1 to R s4 , R s1 or R s3 is a linear alkyl group having 1 to 3 carbon atoms, and the rest is a hydrogen atom, or R s1 is a linear alkyl group having 1 to 3 carbon atoms. It is preferable that R s2 to R s4 are hydrogen atoms. In this case, the methyl group is preferable as the linear alkyl group having 1 to 3 carbon atoms.
Further, as R s5 , a linear alkyl group or a phenyl group having 2 to 4 carbon atoms is preferable.
このような炭化水素化合物としては、ベンゼン、トルエン、キシレン、エチルベンゼン、ビフェニル、ナフタレン、アントラセン、フェナントレン等が挙げられる。
なお、上記炭化水素基は、その水素原子の一部または全部が、更に置換基で置換されていてもよく、このような置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ニトロ、シアノ、ヒドロキシ、アミノ、シラノール、チオール、カルボキシ、スルホン酸エステル、リン酸、リン酸エステル、エステル、チオエステル、アミド、オルガノオキシ、オルガノアミノ、オルガノシリル、オルガノチオ、アシル、スルホ、1価炭化水素基等が挙げられる。
これらの中でも、A14としては、ベンゼン、ビフェニル等から誘導される基が好ましい。 In the formula (H7), A 14 is an m-valent hydrocarbon group having 6 to 20 carbon atoms containing one or more aromatic rings which may be substituted, and the hydrocarbon group may be one or more. It is a group obtained by removing m hydrogen atoms from a hydrocarbon compound having 6 to 20 carbon atoms containing an aromatic ring.
Examples of such a hydrocarbon compound include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, phenanthrene and the like.
In the above-mentioned hydrocarbon group, a part or all of the hydrogen atom may be further substituted with a substituent, and examples of such a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a nitro. , Cyano, hydroxy, amino, silanol, thiol, carboxy, sulfonic acid ester, phosphoric acid, phosphoric acid ester, ester, thioester, amide, organooxy, organoamino, organosilyl, organothio, acyl, sulfo, monovalent hydrocarbon group And so on.
Among these, as A 14 , a group derived from benzene, biphenyl or the like is preferable.
A16は、炭素数6~20の(n+1)価の芳香族炭化水素基であり、この芳香族炭化水素基は、炭素数6~20の芳香族炭化水素化合物の芳香環上から(n+1)個の水素原子を取り除いて得られる基である。
このような芳香族炭化水素化合物としては、ベンゼン、トルエン、キシレン、ビフェニル、ナフタレン、アントラセン、ピレン等が挙げられる。
中でも、A16としては、ナフタレンまたはアントラセンから誘導される基が好ましく、ナフタレンから誘導される基がより好ましい。 Further, A 15 is —O— or —S—, but —O— is preferable.
A 16 is a (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the aromatic hydrocarbon group is (n + 1) from the aromatic ring of the aromatic hydrocarbon compound having 6 to 20 carbon atoms. It is a group obtained by removing individual hydrogen atoms.
Examples of such aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene and the like.
Among them, as A 16 , a group derived from naphthalene or anthracene is preferable, and a group derived from naphthalene is more preferable.
上記直鎖状または分岐鎖状の1価脂肪族炭化水素基の具体例としては、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、t-ブチル、n-ヘキシル、n-オクチル、2-エチルヘキシル、デシル基等の炭素数1~20のアルキル基;ビニル、1-プロペニル、2-プロペニル、イソプロペニル、1-メチル-2-プロペニル、1-ブテニル、2-ブテニル、3-ブテニル、ヘキセニル基等の炭素数2~20のアルケニル基などが挙げられる。
これらの中でも、Rs6は水素原子が好ましく、Rs7およびRs8は、それぞれ独立して、炭素数1~6のアルキル基が好ましい。 R s6 and R s7 are independently hydrogen atoms or linear or branched chain monovalent aliphatic hydrocarbon groups, and R s8 is a linear or branched chain monovalent aliphatic hydrocarbon. It is a hydrocarbon group. However, the total number of carbon atoms of R s6 , R s7 and R s8 is 6 or more. The upper limit of the total number of carbon atoms of R s6 , R s7 and R s8 is not particularly limited, but is preferably 20 or less, and more preferably 10 or less.
Specific examples of the linear or branched monovalent aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, n-octyl, and the like. Alkyl groups having 1 to 20 carbon atoms such as 2-ethylhexyl and decyl groups; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as a hexenyl group.
Among these, R s6 is preferably a hydrogen atom, and R s7 and R s8 are each independently preferably an alkyl group having 1 to 6 carbon atoms.
炭素数1~10のアルキル基は、直鎖状、分岐鎖状、環状のいずれでもよく、その具体例としては、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、s-ブチル、t-ブチル、n-ペンチル、シクロペンチル、n-ヘキシル、シクロヘキシル、n-ヘプチル、n-オクチル、n-ノニル、n-デシル基等が挙げられる。 In the formula (H8), R s9 to R s13 independently represent a hydrogen atom, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkyl halide group having 1 to 10 carbon atoms. Alternatively, it is an alkenyl halide group having 2 to 10 carbon atoms.
The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and s-butyl. Examples thereof include t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl group and the like.
Rs10~Rs13としては、ハロゲン原子が好ましく、フッ素原子がより好ましい。 Among these, as R s9 , a nitro group, a cyano group, an alkyl halide group having 1 to 10 carbon atoms, and an alkenyl halide group having 2 to 10 carbon atoms are preferable, and a nitro group, a cyano group, and 1 to 4 carbon atoms are preferable. The alkyl halide group and the alkenyl halide group having 2 to 4 carbon atoms are more preferable, and the nitro group, the cyano group, the trifluoromethyl group and the perfluoropropenyl group are even more preferable.
As R s10 to R s13 , a halogen atom is preferable, and a fluorine atom is more preferable.
A18は、炭素数6~20の(n+1)価の芳香族炭化水素基であり、この芳香族炭化水素基は、炭素数6~20の芳香族炭化水素化合物の芳香環上から(n+1)個の水素原子を取り除いて得られる基である。
このような芳香族炭化水素化合物としては、ベンゼン、トルエン、キシレン、ビフェニル、ナフタレン、アントラセン、ピレン等が挙げられる。
これらの中でも、A18としては、ナフタレンまたはアントラセンから誘導される基が好ましく、ナフタレンから誘導される基がより好ましい。 A 17 is -O-, -S- or -NH-, but -O- is preferable.
A 18 is a (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the aromatic hydrocarbon group is (n + 1) from the aromatic ring of the aromatic hydrocarbon compound having 6 to 20 carbon atoms. It is a group obtained by removing individual hydrogen atoms.
Examples of such aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene and the like.
Among these, as A 18 , a group derived from naphthalene or anthracene is preferable, and a group derived from naphthalene is more preferable.
1価脂肪族炭化水素基の具体例としては、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、s-ブチル、t-ブチル、n-ペンチル、シクロペンチル、n-ヘキシル、シクロヘキシル、n-ヘプチル、n-オクチル、n-ノニル、n-デシル、n-ウンデシル、n-ドデシル基等の炭素数1~20のアルキル基;ビニル、1-プロペニル、2-プロペニル、イソプロペニル、1-メチル-2-プロペニル、1-ブテニル、2-ブテニル、3-ブテニル、ヘキセニル基等の炭素数2~20のアルケニル基などが挙げられるが、炭素数1~20のアルキル基が好ましく、炭素数1~10のアルキル基がより好ましく、炭素数1~8のアルキル基がより一層好ましい。 R s14 to R s17 are independently hydrogen atoms or linear or branched chain monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms.
Specific examples of the monovalent aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl and n. -Alkyl groups having 1 to 20 carbon atoms such as heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl groups; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl Examples thereof include alkenyl groups having 2 to 20 carbon atoms such as -2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl and hexenyl groups, but alkyl groups having 1 to 20 carbon atoms are preferable, and alkyl groups having 1 to 20 carbon atoms are preferable. An alkyl group of 10 is more preferable, and an alkyl group having 1 to 8 carbon atoms is even more preferable.
Rs18の直鎖状または分岐状の炭素数1~20の1価脂肪族炭化水素基としては、上記と同様のものが挙げられる。
Rs18が1価脂肪族炭化水素基である場合、Rs18は、炭素数1~20のアルキル基が好ましく、炭素数1~10のアルキル基がより好ましく、炭素数1~8のアルキル基がより一層好ましい。
Rs19の炭素数2~20の1価炭化水素基としては、前述した1価脂肪族炭化水素基のうちメチル基以外のもののほか、フェニル、ナフチル、フェナントリル基等のアリール基などが挙げられる。
これらの中でも、Rs19は、炭素数2~4の直鎖アルキル基またはフェニル基が好ましい。
なお、上記1価炭化水素基が有していてもよい置換基としては、フッ素原子、炭素数1~4のアルコキシ基、ニトロ基、シアノ基等が挙げられる。 R s18 is a linear or branched chain monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or OR s19 . R s19 is a monovalent hydrocarbon group having 2 to 20 carbon atoms which may be substituted.
Examples of the linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms of R s18 include the same groups as described above.
When R s18 is a monovalent aliphatic hydrocarbon group, R s18 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. Even more preferable.
Examples of the monovalent hydrocarbon group having 2 to 20 carbon atoms of R s19 include those other than the methyl group among the above-mentioned monovalent aliphatic hydrocarbon groups, and aryl groups such as phenyl, naphthyl, and phenanthryl groups.
Among these, R s19 is preferably a linear alkyl group or a phenyl group having 2 to 4 carbon atoms.
Examples of the substituent that the monovalent hydrocarbon group may have include a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group, and a cyano group.
アリールスルホン酸エステル化合物は市販品を用いてもよいが、国際公開第2017/217455号、国際公開第2017/217457号、国際公開第2019/124412号等に記載の公知の方法で合成することもできる。 The amount of the aryl sulfonic acid ester compound used is preferably about 0.01 to 20, more preferably about 0.05 to 10 with respect to the charge transporting substance 1 in terms of the amount of substance (molar) ratio.
A commercially available product may be used as the aryl sulfonic acid ester compound, but it may also be synthesized by a known method described in International Publication No. 2017/217455, International Publication No. 2017/217457, International Publication No. 2019/124412 and the like. it can.
クロロホルム、クロロベンゼン等の塩素系溶媒;
トルエン、キシレン、テトラリン、シクロヘキシルベンゼン、デシルベンゼン等の芳香族炭化水素系溶媒;
1-オクタノール、1-ノナノール、1-デカノール等の脂肪族アルコール系溶媒;
テトラヒドロフラン、ジオキサン、アニソール、4-メトキシトルエン、3-フェノキシトルエン、ジベンジルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールブチルメチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールブチルメチルエーテル等のエーテル系溶媒;
安息香酸メチル、安息香酸エチル、安息香酸ブチル、安息香酸イソアミル、フタル酸ビス(2-エチルヘキシル)、マレイン酸ジブチル、シュウ酸ジブチル、酢酸ヘキシル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート等のエステル系溶媒
等が挙げられる。 Examples of low polar solvents include, for example.
Chlorine-based solvents such as chloroform and chlorobenzene;
Aromatic hydrocarbon solvents such as toluene, xylene, tetralin, cyclohexylbenzene, decylbenzene;
Aliphatic alcohol solvents such as 1-octanol, 1-nonanol, 1-decanol;
Ether-based solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether;
Esters such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis (2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. Examples include a solvent.
N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N,N-ジメチルイソブチルアミド、N-メチルピロリドン、1,3-ジメチル-2-イミダゾリジノン等のアミド系溶媒;
エチルメチルケトン、イソホロン、シクロヘキサノン等のケトン系溶媒;
アセトニトリル、3-メトキシプロピオニトリル等のシアノ系溶媒;
エチレングリコール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、1,3-ブタンジオール、2,3-ブタンジオール等の多価アルコール系溶媒;
ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノフェニルエーテル、トリエチレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ベンジルアルコール、2-フェノキシエタノール、2-ベンジルオキシエタノール、3-フェノキシベンジルアルコール、テトラヒドロフルフリルアルコール等の脂肪族アルコール以外の1価アルコール系溶媒;
ジメチルスルホキシド等のスルホキシド系溶媒
等が挙げられる。 Further, as a highly polar solvent, for example,
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutyramide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone;
Ketone solvents such as ethyl methyl ketone, isophorone, cyclohexanone;
Cyan-based solvents such as acetonitrile and 3-methoxypropionitrile;
Polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol;
Other than aliphatic alcohols such as diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol. Monohydric alcohol solvent;
Examples thereof include sulfoxide-based solvents such as dimethyl sulfoxide.
また、電荷輸送性ワニスの固形分濃度は、ワニスの粘度および表面張力等や、作製する薄膜の厚み等を勘案して適宜設定されるものではあるが、通常、0.1~20.0質量%程度であり、ワニスの塗布性を向上させることを考慮すると、好ましくは0.5~10.0質量%程度、より好ましくは1.0~5.0質量%程度である。 The viscosity of the charge-transporting varnish is appropriately determined depending on the thickness of the thin film to be produced and the solid content concentration, but is usually 1 to 50 mPa · s at 25 ° C. In the present invention, the solid content means a component other than the solvent contained in the charge transporting varnish of the present invention.
The solid content concentration of the charge-transporting varnish is appropriately set in consideration of the viscosity and surface tension of the varnish, the thickness of the thin film to be produced, and the like, but is usually 0.1 to 20.0 mass. It is about%, preferably about 0.5 to 10.0% by mass, and more preferably about 1.0 to 5.0% by mass in consideration of improving the coatability of the varnish.
この場合、電荷輸送性薄膜は、上述した電荷輸送性ワニスを基材上に塗布して焼成して形成することができる。
ワニスの塗布方法としては、特に限定されるものではなく、ディップ法、スピンコート法、転写印刷法、ロールコート法、刷毛塗り、インクジェット法、スプレー法、スリットコート法等が挙げられ、塗布方法に応じてワニスの粘度および表面張力を調節することが好ましい。 Since the charge transporting varnish described above can easily produce a charge transporting thin film by using the varnish, it can be suitably used when manufacturing an electronic device, particularly an organic EL device.
In this case, the charge-transporting thin film can be formed by applying the above-mentioned charge-transporting varnish on a substrate and firing it.
The varnish coating method is not particularly limited, and examples thereof include a dip method, a spin coating method, a transfer printing method, a roll coating method, a brush coating, an inkjet method, a spray method, and a slit coating method. It is preferable to adjust the viscosity and surface tension of the varnish accordingly.
なお、焼成の際、より高い均一成膜性を発現させたり、基材上で反応を進行させたりする目的で、2段階以上の温度変化をつけてもよく、加熱は、例えば、ホットプレートやオーブン等、適当な機器を用いて行えばよい。 The firing temperature is appropriately set within the range of about 100 to 260 ° C. in consideration of the intended use of the obtained thin film, the degree of charge transportability applied to the obtained thin film, the type of solvent, the boiling point, etc., and the obtained thin film is obtained. When used as a hole injection layer for an organic EL element, it is preferably about 140 to 250 ° C., more preferably about 145 to 240 ° C., but when the arylamine compound of the present invention is used as a charge transporting substance, it is as low as 200 ° C. or less. Even by firing, a thin film having good charge transportability can be formed.
At the time of firing, a temperature change of two or more steps may be applied for the purpose of exhibiting higher uniform film forming property or allowing the reaction to proceed on the substrate, and heating may be performed by, for example, a hot plate or the like. It may be carried out using an appropriate device such as an oven.
有機EL素子の代表的な構成としては、以下(a)~(f)が挙げられるが、これらに限定されるわけではない。なお、下記構成において、必要に応じて、発光層と陽極の間に電子ブロック層等を、発光層と陰極の間にホール(正孔)ブロック層等を設けることもできる。また、正孔注入層、正孔輸送層あるいは正孔注入輸送層が電子ブロック層等としての機能を兼ね備えていてもよく、電子注入層、電子輸送層あるいは電子注入輸送層がホール(正孔)ブロック層等としての機能を兼ね備えていてもよい。さらに、必要に応じて各層の間に任意の機能層を設けることも可能である。
(a)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
(b)陽極/正孔注入層/正孔輸送層/発光層/電子注入輸送層/陰極
(c)陽極/正孔注入輸送層/発光層/電子輸送層/電子注入層/陰極
(d)陽極/正孔注入輸送層/発光層/電子注入輸送層/陰極
(e)陽極/正孔注入層/正孔輸送層/発光層/陰極
(f)陽極/正孔注入輸送層/発光層/陰極 When the above-mentioned charge-transporting thin film is applied to an organic EL element, the above-mentioned charge-transporting thin film can be provided between a pair of electrodes constituting the organic EL element.
Typical configurations of the organic EL element include, but are not limited to, the following (a) to (f). In the following configuration, if necessary, an electron block layer or the like may be provided between the light emitting layer and the anode, and a hole (hole) block layer or the like may be provided between the light emitting layer and the cathode. Further, the hole injection layer, the hole transport layer or the hole injection transport layer may also have a function as an electron block layer or the like, and the electron injection layer, the electron transport layer or the electron injection transport layer is a hole (hole). It may also have a function as a block layer or the like. Further, if necessary, an arbitrary functional layer can be provided between the layers.
(A) Electron / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (b) anode / hole injection layer / hole transport layer / light emitting layer / electron injection transport layer / Cathode (c) anode / hole injection transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (d) anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode (e) anode / positive Hole injection layer / hole transport layer / light emitting layer / cathode (f) anode / hole injection transport layer / light emitting layer / cathode
「電子注入層」、「電子輸送層」および「電子注入輸送層」とは、発光層と陰極との間に形成される層であって、電子を陰極から発光層へ輸送する機能を有するものであり、発光層と陰極の間に、電子輸送性材料の層が1層のみ設けられる場合、それが「電子注入輸送層」であり、発光層と陰極の間に、電子輸送性材料の層が2層以上設けられる場合、陰極に近い層が「電子注入層」であり、それ以外の層が「電子輸送層」である。
「発光層」とは、発光機能を有する有機層であって、ドーピングシステムを採用する場合、ホスト材料とドーパント材料を含んでいる。このとき、ホスト材料は、主に電子と正孔の再結合を促し、励起子を発光層内に閉じ込める機能を有し、ドーパント材料は、再結合で得られた励起子を効率的に発光させる機能を有する。燐光素子の場合、ホスト材料は主にドーパントで生成された励起子を発光層内に閉じ込める機能を有する。 The "hole injection layer", "hole transport layer" and "hole injection transport layer" are layers formed between the light emitting layer and the anode, and transport holes from the anode to the light emitting layer. When it has a function and only one layer of hole transporting material is provided between the light emitting layer and the anode, it is a "hole injection transport layer", and between the light emitting layer and the anode, When two or more layers of the hole transporting material are provided, the layer close to the anode is the “hole injection layer” and the other layers are the “hole transport layer”. In particular, as the hole injection (transport) layer, a thin film having excellent not only hole acceptability from the anode but also hole injection property into the hole transport (emission) layer is used.
The "electron injection layer", "electron transport layer" and "electron transport layer" are layers formed between the light emitting layer and the cathode and have a function of transporting electrons from the cathode to the light emitting layer. When only one layer of electron transporting material is provided between the light emitting layer and the cathode, it is an "electron injection transporting layer", and a layer of electron transporting material is provided between the light emitting layer and the cathode. When two or more layers are provided, the layer close to the cathode is the "electron injection layer", and the other layers are the "electron transport layer".
The "light emitting layer" is an organic layer having a light emitting function, and includes a host material and a dopant material when a doping system is adopted. At this time, the host material mainly has a function of promoting the recombination of electrons and holes and confining excitons in the light emitting layer, and the dopant material efficiently emits excitons obtained by recombination. Has a function. In the case of a phosphorescent device, the host material mainly has a function of confining excitons generated by the dopant in the light emitting layer.
上記電荷輸送性ワニスから得られる薄膜からなる正孔注入層を有するOLED素子の作製方法の一例は、以下のとおりである。なお、電極は、電極に悪影響を与えない範囲で、アルコール、純水等による洗浄や、UVオゾン処理、酸素-プラズマ処理等による表面処理を予め行うことが好ましい。
陽極基板上に、上記の方法により、上記電荷輸送性ワニスを用いて正孔注入層を形成する。これを真空蒸着装置内に導入し、正孔輸送層、発光層、電子輸送層/ホールブロック層、電子注入層、陰極金属を順次蒸着する。あるいは、当該方法において蒸着で正孔輸送層と発光層を形成する代わりに、正孔輸送性高分子を含む正孔輸送層形成用組成物と発光性高分子を含む発光層形成用組成物を用いてウェットプロセスによってこれらの層を形成する。なお、必要に応じて、発光層と正孔輸送層との間に電子ブロック層を設けてよい。 Examples of materials and methods for producing an organic EL device using the charge-transporting varnish of the present invention include, but are not limited to, the following.
An example of a method for manufacturing an OLED device having a hole injection layer made of a thin film obtained from the charge transporting varnish is as follows. It is preferable that the electrode is preliminarily subjected to surface treatment such as cleaning with alcohol, pure water or the like, UV ozone treatment, oxygen-plasma treatment or the like within a range that does not adversely affect the electrode.
A hole injection layer is formed on the anode substrate by the above method using the above charge transporting varnish. This is introduced into a vacuum vapor deposition apparatus, and a hole transport layer, a light emitting layer, an electron transport layer / hole block layer, an electron injection layer, and a cathode metal are sequentially vapor-deposited. Alternatively, instead of forming the hole transport layer and the light emitting layer by vapor deposition in the method, a composition for forming a hole transport layer containing a hole transport polymer and a composition for forming a light emitting layer containing a light emitting polymer are used. These layers are formed by a wet process using. If necessary, an electron block layer may be provided between the light emitting layer and the hole transport layer.
なお、金属陽極を構成するその他の金属としては、金、銀、銅、インジウムやこれらの合金等が挙げられるが、これらに限定されるわけではない。 Examples of the anode material include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), metals typified by aluminum, and metal anodes composed of alloys thereof. Those that have been flattened are preferable. Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used.
Examples of other metals constituting the metal anode include, but are not limited to, gold, silver, copper, indium, and alloys thereof.
また、蒸着で発光層を形成する場合、発光性ドーパントと共蒸着してもよく、発光性ドーパントとしては、トリス(2-フェニルピリジン)イリジウム(III)(Ir(ppy)3)等の金属錯体や、ルブレン等のナフタセン誘導体、キナクリドン誘導体、ペリレン等の縮合多環芳香族環等が挙げられるが、これらに限定されない。 Examples of the material forming the light emitting layer include a metal complex such as an aluminum complex of 8-hydroxyquinoline, a metal complex of 10-hydroxybenzo [h] quinoline, a bisstyrylbenzene derivative, a bisstyrylarylene derivative, and (2-hydroxyphenyl) benzo. Low molecular weight luminescent materials such as thiazole metal complexes and silol derivatives; poly (p-phenylene vinylene), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene], poly (3-alkyl Examples thereof include, but are not limited to, a system in which a light emitting material and an electron transfer material are mixed with a polymer compound such as thiophene) and polyvinylcarbazole.
When the light emitting layer is formed by vapor deposition, it may be co-deposited with a light emitting dopant, and the light emitting dopant is a metal complex such as tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3 ). , A naphthacene derivative such as rubrene, a quinacridone derivative, a condensed polycyclic aromatic ring such as perylene, and the like, but are not limited thereto.
陰極材料としては、アルミニウム、マグネシウム-銀合金、アルミニウム-リチウム合金等が挙げられるが、これらに限定されない。
電子ブロック層を形成する材料としては、トリス(フェニルピラゾール)イリジウム等が挙げられるが、これに限定されない。 Materials for forming the electron injection layer include metal oxides such as lithium oxide (Li 2 O), magnesium oxide (Mg O), and alumina (Al 2 O 3 ), lithium fluoride (LiF), and sodium fluoride (NaF). Examples include, but are not limited to, metal fluorides such as.
Examples of the cathode material include, but are not limited to, aluminum, magnesium-silver alloy, aluminum-lithium alloy, and the like.
Examples of the material for forming the electron block layer include, but are not limited to, tris (phenylpyrazole) iridium and the like.
[装置]
(1)MALDI-TOF-MS:ブルカー社製、autoflex III smartbeam
(2)1H-NMR:日本電子(株)製 JNM-ECP300 FT NMR SYSTEM
(3)基板洗浄:長州産業(株)製 基板洗浄装置(減圧プラズマ方式)
(4)ワニスの塗布:ミカサ(株)製 スピンコーターMS-A100
(5)膜厚測定:(株)小坂研究所製 微細形状測定機サーフコーダET-4000
(6)素子の作製:長州産業(株)製 多機能蒸着装置システムC-E2L1G1-N
(7)素子の電流密度と輝度の測定:(株)イーエッチシー製 多チャンネルIVL測定装置
(8)EL素子の寿命測定(輝度半減期測定):(株)イーエッチシー製 有機EL輝度寿命評価システムPEL-105S
(9)屈折率(n)および消衰係数(k)の測定:ジェー・エー・ウーラムジャパン製 多入射角分光エリプソメーターVASE Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The equipment and reagents used are as follows.
[apparatus]
(1) MALDI-TOF-MS: manufactured by Bruker, autoflex III smart beam
(2) 1 1 H-NMR: JNM-ECP300 FT NMR SYSTEM manufactured by JEOL Ltd.
(3) Substrate cleaning: Substrate cleaning equipment manufactured by Choshu Sangyo Co., Ltd. (decompression plasma method)
(4) Application of varnish: Spin coater MS-A100 manufactured by Mikasa Co., Ltd.
(5) Film thickness measurement: Kosaka Laboratory Co., Ltd. Fine shape measuring machine Surfcoder ET-4000
(6) Manufacture of element: Multi-function vapor deposition equipment system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd.
(7) Measurement of element current density and brightness: Multi-channel IVL measuring device manufactured by EHC Co., Ltd. (8) Life measurement of EL element (brightness half-life measurement): Organic EL brightness life manufactured by EHC Co., Ltd. Evaluation system PEL-105S
(9) Measurement of refractive index (n) and extinction coefficient (k): Multi-incident angle spectroscopic ellipsometer VASE manufactured by JA Woolam Japan
RuPhos Aldrich社製
t-BuXPhos Aldrich社製
t-Bu3PHBF4 富士フイルムワコーケミカル(株)製
ヨウ化銅(I) 富士フイルムワコーケミカル(株)製
エチレンジアミン 富士フイルムワコーケミカル(株)製
Pd(DBA)2 東京化成工業(株)製
Pd(ОAc)2 東京化成工業(株)製
Pd[P(C6H5)3)]4 東京化成工業(株)製
Pd(dppf)Cl2 東京化成工業(株)製
3-ブロモ-9-フェニルカルバゾール 東京化成工業(株)製
3-ブロモカルバゾール 東京化成工業(株)製
4-ヨードトルエン 東京化成工業(株)製
4-ヨードアニソール 東京化成工業(株)製
18-クラウン-6 東京化成工業(株)製
ビス(ピナコラート)ジボロン 東京化成工業(株)製
3,3’,5,5’-テトラメチルベンジジン 東京化成工業(株)製
リチウムヘキサメチルジシラジド(LHMDS)1.3mol/Lテトラヒドロフラン溶液 東京化成工業(株)製
2-ブロモ-7-ヨードフルオレン 東京化成工業(株)製
ベンジルトリエチルアンモニウムクロライド 東京化成工業(株)製
3-ニトロアニリン 東京化成工業(株)製
1-ブロモ-3-ニトロベンゼン 東京化成工業(株)製
塩化水素(約1mоl/L酢酸エチル溶液) 東京化成工業(株)製
4,4’-ジアミノジフェニルアミン 東京化成工業(株)製
t-BuONa 東京化成工業(株)製
(9-フェニル-9H-カルバゾール-3-イル)ボロン酸 東京化成工業(株)製
1,4-ジオキサン 関東化学(株)製
2,2’-ビス(トリフルオロメチル)ベンジジン 関東化学(株)製
ビス(4-アミノフェニル)スルフォン 関東化学(株)製
1,4-ビス(4-アミノ-2-トリフルオロメチルフェノキシ)ベンゼン 関東化学(株)製
シリカゲルN60 関東化学(株)製
ジメチルスルホキシド 純正化学(株)製
ヨードメタン 純正化学(株)製
炭酸カリウム 純正化学(株)製
酢酸カリウム 東京化成工業(株)製
トルエン 純正化学(株)製
テトラヒドロフラン 純正化学(株)製
酢酸エチル 純正化学(株)製
メタノール 純正化学 社製
ヘキサン 純正化学(株)製
m-トリジン 和歌山精化工業(株)製
N,N’-ビス(4-アミノフェニル)テレフタルアミド 和歌山精化工業(株)製
Pd/C CGS-10DR [H2O]=54.40% N.E.ケムキャット社製
3-(7-ブロモ-9,9-ジメチル-9H-フルオレン-2-イル)-9-フェニル-9H-カルバゾール Beijing aglaia technology development co., ltd 製 [reagent]
RuPhos Aldrich t-BuXPhos Aldrich t-Bu 3 PHBF 4 Fujifilm Wako Chemical Co., Ltd. Copper Iodide (I) Fujifilm Wako Chemical Co., Ltd. Toluene Diamine Fujifilm Wako Chemical Co., Ltd. Pd (DBA) ) 2 Pd (ОAc) manufactured by Tokyo Kasei Kogyo Co., Ltd. 2 Pd [P (C 6 H 5 ) 3 )] manufactured by Tokyo Kasei Kogyo Co., Ltd. 4 Pd (dppf) Cl 2 manufactured by Tokyo Kasei Kogyo Co., Ltd. 3-Bromo-9-Phenylcarbazole manufactured by Tokyo Kasei Kogyo Co., Ltd. 3-Bromocarbazole manufactured by Tokyo Kasei Kogyo Co., Ltd. 4-Iodotoluene manufactured by Tokyo Kasei Kogyo Co., Ltd. 4-iodoanisol Tokyo Kasei Kogyo Co., Ltd. ) 18-Crown-6 Tokyo Kasei Kogyo Co., Ltd. Bis (Pinacolat) Diboron Tokyo Kasei Kogyo Co., Ltd. 3,3', 5,5'-Tetramethylbenzidine Tokyo Kasei Kogyo Co., Ltd. Lithium Hexamethyldi Shirajide (LHMDS) 1.3 mol / L tetrahydrofuran solution 2-Bromo-7-iodofluorene manufactured by Tokyo Kasei Kogyo Co., Ltd. benzyltriethylammonium chloride manufactured by Tokyo Kasei Kogyo Co., Ltd. 3-Nitroaniline manufactured by Tokyo Kasei Kogyo Co., Ltd. Tokyo 1-Bromo-3-nitrobenzene manufactured by Kasei Kogyo Co., Ltd. Hydrogen chloride (approx. 1 mL / L ethyl acetate solution) manufactured by Tokyo Kasei Kogyo Co., Ltd. 4,4'-diaminodiphenylamine manufactured by Tokyo Kasei Kogyo Co., Ltd. Tokyo Kasei Kogyo Co., Ltd. ) T-BuONa Tokyo Kasei Kogyo Co., Ltd. (9-Phenyl-9H-carbazole-3-yl) boronic acid Tokyo Kasei Kogyo Co., Ltd. 1,4-dioxane Kanto Chemical Co., Ltd. 2,2'- Bis (Trifluoromethyl) benzidine Kanto Chemical Co., Ltd. Bis (4-aminophenyl) Sulfone Kanto Chemical Co., Ltd. 1,4-Bis (4-amino-2-trifluoromethylphenoxy) benzene Kanto Chemical Co., Ltd. Silica Silica N60 dimethylsulfoxide manufactured by Kanto Chemical Co., Ltd. Iodomethane manufactured by Genuine Chemical Co., Ltd. Potassium carbonate manufactured by Genuine Chemical Co., Ltd. Potassium acetate manufactured by Genuine Chemical Co., Ltd. Toluene manufactured by Tokyo Kasei Kogyo Co., Ltd. Ethyl acetate manufactured by Chemical Co., Ltd. Methanol manufactured by Genuine Chemical Co., Ltd. Hexene manufactured by Genuine Chemical Co., Ltd. m-trizine manufactured by Genuine Chemical Co., Ltd. N, N'-bis (4-aminophenyl) terephthalamide manufactured by Wakayama Seika Kogyo Co., Ltd. Wakayama Seika Kogyo Co., Ltd. Pd / C CGS-10DR [H2O] = 54. 40% N. E. Chemcat 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole Beijing aglaia technology development co., Ltd
そこへ、別途調製した水酸化ナトリウム50質量%水溶液14gを加えてから10分間撹拌した後、ヨードメタン72.5mmol(10.3g)を滴下し、室温で終夜撹拌した。なお、途中、フラスコ内の溶液を微量採取し、液体クロマトグラフィーを用いて反応を追跡した。原料に帰属できるピークの面積の減少に伴い目的物に帰属できるピークの面積が増加した。その際、副生成物に対応するような目立ったピークは確認されなかった。
得られた反応混合物をメタノールと水の混合溶媒(3/1(v/v))800mLに加え、析出した固体をメンブランフィルターで濾別した。
最後に、回収した固体を60℃で減圧乾燥し、2-ブロモ-7-ヨード-9,9-ジメチル-9H-フルオレン6.26g(78.4%)を得た。得られた化合物の1H-NMRスペクトル(測定溶媒:重DMSO)を図1に示す。 Weigh 30 mmol (11.1 g) of 2-bromo-7-iodofluorene and 3 mmol (683.3 mg) of benzyltriethylammonium chloride into a 100 mL reaction flask, add 60 mL of dimethyl sulfoxide, and stir for 10 minutes while substituting with nitrogen. did.
After adding 14 g of a separately prepared 50 mass% sodium hydroxide aqueous solution and stirring for 10 minutes, 72.5 mmol (10.3 g) of iodomethane was added dropwise thereto, and the mixture was stirred overnight at room temperature. On the way, a small amount of the solution in the flask was sampled, and the reaction was followed by liquid chromatography. As the area of peaks that can be attributed to raw materials decreased, the area of peaks that could be attributed to the target product increased. At that time, no conspicuous peak corresponding to the by-product was confirmed.
The obtained reaction mixture was added to 800 mL of a mixed solvent of methanol and water (3/1 (v / v)), and the precipitated solid was filtered off by a membrane filter.
Finally, the recovered solid was dried under reduced pressure at 60 ° C. to obtain 6.26 g (78.4%) of 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene. The 1 H-NMR spectrum (measurement solvent: heavy DMSO) of the obtained compound is shown in FIG.
得られた反応混合物を室温まで冷却した後、不溶物をセライトろ過により取り除き、得られたろ液を濃縮し、濃縮物をカラムクロマトグラフィーで精製し、3-ブロモ-9-(4-トリル)カルバゾール2.84g(42.2%)を得た。得られた化合物の1H-NMRスペクトル(測定溶媒:重THF)を図2~4に示す。 In a 200 mL two-necked flask, 20 mmоl (4.93 g) of 3-bromocarbazole, 44 mmоl (9.61 g) of 4-iodotoluene, 16 mmоl (3.05 g) of copper (I) iodide, and 50 mmоl (16.3 g) of cesium carbonate. ), 100 mL of toluene was added, and the mixture was stirred at room temperature for 5 minutes under a nitrogen stream, 30 mmоl (1.82 g) of ethylenediamine was added thereto, and the mixture was stirred overnight under heating and reflux.
After cooling the resulting reaction mixture to room temperature, the insoluble material is removed by filtration through Celite, the obtained filtrate is concentrated, and the concentrate is purified by column chromatography to purify 3-bromo-9- (4-tolyl) carbazole. 2.84 g (42.2%) was obtained. 1 H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 2 to 4.
反応混合物を室温まで冷却した後、不溶物をセライトろ過により取り除き、得られたろ液を濃縮し、濃縮物をカラムクロマトグラフィー(展開溶媒:n-ヘキサン/酢酸エチル=100/0→95/5)で精製し、3-ブロモ-9-(チオフェン-2-イル)カルバゾール5.80g(29.5%)を得た。得られた化合物の1H-NMRスペクトル(測定溶媒:重THF)を図7および8に示す。 In a 200 mL two-necked flask, 3-
After cooling the reaction mixture to room temperature, the insoluble material is removed by Celite filtration, the obtained filtrate is concentrated, and the concentrate is column chromatographed (developing solvent: n-hexane / ethyl acetate = 100/0 → 95/5). To obtain 5.80 g (29.5%) of 3-bromo-9- (thiophene-2-yl) carbazole. 1 H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 7 and 8.
反応混合物と、水75mLと、塩化メチレン75mLとを混合して抽出を行い、有機層を回収した。回収した有機層を硫酸マグネシウムで乾燥し、ろ過により硫酸マグネシウムを取り除いた。得られたろ液を濃縮し、濃縮物をカラムクロマトグラフィーで精製し、9-(p-トリル)カルバゾール-3-ボロン酸ピナコラート1.42g(74.3%)を得た。得られた化合物の1H-NMRスペクトル(測定溶媒:重THF)を図11および12に示す。 In a 100 mL reaction flask, 5-bromo-9- (p-tolyl) carbazole 5 mmоl (1.68 g), bis (pinacolat) diboron 5.05 mmоl (1.28 g), potassium acetate 15 mmоl (1.47 g), Pd ( dppf) Cl 2 0.15 mmоl (0.125 g) and 50 mL of N, N-dimethylformamide were added, nitrogen was replaced with stirring at room temperature for 10 minutes, the temperature was raised to 90 ° C., and the mixture was further stirred overnight.
The reaction mixture, 75 mL of water, and 75 mL of methylene chloride were mixed and extracted, and the organic layer was recovered. The recovered organic layer was dried over magnesium sulfate, and magnesium sulfate was removed by filtration. The obtained filtrate was concentrated, and the concentrate was purified by column chromatography to obtain 1.42 g (74.3%) of 9- (p-tolyl) carbazole-3-boronic acid pinacolate. 1 H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 11 and 12.
得られた反応混合物をメタノールと水の混合溶媒(3/1(v/v))400mLに加え、析出した固体をメンブランフィルターで濾別し、濾別した固体を60℃で減圧乾燥した。
さらに、乾燥した固体をテトラヒドロフラン20mLに溶解させ、得られた溶液をn-ヘキサン200mLに加え、析出した固体をメンブランフィルターで濾別し、濾別した固体を60℃で減圧乾燥した。
最後に、乾燥した固体をテトラヒドロフラン20mLに溶解させ、得られた溶液をメタノールと水の混合溶媒(3/1(v/v))200mLに加え、析出した固体をメンブランフィルターで濾別した。得られた固体を60℃で減圧乾燥し、3-(7-ブロモ-9,9-ジメチル-9H-フルオレン-2-イル)-9-フェニル-9H-カルバゾール1.28g(49.8%)を得た。得られた化合物の1H-NMRスペクトル(測定溶媒:重THF)を図19に示す。 In a 100 mL reaction flask, 5 mmol (1.44 g) of (9-phenyl-9H-carbazole-3-yl) boronic acid, 5.25 mmol (2) of 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene. .95 g), 15 mmol (600 mg) of sodium hydroxide, 75 mL of mixed solvent of tetrahydrofuran and water (2/1 (v / v)) and Pd [P (C 6 H 5 ) 3 )] 4 0.15 mmol (173.5 mg) ) Was added, and the mixture was stirred at room temperature for 10 minutes while substituting with nitrogen, and then stirred at 60 ° C. for 5 hours. On the way, a small amount of the solution in the flask was sampled, and the reaction was followed by liquid chromatography. As the area of peaks that can be attributed to raw materials decreased, the area of peaks that could be attributed to the target product increased. At that time, no conspicuous peak corresponding to the by-product was confirmed.
The obtained reaction mixture was added to 400 mL of a mixed solvent of methanol and water (3/1 (v / v)), the precipitated solid was filtered off with a membrane filter, and the filtered solid was dried under reduced pressure at 60 ° C.
Further, the dried solid was dissolved in 20 mL of tetrahydrofuran, the obtained solution was added to 200 mL of n-hexane, the precipitated solid was filtered off by a membrane filter, and the filtered solid was dried under reduced pressure at 60 ° C.
Finally, the dried solid was dissolved in 20 mL of tetrahydrofuran, the obtained solution was added to 200 mL of a mixed solvent of methanol and water (3/1 (v / v)), and the precipitated solid was filtered off by a membrane filter. The obtained solid was dried under reduced pressure at 60 ° C. to 1.28 g (49.8%) of 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole. Got The 1 H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.
得られた反応混合物を室温まで冷却した後、水層を除去した。得られた有機層を、メタノールと水の混合溶媒(3/1(v/v))に滴下し、析出した固体をメンブランフィルターで濾別し、濾別した固体を60℃で減圧乾燥した。
さらに、乾燥した固体をテトラヒドロフラン20mLに溶解させ、得られた溶液をn-ヘキサン200mLに加え、析出した固体をメンブランフィルターで濾別し、濾別した固体を60℃で減圧乾燥した。3-(7-ブロモ-9,9-ジメチル-9H-フルオレン-2-イル)-9-(p-トリル)-9H-カルバゾール1.10g(83.3%)を得た。得られた化合物の1H-NMRスペクトル(測定溶媒:重THF)を図20および21に示す。 In a 100 mL reaction flask, 2.5 mmоl (0.958 g) of 9- (p-tolyl) carbazole-3-boronic acid pinacolaate, 2.63 mmоl of 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene ( 1.05 g), 7.5 mmol (300 mg) of sodium hydroxide, 37.5 mL of mixed solvent of tetrahydrofuran and water (2/1 (v / v)) and Pd [P (C 6 H 5 ) 3 )] 40 . 075 mmol (86.7 mg) was added, and the mixture was stirred at room temperature for 10 minutes while substituting with nitrogen, and then stirred at 60 ° C. overnight.
After cooling the obtained reaction mixture to room temperature, the aqueous layer was removed. The obtained organic layer was added dropwise to a mixed solvent of methanol and water (3/1 (v / v)), the precipitated solid was filtered off with a membrane filter, and the filtered solid was dried under reduced pressure at 60 ° C.
Further, the dried solid was dissolved in 20 mL of tetrahydrofuran, the obtained solution was added to 200 mL of n-hexane, the precipitated solid was filtered off by a membrane filter, and the filtered solid was dried under reduced pressure at 60 ° C. 3- (7-Bromo-9,9-dimethyl-9H-fluorene-2-yl) -9- (p-tolyl) -9H-carbazole 1.10 g (83.3%) was obtained. 1 H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 20 and 21.
反応液を室温まで冷やし、シリカゲルN60 200gを詰めたろ過器でろ過し、得られたろ液を重さが100gになるまで濃縮し、濃縮物をトルエン1000mLに滴下して生じた固体を濾別した。得られた固体を乾燥し、ビス(3-ニトロフェニル)アミン24.1gを得た(収率93.1%)。 Reaction flask 1000mL fitted with a reflux column, Pd (DBA) 2 5mmol ( 2.88g), t-BuXPhos10mmol (4.25g), potassium carbonate 300mmol (41.46g), 3- nitroaniline 100 mmol (13.82 g ), 110 mmol (22.22 g) of 1-bromo-3-nitrobenzene and 1000 mL of toluene were added to replace the inside of the flask with nitrogen, and then the mixture was stirred overnight in a bath at 80 ° C. On the way, a small amount of the solution in the flask was sampled, and the reaction was followed by liquid chromatography. As the area of peaks that can be attributed to raw materials decreased, the area of peaks that could be attributed to the target product increased. At that time, no conspicuous peak corresponding to the by-product was confirmed.
The reaction mixture was cooled to room temperature, filtered through a filter filled with 200 g of silica gel N60, the obtained filtrate was concentrated to a weight of 100 g, the concentrate was added dropwise to 1000 mL of toluene, and the resulting solid was filtered off. .. The obtained solid was dried to obtain 24.1 g of bis (3-nitrophenyl) amine (yield 93.1%).
そこへジオキサン10mLを加え、室温で5分間撹拌し、次いでLHMDS1.3mol/Lテトラヒドロフラン溶液1.69mL(LHMDS2.2mmol相当)を加え、室温で5分間撹拌した後、110℃の浴中で8時間加熱撹拌した(内温92℃)。なお、途中、フラスコ内の溶液を微量採取し、液体クロマトグラフィーを用いて反応を追跡した。原料に帰属できるピークの面積の減少に伴い目的物に帰属できるピークの面積が増加した。その際、副生成物に対応するような目立ったピークは確認されなかった。
反応混合物を室温まで冷却した後、冷却した反応混合物を飽和塩化アンモニウム水溶液50mL、酢酸エチルとテトラヒドロフランの混合溶媒(2/1(v/v))50mLとともに分液漏斗に入れて抽出を行い、分液漏斗に有機層を残し、水層を回収した。飽和食塩水50mLを分液漏斗に入れて残った有機層を洗浄し、水層、有機層をそれぞれ回収した。そして、回収した全ての水層を併せて分液漏斗に入れ、そこへ酢酸エチル20mLを入れて抽出を行い、有機層を回収し、回収した全ての有機層を併せ、これを硫酸マグネシウムで乾燥した。
硫酸マグネシウムを濾過により除去し、得られた濾液からロータリーエバポレーターにより溶媒を留去した。得られた残渣をトルエン3mLに溶解させて得られた溶液を用いてカラムクロマトグラフィー(展開溶媒:n-ヘキサン/塩化メチレン=60/40→0/100)を行い、目的物を含むフラクションを分取した。
最後に、分取したフラクションから溶媒を取り除き、70℃で減圧乾燥後、アリールアミン化合物C2d 0.56g(>99%)を得た。得られた化合物の1H-NMRスペクトル(測定溶媒:重THF)を図27に示す。 Pd (DBA) 2 0.1 mmol (57.6 mg), RuPhos 0.15 mmol (70.0 mg), 3,3', 5,5'-tetramethylbenzidine 0.5 mmol in a 30 mL reaction flask equipped with a reflux column. Weigh in (120.2 mg), 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole 2.1 mmol (1080.4 mg), and pour through the system. Nitrogen substituted.
10 mL of dioxane is added thereto, and the mixture is stirred at room temperature for 5 minutes, then 1.69 mL of LHMDS 1.3 mol / L tetrahydrofuran solution (equivalent to 2.2 mmol of LHMDS) is added, and the mixture is stirred at room temperature for 5 minutes and then in a bath at 110 ° C. for 8 hours. The mixture was heated and stirred (internal temperature 92 ° C.). On the way, a small amount of the solution in the flask was sampled, and the reaction was followed by liquid chromatography. As the area of peaks that can be attributed to raw materials decreased, the area of peaks that could be attributed to the target product increased. At that time, no conspicuous peak corresponding to the by-product was confirmed.
After cooling the reaction mixture to room temperature, the cooled reaction mixture is placed in a separatory funnel together with 50 mL of a saturated aqueous solution of ammonium chloride and 50 mL of a mixed solvent of ethyl acetate and tetrahydrofuran (2/1 (v / v)) for extraction. The organic layer was left in the liquid funnel, and the aqueous layer was recovered. 50 mL of saturated saline was placed in a separatory funnel to wash the remaining organic layer, and the aqueous layer and the organic layer were recovered, respectively. Then, all the recovered aqueous layers are put together in a separating funnel, 20 mL of ethyl acetate is put therein and extraction is performed, the organic layer is recovered, all the recovered organic layers are put together, and this is dried with magnesium sulfate. did.
Magnesium sulfate was removed by filtration, and the solvent was distilled off from the obtained filtrate by a rotary evaporator. Column chromatography (developing solvent: n-hexane / methylene chloride = 60/40 → 0/100) was performed using the solution obtained by dissolving the obtained residue in 3 mL of toluene, and the fraction containing the desired product was separated. I took it.
Finally, the solvent was removed from the fraction, and the mixture was dried under reduced pressure at 70 ° C. to obtain 0.56 g (> 99%) of the arylamine compound C2d. The 1 H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 27.
反応混合物を室温まで冷やし、メンブランフィルターでろ過した。ろ液を濃縮し、得られた濃縮物をトルエン10mLで希釈して得られた溶液を用いたカラムクロマトグラフィーを行い(展開溶媒:n-ヘキサン/塩化メチレン=70/30(v/v)→55/45(v/v))、目的物のフラクションを集め、集めたフラクションを濃縮し、得られた濃縮物をトルエン10mLで希釈して得られた溶液を用いて再度同条件でカラムクロマトグラフィーを行い、目的物のフラクションを集めた。集めたフラクションを濃縮し、濃縮物をテトラヒドロフラン30mLに溶解し、得られた溶液を酢酸エチルとメタノールの混合溶媒(1/1(v/v))に滴下し、析出した固体をメンブランフィルターで回収した。得られた固体を乾燥し、アリールアミン化合物H3d 2.67g(28.2%)を得た。得られた化合物の1H-NMRスペクトル(測定溶媒:重THF)を図36に示す。 Reaction flask fitted with a reflux column 200mL, Pd (ОAc) 2 2mmol (0.45g), t-Bu 3 PHBF 4 4mmol (1.16g), t-BuONa40mmol (3.84g), 4,4'- Weigh 4 mmol (797.0 mg) of diaminodiphenylamine and 20.6 mmol (10.61 g) of 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole. The inside of the flask was replaced with nitrogen. Toluene (50 mL) was added thereto, and the mixture was stirred overnight in a bath at 110 ° C. On the way, a small amount of the solution in the flask was sampled, and the reaction was followed by liquid chromatography. As the area of peaks that can be attributed to raw materials decreased, the area of peaks that could be attributed to the target product increased. At that time, no conspicuous peak corresponding to the by-product was confirmed.
The reaction mixture was cooled to room temperature and filtered through a membrane filter. The filtrate was concentrated, and the obtained concentrate was diluted with 10 mL of toluene and column chromatography was performed using the obtained solution (developing solvent: n-hexane / methylene chloride = 70/30 (v / v) → 55/45 (v / v)), collect the fractions of interest, concentrate the collected fractions, dilute the resulting concentrate with 10 mL of toluene and use the resulting solution for column chromatography again under the same conditions. And collected the fractions of the target object. The collected fractions are concentrated, the concentrate is dissolved in 30 mL of tetrahydrofuran, the obtained solution is added dropwise to a mixed solvent of ethyl acetate and methanol (1/1 (v / v)), and the precipitated solid is recovered by a membrane filter. did. The obtained solid was dried to obtain 2.67 g (28.2%) of the arylamine compound H3d. The 1 H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.
反応混合物を室温まで冷却し、メンブランフィルターでろ過した。ろ液を濃縮し、得られた濃縮物をトルエン5mLで希釈して得られた溶液を用いたカラムクロマトグラフィーを行い(展開溶媒:n-ヘキサン/塩化メチレン=70/30(v/v)→55/45(v/v))、目的物のフラクションを集め、集めたフラクションを濃縮し、得られた濃縮物をトルエン5mLで希釈して得られた溶液を用いて再度同条件でカラムクロマトグラフィーを行い、目的物のフラクションを集めた。集めたフラクションを濃縮し、濃縮物をテトラヒドロフラン30mLに溶解し、得られた溶液を酢酸エチルとメタノールの混合溶媒(1/1(v/v))に滴下し、析出した固体をメンブランフィルターで回収した。得られた固体を乾燥し、アリールアミン化合物I3d 2.34g(39.5%)を得た。得られた化合物の1H-NMRスペクトル(測定溶媒:重THF)を図37に示す。 Reaction flask fitted with a reflux column 30mL, Pd (ОAc) 2 2.5mmol (0.56g), t-Bu 3 PHBF 4 5mmol (1.45g), t-BuONa25mmol (2.40g), 3,3 '-Diaminodiphenylamine dihydrochloride 2.5 mmol (80.4 mg), 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9-phenyl-9H-carbazole 12.6 mmol (6) .49 g) was weighed and the inside of the flask was replaced with nitrogen. Toluene (50 mL) was added thereto, and the mixture was stirred overnight in a bath at 110 ° C. On the way, a small amount of the solution in the flask was sampled, and the reaction was followed by liquid chromatography. As the area of peaks that can be attributed to raw materials decreased, the area of peaks that could be attributed to the target product increased. At that time, no conspicuous peak corresponding to the by-product was confirmed.
The reaction mixture was cooled to room temperature and filtered through a membrane filter. The filtrate was concentrated, and the obtained concentrate was diluted with 5 mL of toluene and column chromatography was performed using the obtained solution (developing solvent: n-hexane / methylene chloride = 70/30 (v / v) → 55/45 (v / v)), collect the fractions of interest, concentrate the collected fractions, dilute the resulting concentrate with 5 mL of toluene and use the resulting solution for column chromatography again under the same conditions. And collected the fractions of the target object. The collected fractions are concentrated, the concentrate is dissolved in 30 mL of tetrahydrofuran, the obtained solution is added dropwise to a mixed solvent of ethyl acetate and methanol (1/1 (v / v)), and the precipitated solid is recovered by a membrane filter. did. The obtained solid was dried to obtain 2.34 g (39.5%) of arylamine compound I3d. The 1 H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 37.
反応混合物を室温まで冷却した後、冷却した反応混合物から水層を除去し、得られた有機層を、メタノールと水の混合溶媒(メタノール/水=3/1(v/v))に滴下した。析出した固体をろ過で回収し、得られた固体をテトラヒドロフランに溶解させ、この溶液をn-ヘキサンに滴下した。得られた固体をろ過で回収し、減圧下で乾燥し、アリールアミン化合物I3e 210mg(21.5%)を得た。得られた化合物の1H-NMRスペクトル(測定溶媒:重THF)を図38および39に示す。 In a 50 mL flask, 0.4 mmоl (108.9 mg) of 3,3'-diaminodiphenylamine dihydrochloride, 3- (7-bromo-9,9-dimethyl-9H-fluorene-2-yl) -9- (p) -Trill) -9H-carbazole 2.02 mmоl (1067.5 mg), Pd (ОAc) 2 0.4 mmоl (89.8 mg), t-Bu 3 PHBF 4 0.8 mmоl (232.1 mg), t-BuONa 4 mmоl (384) After adding (0.4 mg) and replacing with nitrogen, 8 mL of toluene was added, and the mixture was stirred for 10 minutes, and then stirred overnight under heating and reflux conditions.
After cooling the reaction mixture to room temperature, the aqueous layer was removed from the cooled reaction mixture, and the obtained organic layer was added dropwise to a mixed solvent of methanol and water (methanol / water = 3/1 (v / v)). .. The precipitated solid was collected by filtration, the obtained solid was dissolved in tetrahydrofuran, and this solution was added dropwise to n-hexane. The obtained solid was collected by filtration and dried under reduced pressure to obtain 210 mg (21.5%) of arylamine compound I3e. 1 H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 38 and 39.
反応混合物を室温まで冷却した後、冷却した反応混合物をメンブランフィルターでろ過し、得られたろ液に活性炭を加えて1時間撹拌した。活性炭をろ過で取り除き、得られたろ液を濃縮し、濃縮物をシリカゲルクロマトグラフィー(展開溶媒:n-ヘキサン/ジクロロメタン=3/2(v/v))で精製し、アリールアミン化合物B3b 311.8mg(44.6%)を得た。得られた化合物の1H-NMRスペクトル(測定溶媒:重THF)を図47に示す。 Octafluorobiphenyl-4,4'-diamine 0.5 mmоl (164 mg), 3- (4-bromophenyl) -9-phenylcarbazole 2.1 mmol (836 mg), Pd (ОAc) 20 in a 50 mL reaction flask. After adding 2 mmоl (45 mg), t-Bu 3 PHBF 4 0.4 mmоl (166 mg) and t-BuONa 4 mmоl (385 mg) for nitrogen substitution, add 10 mL of toluene, stir at room temperature for 5 minutes, and then stir at 100 ° C. for 6 hours. Stirred.
After cooling the reaction mixture to room temperature, the cooled reaction mixture was filtered through a membrane filter, activated carbon was added to the obtained filtrate, and the mixture was stirred for 1 hour. Activated carbon was removed by filtration, the obtained filtrate was concentrated, and the concentrate was purified by silica gel chromatography (developing solvent: n-hexane / dichloromethane = 3/2 (v / v)), and the arylamine compound B3b 311.8 mg. (44.6%) was obtained. The 1 H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 47.
反応混合物を室温まで冷却した後、冷却した反応混合物をメンブランフィルターでろ過し、得られたろ液に活性炭を加えて1時間撹拌した。活性炭をろ過で取り除き、得られたろ液を濃縮し、濃縮物をシリカゲルクロマトグラフィー(展開溶媒:n-ヘキサン/ジクロロメタン=3/2(v/v))で精製し、アリールアミン化合物B2b 419.0mg(87.0%)を得た。得られた化合物の1H-NMRスペクトル(測定溶媒:重DMSO)を図50に示す。 Octafluorobiphenyl-4,4'-diamine 0.5 mmоl (164 mg), 3- (4-bromophenyl) -9-phenylcarbazole 2.1 mmol (836 mg), Pd (DBA) 20 in a 50 mL reaction flask. After adding 1 mmоl (57.5 mg), t-Bu 3 PHBF 4 0.2 mmоl (84 mg) and t-
After cooling the reaction mixture to room temperature, the cooled reaction mixture was filtered through a membrane filter, activated carbon was added to the obtained filtrate, and the mixture was stirred for 1 hour. Activated carbon was removed by filtration, the obtained filtrate was concentrated, and the concentrate was purified by silica gel chromatography (developing solvent: n-hexane / dichloromethane = 3/2 (v / v)), and the arylamine compound B2b 419.0 mg. (87.0%) was obtained. The 1 H-NMR spectrum (measurement solvent: heavy DMSO) of the obtained compound is shown in FIG.
[比較例2-1]
クロロホルム(10g)に、アリールアミン化合物A3a(0.025g)と下記式で表されるアリールスルホン酸エステルA(0.025g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスA3a-1を得た。 [2] Preparation of varnish for hole injection layer [Comparative Example 2-1]
A solution obtained by adding an arylamine compound A3a (0.025 g) and an aryl sulfonic acid ester A (0.025 g) represented by the following formula to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared. A charge-transporting varnish A3a-1 was obtained by filtering with a syringe filter having a pore size of 0.2 μm.
クロロホルム(10g)に、アリールアミン化合物A3b(0.028g)と、アリールスルホン酸エステルA(0.022g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスA3b-1を得た。 [Example 2-1]
A solution obtained by adding arylamine compound A3b (0.028 g) and aryl sulfonic acid ester A (0.022 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared having a pore size of 0.2 μm. The mixture was filtered through a syringe filter to obtain a charge-transporting varnish A3b-1.
クロロホルム(10g)に、アリールアミン化合物A3c(0.030g)とアリールスルホン酸エステルA(0.020g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスA3c-1を得た。 [Example 2-2]
The solution obtained by adding arylamine compound A3c (0.030 g) and aryl sulfonic acid ester A (0.020 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish A3c-1.
クロロホルム(10g)に、アリールアミン化合物A3d(0.031g)とアリールスルホン酸エステルA(0.019g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスA3d-1を得た。 [Example 2-3]
The solution obtained by adding arylamine compound A3d (0.031 g) and aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish A3d-1.
クロロホルム(10g)に、アリールアミン化合物A3e(0.031g)とアリールスルホン酸エステルA(0.019g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスA3e-1を得た。 [Example 2-4]
The solution obtained by adding arylamine compound A3e (0.031 g) and aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish A3e-1.
クロロホルム(10g)に、アリールアミン化合物A3f(0.032g)とアリールスルホン酸エステルA(0.018g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスA3f-1を得た。 [Example 2-5]
The solution obtained by adding arylamine compound A3f (0.032 g) and aryl sulfonic acid ester A (0.018 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. The mixture was filtered through a filter to obtain a charge-transporting varnish A3f-1.
クロロホルム(10g)に、アリールアミン化合物A3g(0.031g)とアリールスルホン酸エステルA(0.019g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスA3g-1を得た。 [Example 2-6]
The solution obtained by adding 3 g (0.031 g) of the arylamine compound A (0.031 g) and the aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish A3g-1.
クロロホルム(10g)に、アリールアミン化合物A3h(0.031g)とアリールスルホン酸エステルA(0.019g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスA3h-1を得た。 [Example 2-7]
The solution obtained by adding arylamine compound A3h (0.031 g) and aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. The mixture was filtered through a filter to obtain a charge-transporting varnish A3h-1.
クロロホルム(10g)に、アリールアミン化合物B3a(0.026g)とアリールスルホン酸エステルA(0.024g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスB3a-1を得た。 [Comparative Example 2-2]
The solution obtained by adding arylamine compound B3a (0.026 g) and aryl sulfonic acid ester A (0.024 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B3a-1.
クロロホルム(10g)に、アリールアミン化合物B3b(0.029g)とアリールスルホン酸エステルA(0.021g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスB3b-1を得た。 [Example 2-8]
The solution obtained by adding arylamine compound B3b (0.029 g) and aryl sulfonic acid ester A (0.021 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B3b-1.
クロロホルム(10g)に、アリールアミン化合物B3c(0.030g)とアリールスルホン酸エステルA(0.020g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスB3c-1を得た。 [Example 2-9]
The solution obtained by adding arylamine compound B3c (0.030 g) and aryl sulfonic acid ester A (0.020 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B3c-1.
クロロホルム(10g)に、アリールアミン化合物B3d(0.031g)とアリールスルホン酸エステルA(0.019g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスB3d-1を得た。 [Example 2-10]
The solution obtained by adding arylamine compound B3d (0.031 g) and aryl sulfonic acid ester A (0.019 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B3d-1.
クロロホルム(10g)に、アリールアミン化合物B2a(0.020g)とアリールスルホン酸エステルA(0.030g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスB2a-1を得た。 [Comparative Example 2-3]
The solution obtained by adding arylamine compound B2a (0.020 g) and aryl sulfonic acid ester A (0.030 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B2a-1.
クロロホルム(10g)に、アリールアミン化合物B2b(0.022g)とアリールスルホン酸エステルA(0.028g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスB2b-1を得た。 [Example 2-11]
The solution obtained by adding arylamine compound B2b (0.022 g) and aryl sulfonic acid ester A (0.028 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B2b-1.
クロロホルム(10g)に、アリールアミン化合物B2c(0.024g)とアリールスルホン酸エステルA(0.026g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスB2c-1を得た。 [Example 2-12]
The solution obtained by adding arylamine compound B2c (0.024 g) and aryl sulfonic acid ester A (0.026 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B2c-1.
クロロホルム(10g)に、アリールアミン化合物B2d(0.025g)とアリールスルホン酸エステルA(0.025g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスB2d-1を得た。 [Example 2-13]
The solution obtained by adding arylamine compound B2d (0.025 g) and aryl sulfonic acid ester A (0.025 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish B2d-1.
クロロホルム(10g)に、アリールアミン化合物H3d(0.033g)とアリールスルホン酸エステルA(0.017g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスH3d-1を得た。 [Example 2-14]
The solution obtained by adding arylamine compound H3d (0.033 g) and aryl sulfonic acid ester A (0.017 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish H3d-1.
クロロホルム(10g)に、アリールアミン化合物I3d(0.033g)とアリールスルホン酸エステルA(0.017g)とを加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスI3d-1を得た。 [Example 2-15]
The solution obtained by adding arylamine compound I3d (0.033 g) and aryl sulfonic acid ester A (0.017 g) to chloroform (10 g) and stirring at room temperature to dissolve the solution was prepared with a syringe having a pore size of 0.2 μm. Filtering with a filter gave a charge-transporting varnish I3d-1.
[比較例3-1]
クロロホルム(10g)に、アリールアミン化合物A3a(0.040g)を加えて室温で撹拌して溶解させて得られた溶液を、孔径0.2μmのシリンジフィルターで濾過して電荷輸送性ワニスA3a-2を得た。 [3] Preparation of varnish for hole transport layer [Comparative Example 3-1]
The solution obtained by adding arylamine compound A3a (0.040 g) to chloroform (10 g) and stirring at room temperature to dissolve it is filtered through a syringe filter having a pore size of 0.2 μm to carry charge-transporting varnish A3a-2. Got
アリールアミン化合物A3aの代わりに、アリールアミン化合物A3b,A3c,A3d,A3e,A3f,A3g,A3h,B3d,B2d,H3d,またはI3dをそれぞれ用いた以外は、比較例3-1と同様の方法で電荷輸送性ワニスA3b-2,A3c-2,A3d-2,A3e-2,A3f-2,A3g-2,A3h-2,B3d-2,B2d-2,H3d-2,またはI3d-2を得た。 [Examples 3-1 to 3-11]
In the same manner as in Comparative Example 3-1 except that the arylamine compounds A3b, A3c, A3d, A3e, A3f, A3g, A3h, B3d, B2d, H3d, or I3d were used instead of the arylamine compound A3a. Obtains charge-transporting varnishes A3b-2, A3c-2, A3d-2, A3e-2, A3f-2, A3g-2, A3h-2, B3d-2, B2d-2, H3d-2, or I3d-2. It was.
[比較例4-1、実施例4-1~4-3]
電荷輸送性ワニスA3a-1,A3b-1,A3c-1,およびA3d-1を、それぞれスピンコーターを用いて石英基板に塗布した後、大気焼成下、120℃で1分間乾燥した。次に、乾燥させた石英基板を大気雰囲気下、200℃で15分間焼成し、石英基板上に50nmの均一な薄膜を形成した。
得られた膜付き石英基板を用いて、波長400~800nmにおける可視域平均屈折率(n)および可視域平均消衰係数(k)の測定を行った。結果を表23に示す。 [4] Production of thin film and evaluation of film physical properties [Comparative Example 4-1 and Examples 4-1 to 4-3]
The charge-transporting varnishes A3a-1, A3b-1, A3c-1, and A3d-1 were each applied to a quartz substrate using a spin coater, and then dried at 120 ° C. for 1 minute under atmospheric firing. Next, the dried quartz substrate was calcined at 200 ° C. for 15 minutes in an air atmosphere to form a uniform thin film of 50 nm on the quartz substrate.
Using the obtained quartz substrate with a film, the visible region average refractive index (n) and the visible region average extinction coefficient (k) at a wavelength of 400 to 800 nm were measured. The results are shown in Table 23.
[比較例5-1]
ITO基板として、インジウム錫酸化物(ITO)が表面上に膜厚150nmでパターニングされた25mm×25mm×0.7tのガラス基板を用い、使用前にO2プラズマ洗浄装置(150W、30秒間)によって表面上の不純物を除去した。続いて、後述の方法で得た正孔注入層形成用組成物をスピンコートにより塗布し、大気中、ホットプレート上で80℃に加熱して1分間乾燥後、さらに230℃で15分間焼成し、正孔注入層(膜厚:30nm)を形成した。
次に、電荷輸送性ワニスA3a-2を、スピンコーターを用いて正孔注入層上に塗布した後、大気雰囲気下、130℃で10分間焼成し、正孔輸送層(膜厚:40nm)を形成した。
この上に、蒸着装置(真空度1.0×10-5Pa)を用いて0.2nm/秒にて80nmのアルミニウム薄膜を形成してホールオンリー素子(HOD)を得た。
なお、正孔注入層形成用組成物は、次の手順で調製した。国際公開第2013/084664号記載の方法に従って合成した式(3)で表されるアニリン誘導体0.137gと、国際公開第2006/025342号記載の方法に従って合成した式(4)で表されるアリールスルホン酸0.271gとを、窒素雰囲気下で1,3-ジメチル-2-イミダゾリジノン6.7gに溶解させた。得られた溶液に、シクロヘキサノール10g、プロピレングリコール3.3gを順次加えて撹拌し、正孔注入層形成用組成物を得た(以下同様)。 [5] Fabrication and characterization of hole-only devices (HOD) [Comparative Example 5-1]
As the ITO substrate, a 25 mm × 25 mm × 0.7 t glass substrate in which indium tin oxide (ITO) is patterned on the surface with a film thickness of 150 nm is used, and before use, an O 2 plasma cleaning device (150 W, 30 seconds) is used. Impurities on the surface were removed. Subsequently, the composition for forming a hole injection layer obtained by the method described later is applied by spin coating, heated to 80 ° C. on a hot plate in the air, dried for 1 minute, and then fired at 230 ° C. for 15 minutes. , A hole injection layer (film thickness: 30 nm) was formed.
Next, the charge-transporting varnish A3a-2 was applied onto the hole injection layer using a spin coater, and then fired at 130 ° C. for 10 minutes in an air atmosphere to form a hole transport layer (film thickness: 40 nm). Formed.
A hole-only element (HOD) was obtained by forming an aluminum thin film of 80 nm at 0.2 nm / sec using a vapor deposition apparatus (vacuum degree 1.0 × 10 -5 Pa).
The composition for forming a hole injection layer was prepared by the following procedure. 0.137 g of the aniline derivative represented by the formula (3) synthesized according to the method described in WO2013 / 084664 and the aryl represented by the formula (4) synthesized according to the method described in WO 2006/025432. 0.271 g of sulfonic acid was dissolved in 6.7 g of 1,3-dimethyl-2-imidazolidinone under a nitrogen atmosphere. To the obtained solution, 10 g of cyclohexanol and 3.3 g of propylene glycol were sequentially added and stirred to obtain a composition for forming a hole injection layer (the same applies hereinafter).
電荷輸送性ワニスA3a-2の代わりに、電荷輸送性ワニスA3b-2,A3c-2,A3d-2,A3e-2,A3f-2,A3g-2,A3h-2,B3d-2,B2d-2,H3d-2,またはI3d-2をそれぞれ用いた以外は、実施例5-1と同様の方法でHODを作製した。 [Examples 5-1 to 5-11]
Instead of the charge-transporting varnish A3a-2, the charge-transporting varnish A3b-2, A3c-2, A3d-2, A3e-2, A3f-2, A3g-2, A3h-2, B3d-2, B2d-2 , H3d-2, or I3d-2 were used, respectively, and HOD was prepared in the same manner as in Example 5-1.
[比較例6-1]
ITO基板として、インジウム錫酸化物(ITO)が表面上に膜厚150nmでパターニングされた25mm×25mm×0.7tのガラス基板を用い、使用前にO2プラズマ洗浄装置(150W、30秒間)によって表面上の不純物を除去した。
電荷輸送性ワニスA3a-1を、ITO基板上にスピンコートにより塗布し、大気下、120℃で1分間乾燥後、200℃で15分間焼成し、ITO基板上に正孔注入層(膜厚:50nm)を形成した。
この上に、蒸着装置(真空度1.0×10-5Pa)を用いて0.2nm/秒にて80nmのアルミニウム薄膜を形成して単層素子(SLD)を得た。 [6] Fabrication of single-layer device (SLD) and HOD and evaluation of relative strength of HOD current density with respect to SLD current density [Comparative Example 6-1]
As the ITO substrate, a 25 mm × 25 mm × 0.7 t glass substrate in which indium tin oxide (ITO) is patterned on the surface with a film thickness of 150 nm is used, and before use, an O 2 plasma cleaning device (150 W, 30 seconds) is used. Impurities on the surface were removed.
Charge-transporting varnish A3a-1 is applied onto an ITO substrate by spin coating, dried in the air at 120 ° C. for 1 minute, and then fired at 200 ° C. for 15 minutes, and a hole injection layer (film thickness:: 50 nm) was formed.
On this, an aluminum thin film of 80 nm was formed at 0.2 nm / sec using a vapor deposition apparatus (vacuum degree 1.0 × 10 -5 Pa) to obtain a single-layer device (SLD).
電荷輸送性ワニスA3a-1の代わりに、電荷輸送性ワニスA3b-1,A3c-1,A3d-1,A3e-1,A3f-1,A3g-1,A3h-1,B3b-1,B3d-1,B2d-1,H3d-1,I3d-1,またはB3a-1をそれぞれ用いた以外は、比較例6-1と同様の方法でSLDを作製した。 [Examples 6-1 to 6-12, Comparative Example 6-2]
Instead of the charge-transporting varnish A3a-1, the charge-transporting varnish A3b-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3h-1, B3b-1, B3d-1 , B2d-1, H3d-1, I3d-1, or B3a-1 were used, but SLD was prepared in the same manner as in Comparative Example 6-1.
電荷輸送性ワニスA3a-1を、スピンコーターを用いてITO基板に塗布した後、大気下で、120℃で1分間乾燥し、次いで200℃で15分間焼成し、ITO基板上に50nmの薄膜を形成した。なお、ITO基板として、比較例6-1と同様のITO基板を用いた。
その上に、蒸着装置(真空度2.0×10-5Pa)を用いてα-NPDおよびアルミニウムの薄膜を順次積層し、HODを得た。蒸着は、蒸着レート0.2nm/秒の条件で行った。α-NPDおよびアルミニウムの薄膜の膜厚は、それぞれ30nmおよび80nmとした。 [Comparative Example 7-1]
The charge-transporting varnish A3a-1 is applied to an ITO substrate using a spin coater, dried in the air at 120 ° C. for 1 minute, and then fired at 200 ° C. for 15 minutes to form a 50 nm thin film on the ITO substrate. Formed. As the ITO substrate, the same ITO substrate as in Comparative Example 6-1 was used.
A thin film of α-NPD and aluminum was sequentially laminated on it using a thin film deposition apparatus (vacuum degree 2.0 × 10 -5 Pa) to obtain HOD. The vapor deposition was carried out under the condition of a vapor deposition rate of 0.2 nm / sec. The film thicknesses of the α-NPD and aluminum thin films were 30 nm and 80 nm, respectively.
電荷輸送性ワニスA3a-1の代わりに、それぞれ電荷輸送性ワニスA3b-1,A3c-1,A3d-1,A3e-1,A3f-1,A3g-1,A3h-1,B3b-1,B3d-1,B2d-1,H3d-1,I3d-1,またはB3a-1を用いた以外は、比較例7-1と同様の方法でHODを作製した。 [Examples 7-1 to 7-12, Comparative Example 7-2]
Instead of the charge-transporting varnish A3a-1, the charge-transporting varnishes A3b-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3h-1, B3b-1, B3d-, respectively. HOD was prepared in the same manner as in Comparative Example 7-1 except that 1, B2d-1, H3d-1, I3d-1, or B3a-1 was used.
[比較例8-1]
電荷輸送性ワニスA3a-1を、スピンコーターを用いてITO基板に塗布した後、大気下で、120℃で1分間乾燥し、次いで200℃で15分間焼成し、ITO基板上に50nmの薄膜を形成した。なお、ITO基板として、比較例6-1と同様のITO基板を用いた。
次いで、薄膜を形成したITO基板に対し、蒸着装置(真空度1.0×10-5Pa)を用いてα-NPDを0.2nm/秒にて30nm成膜した。次に、関東化学(株)製の電子ブロック材料HTEB-01を10nm成膜した。次いで、新日鉄住金化学(株)製の発光層ホスト材料NS60と発光層ドーパント材料Ir(ppy)3を共蒸着した。共蒸着は、Ir(ppy)3の濃度が6%になるように蒸着レートをコントロールし、40nm積層させた。次いで、Alq3、フッ化リチウムおよびアルミニウムの薄膜を順次積層して有機EL素子を得た。この際、蒸着レートは、Alq3およびアルミニウムについては0.2nm/秒、フッ化リチウムについては0.02nm/秒の条件でそれぞれ行い、膜厚は、それぞれ20nm、0.5nmおよび80nmとした。
なお、空気中の酸素、水等の影響による特性劣化を防止するため、有機EL素子は封止基板により封止した後、その特性を評価した。封止は、以下の手順で行った。酸素濃度2ppm以下、露点-76℃以下の窒素雰囲気中で、有機EL素子を封止基板の間に収め、封止基板を接着剤((株)MORESCO製、モレスコモイスチャーカットWB90US(P))により貼り合わせた。この際、捕水剤(ダイニック(株)製HD-071010W-40)を有機EL素子と共に封止基板内に収めた。貼り合わせた封止基板に対し、UV光を照射(波長:365nm、照射量:6,000mJ/cm2)した後、80℃で1時間、アニーリング処理して接着剤を硬化させた。 [7] Fabrication and characterization of organic EL devices [Comparative Example 8-1]
The charge-transporting varnish A3a-1 is applied to an ITO substrate using a spin coater, dried in the air at 120 ° C. for 1 minute, and then fired at 200 ° C. for 15 minutes to form a 50 nm thin film on the ITO substrate. Formed. As the ITO substrate, the same ITO substrate as in Comparative Example 6-1 was used.
Next, on the ITO substrate on which the thin film was formed, α-NPD was deposited at 0.2 nm / sec at 30 nm using a thin film deposition apparatus (vacuum degree 1.0 × 10 -5 Pa). Next, a 10 nm film was formed on the electronic block material HTEB-01 manufactured by Kanto Chemical Co., Inc. Next, the light emitting layer host material NS60 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and the light emitting layer dopant material Ir (ppy) 3 were co-deposited. For co-evaporation, the vapor deposition rate was controlled so that the concentration of Ir (ppy) 3 was 6%, and 40 nm was laminated. Next, thin films of Alq 3 , lithium fluoride and aluminum were sequentially laminated to obtain an organic EL device. At this time, the vapor deposition rate was 0.2 nm / sec for Alq 3 and aluminum, and 0.02 nm / sec for lithium fluoride, respectively, and the film thicknesses were 20 nm, 0.5 nm, and 80 nm, respectively.
In order to prevent the deterioration of the characteristics due to the influence of oxygen, water, etc. in the air, the organic EL element was sealed with a sealing substrate and then the characteristics were evaluated. Sealing was performed by the following procedure. In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -76 ° C or less, an organic EL element is placed between the sealing substrates, and the sealing substrate is an adhesive (Matsumura Oil Research Corp., Moresco Moisture Cut WB90US (P)). It was pasted together. At this time, a water catching agent (HD-071010W-40 manufactured by Dynic Co., Ltd.) was housed in the sealing substrate together with the organic EL element. The bonded substrate was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ / cm 2 ) and then annealed at 80 ° C. for 1 hour to cure the adhesive.
電荷輸送性ワニスA3a-1の代わりに、それぞれ電荷輸送性ワニスA3b-1,A3c-1,A3d-1,A3e-1,A3f-1,A3g-1,A3h-1,B3b-1,B3d-1,B2d-1,H3d-1,またはI3d-1を用いた以外は、比較例8-1と同様の方法で有機EL素子を作製した。 [Examples 8-1 to 8-12]
Instead of the charge-transporting varnish A3a-1, the charge-transporting varnishes A3b-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3h-1, B3b-1, B3d-, respectively. An organic EL device was produced in the same manner as in Comparative Example 8-1 except that 1, B2d-1, H3d-1, or I3d-1 was used.
Claims (12)
- 下記式(1)~(6)のいずれかで表されることを特徴とするアリールアミン化合物(ただし、下記式(P1)~(P4)で表される化合物を除く。)。
Xは、それぞれ独立して、置換されていてもよいとともに、ヘテロ原子を含んでいてもよいアリーレン基を表し、
Yは、それぞれ独立して、置換されていてもよいフェニレン基を表し、
gは、それぞれ独立して、1~10の整数を表す。
X represents an arylene group which may be independently substituted and may contain a heteroatom.
Y represents a phenylene group which may be substituted independently of each other.
g represents an integer of 1 to 10 independently of each other.
- 前記Arsが、下記式(101)~(118)のいずれかで表される請求項1記載のアリールアミン化合物。
- 前記Xが、下記式(201)~(207)のいずれかで表される請求項1~4のいずれか1項記載のアリールアミン化合物。
- 前記Arcが、同一の基である請求項1~7のいずれか1項記載のアリールアミン化合物。 Wherein Ar c is an arylamine compound as claimed in any one of claims 1 to 7 of the same group.
- 請求項1~8のいずれか1項記載のアリールアミン化合物と、有機溶媒とを含む電荷輸送性ワニス。 A charge-transporting varnish containing the arylamine compound according to any one of claims 1 to 8 and an organic solvent.
- ドーパント物質を含む請求項9記載の電荷輸送性ワニス。 The charge transporting varnish according to claim 9, which contains a dopant substance.
- 請求項9または10の電荷輸送性ワニスを用いて作製される電荷輸送性薄膜。 A charge-transporting thin film produced by using the charge-transporting varnish of claim 9 or 10.
- 請求項11記載の電荷輸送性薄膜を備える電子素子。 An electronic device including the charge transporting thin film according to claim 11.
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