JPH09194441A - Naphthyl group-bearing diamine derivative and organic electroluminescence element using the same - Google Patents
Naphthyl group-bearing diamine derivative and organic electroluminescence element using the sameInfo
- Publication number
- JPH09194441A JPH09194441A JP8003585A JP358596A JPH09194441A JP H09194441 A JPH09194441 A JP H09194441A JP 8003585 A JP8003585 A JP 8003585A JP 358596 A JP358596 A JP 358596A JP H09194441 A JPH09194441 A JP H09194441A
- Authority
- JP
- Japan
- Prior art keywords
- organic
- diamine derivative
- light emitting
- layer
- emitting layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000004985 diamines Chemical class 0.000 title claims abstract description 65
- 238000005401 electroluminescence Methods 0.000 title claims description 6
- 125000001624 naphthyl group Chemical group 0.000 title description 5
- 230000005525 hole transport Effects 0.000 claims abstract description 40
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 46
- 150000001875 compounds Chemical class 0.000 abstract description 30
- 239000002904 solvent Substances 0.000 abstract description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 108091008695 photoreceptors Proteins 0.000 abstract description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 6
- OOLSRHZMXAYDFB-UHFFFAOYSA-N 1-ethyl-4-iodobenzene Chemical compound CCC1=CC=C(I)C=C1 OOLSRHZMXAYDFB-UHFFFAOYSA-N 0.000 abstract description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 2
- SZDXPEWZZGNIBB-UHFFFAOYSA-N n-[4-[4-(naphthalen-1-ylamino)phenyl]phenyl]naphthalen-1-amine Chemical compound C1=CC=C2C(NC=3C=CC(=CC=3)C=3C=CC(NC=4C5=CC=CC=C5C=CC=4)=CC=3)=CC=CC2=C1 SZDXPEWZZGNIBB-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 160
- 238000000034 method Methods 0.000 description 26
- 239000000126 substance Substances 0.000 description 22
- 238000002347 injection Methods 0.000 description 20
- 239000007924 injection Substances 0.000 description 20
- 239000010409 thin film Substances 0.000 description 17
- 239000000758 substrate Substances 0.000 description 15
- -1 diamine compound Chemical class 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 238000007740 vapor deposition Methods 0.000 description 9
- 239000010408 film Substances 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- 238000001771 vacuum deposition Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- UHXOHPVVEHBKKT-UHFFFAOYSA-N 1-(2,2-diphenylethenyl)-4-[4-(2,2-diphenylethenyl)phenyl]benzene Chemical group C=1C=C(C=2C=CC(C=C(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=2)C=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 UHXOHPVVEHBKKT-UHFFFAOYSA-N 0.000 description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- NGQSLSMAEVWNPU-YTEMWHBBSA-N 1,2-bis[(e)-2-phenylethenyl]benzene Chemical compound C=1C=CC=CC=1/C=C/C1=CC=CC=C1\C=C\C1=CC=CC=C1 NGQSLSMAEVWNPU-YTEMWHBBSA-N 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CSPVGJWCKNBRRB-UHFFFAOYSA-N indium;quinolin-8-ol Chemical compound [In].C1=CN=C2C(O)=CC=CC2=C1.C1=CN=C2C(O)=CC=CC2=C1.C1=CN=C2C(O)=CC=CC2=C1 CSPVGJWCKNBRRB-UHFFFAOYSA-N 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 125000006606 n-butoxy group Chemical group 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 229960003540 oxyquinoline Drugs 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000005920 sec-butoxy group Chemical group 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 235000021286 stilbenes Nutrition 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JCXLYAWYOTYWKM-UHFFFAOYSA-N (2,3,4-triphenylcyclopenta-1,3-dien-1-yl)benzene Chemical compound C1C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 JCXLYAWYOTYWKM-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-VOTSOKGWSA-N (e)-2-phenylethenamine Chemical class N\C=C\C1=CC=CC=C1 UWRZIZXBOLBCON-VOTSOKGWSA-N 0.000 description 1
- 150000000183 1,3-benzoxazoles Chemical class 0.000 description 1
- KLCLIOISYBHYDZ-UHFFFAOYSA-N 1,4,4-triphenylbuta-1,3-dienylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)=CC=C(C=1C=CC=CC=1)C1=CC=CC=C1 KLCLIOISYBHYDZ-UHFFFAOYSA-N 0.000 description 1
- QKLPIYTUUFFRLV-YTEMWHBBSA-N 1,4-bis[(e)-2-(2-methylphenyl)ethenyl]benzene Chemical compound CC1=CC=CC=C1\C=C\C(C=C1)=CC=C1\C=C\C1=CC=CC=C1C QKLPIYTUUFFRLV-YTEMWHBBSA-N 0.000 description 1
- BCASZEAAHJEDAL-PHEQNACWSA-N 1,4-bis[(e)-2-(4-methylphenyl)ethenyl]benzene Chemical compound C1=CC(C)=CC=C1\C=C\C(C=C1)=CC=C1\C=C\C1=CC=C(C)C=C1 BCASZEAAHJEDAL-PHEQNACWSA-N 0.000 description 1
- LWGPQZLNJIVUIC-UHFFFAOYSA-N 1,4-bis[2-(2-ethylphenyl)ethenyl]benzene Chemical compound CCC1=CC=CC=C1C=CC(C=C1)=CC=C1C=CC1=CC=CC=C1CC LWGPQZLNJIVUIC-UHFFFAOYSA-N 0.000 description 1
- SWYYRSGBEBXIRE-UHFFFAOYSA-N 1,4-bis[2-(3-ethylphenyl)ethenyl]benzene Chemical compound CCC1=CC=CC(C=CC=2C=CC(C=CC=3C=C(CC)C=CC=3)=CC=2)=C1 SWYYRSGBEBXIRE-UHFFFAOYSA-N 0.000 description 1
- XBDQJALUKGQTAV-UHFFFAOYSA-N 1,4-bis[2-(3-methylphenyl)ethenyl]benzene Chemical compound CC1=CC=CC(C=CC=2C=CC(C=CC=3C=C(C)C=CC=3)=CC=2)=C1 XBDQJALUKGQTAV-UHFFFAOYSA-N 0.000 description 1
- MVLGANVFCMOJHR-UHFFFAOYSA-N 1,4-diethynylbenzene Chemical compound C#CC1=CC=C(C#C)C=C1 MVLGANVFCMOJHR-UHFFFAOYSA-N 0.000 description 1
- QFUYDAGNUJWBSM-UHFFFAOYSA-N 1-iodo-2-phenylbenzene Chemical group IC1=CC=CC=C1C1=CC=CC=C1 QFUYDAGNUJWBSM-UHFFFAOYSA-N 0.000 description 1
- NHPPIJMARIVBGU-UHFFFAOYSA-N 1-iodonaphthalene Chemical compound C1=CC=C2C(I)=CC=CC2=C1 NHPPIJMARIVBGU-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- WQVIVQDHNKQWTM-UHFFFAOYSA-N 1-tert-butyl-4-iodobenzene Chemical compound CC(C)(C)C1=CC=C(I)C=C1 WQVIVQDHNKQWTM-UHFFFAOYSA-N 0.000 description 1
- YTDHEFNWWHSXSU-UHFFFAOYSA-N 2,3,5,6-tetrachloroaniline Chemical compound NC1=C(Cl)C(Cl)=CC(Cl)=C1Cl YTDHEFNWWHSXSU-UHFFFAOYSA-N 0.000 description 1
- SULWTXOWAFVWOY-PHEQNACWSA-N 2,3-bis[(E)-2-phenylethenyl]pyrazine Chemical class C=1C=CC=CC=1/C=C/C1=NC=CN=C1\C=C\C1=CC=CC=C1 SULWTXOWAFVWOY-PHEQNACWSA-N 0.000 description 1
- FZORBZJJXZJZDC-UHFFFAOYSA-N 2,5-bis(2-naphthalen-1-ylethenyl)pyrazine Chemical compound C1=CC=C2C(C=CC3=NC=C(N=C3)C=CC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 FZORBZJJXZJZDC-UHFFFAOYSA-N 0.000 description 1
- OWTKICLARQLANW-UHFFFAOYSA-N 2,5-bis(2-pyren-1-ylethenyl)pyrazine Chemical compound C1=C2C(C=CC3=NC=C(N=C3)C=CC=3C4=CC=C5C=CC=C6C=CC(C4=C65)=CC=3)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 OWTKICLARQLANW-UHFFFAOYSA-N 0.000 description 1
- ZGXQLVRLPJXTIK-LQIBPGRFSA-N 2,5-bis[(e)-2-(4-methoxyphenyl)ethenyl]pyrazine Chemical compound C1=CC(OC)=CC=C1\C=C\C(N=C1)=CN=C1\C=C\C1=CC=C(OC)C=C1 ZGXQLVRLPJXTIK-LQIBPGRFSA-N 0.000 description 1
- PAJSTGVSGZWCGO-UHFFFAOYSA-N 2,5-bis[2-(4-ethylphenyl)ethenyl]pyrazine Chemical compound C1=CC(CC)=CC=C1C=CC(N=C1)=CN=C1C=CC1=CC=C(CC)C=C1 PAJSTGVSGZWCGO-UHFFFAOYSA-N 0.000 description 1
- BFQSAUNFPAHVRZ-UHFFFAOYSA-N 2,5-bis[2-(4-methylphenyl)ethenyl]pyrazine Chemical compound C1=CC(C)=CC=C1C=CC(N=C1)=CN=C1C=CC1=CC=C(C)C=C1 BFQSAUNFPAHVRZ-UHFFFAOYSA-N 0.000 description 1
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 description 1
- BDMRRCGWWDZRRG-UHFFFAOYSA-N 2-[2-(4-chlorophenyl)ethenyl]benzo[e][1,3]benzoxazole Chemical compound C1=CC(Cl)=CC=C1C=CC(O1)=NC2=C1C=CC1=CC=CC=C21 BDMRRCGWWDZRRG-UHFFFAOYSA-N 0.000 description 1
- XFPKINQJEVMALK-UHFFFAOYSA-N 2-[4-[4-(1,3-benzoxazol-2-yl)phenyl]phenyl]-1,3-benzoxazole Chemical group C1=CC=C2OC(C3=CC=C(C=C3)C3=CC=C(C=C3)C=3OC4=CC=CC=C4N=3)=NC2=C1 XFPKINQJEVMALK-UHFFFAOYSA-N 0.000 description 1
- SMRCQMRVIVSYOX-UHFFFAOYSA-N 2-[5-[5,7-bis(2-methylbutan-2-yl)-1,3-benzoxazol-2-yl]-1,3,4-thiadiazol-2-yl]-5,7-bis(2-methylbutan-2-yl)-1,3-benzoxazole Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=C2OC(C3=NN=C(S3)C=3OC4=C(C=C(C=C4N=3)C(C)(C)CC)C(C)(C)CC)=NC2=C1 SMRCQMRVIVSYOX-UHFFFAOYSA-N 0.000 description 1
- HNPLZFFFNHWZPM-UHFFFAOYSA-N 2-[5-[5,7-bis(2-methylbutan-2-yl)-1,3-benzoxazol-2-yl]-3,4-diphenylthiophen-2-yl]-5,7-bis(2-methylbutan-2-yl)-1,3-benzoxazole Chemical compound N=1C2=CC(C(C)(C)CC)=CC(C(C)(C)CC)=C2OC=1C=1SC(C=2OC3=C(C=C(C=C3N=2)C(C)(C)CC)C(C)(C)CC)=C(C=2C=CC=CC=2)C=1C1=CC=CC=C1 HNPLZFFFNHWZPM-UHFFFAOYSA-N 0.000 description 1
- MUMFNDFRZDYMNG-UHFFFAOYSA-N 2-[5-[5,7-bis(2-methylbutan-2-yl)-1,3-benzoxazol-2-yl]thiophen-2-yl]-5,7-bis(2-methylbutan-2-yl)-1,3-benzoxazole Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=C2OC(C3=CC=C(S3)C=3OC4=C(C=C(C=C4N=3)C(C)(C)CC)C(C)(C)CC)=NC2=C1 MUMFNDFRZDYMNG-UHFFFAOYSA-N 0.000 description 1
- TZUPZYHCGXBTIJ-UHFFFAOYSA-N 2-ethyl-1,4-bis[2-(2-methylphenyl)ethenyl]benzene Chemical compound C=1C=C(C=CC=2C(=CC=CC=2)C)C(CC)=CC=1C=CC1=CC=CC=C1C TZUPZYHCGXBTIJ-UHFFFAOYSA-N 0.000 description 1
- SVNTXZRQFPYYHV-UHFFFAOYSA-N 2-methyl-1,4-bis[2-(2-methylphenyl)ethenyl]benzene Chemical compound CC1=CC=CC=C1C=CC(C=C1C)=CC=C1C=CC1=CC=CC=C1C SVNTXZRQFPYYHV-UHFFFAOYSA-N 0.000 description 1
- HQPIRXQACTZROS-UHFFFAOYSA-N 4-[2-(1h-benzimidazol-2-yl)ethenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C=CC1=NC2=CC=CC=C2N1 HQPIRXQACTZROS-UHFFFAOYSA-N 0.000 description 1
- UYEBVQUTQHTYOU-UHFFFAOYSA-N 5-methyl-2-[4-[2-(5-methyl-1,3-benzoxazol-2-yl)ethenyl]phenyl]-1,3-benzoxazole Chemical compound CC1=CC=C2OC(C3=CC=C(C=C3)C=CC=3OC4=CC=C(C=C4N=3)C)=NC2=C1 UYEBVQUTQHTYOU-UHFFFAOYSA-N 0.000 description 1
- XPLXHDHGYSONMX-UHFFFAOYSA-N 5-methyl-2-[5-(5-methyl-1,3-benzoxazol-2-yl)thiophen-2-yl]-1,3-benzoxazole Chemical compound CC1=CC=C2OC(C3=CC=C(S3)C=3OC4=CC=C(C=C4N=3)C)=NC2=C1 XPLXHDHGYSONMX-UHFFFAOYSA-N 0.000 description 1
- WPYMZALMVVFPJZ-UHFFFAOYSA-N 6,7,15,16,24,25,33,34-octamethyl-2,11,20,29,37,38,39,40-octazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1,3,5,7,9,11,13(18),14,16,19,21(38),22(27),23,25,28,30(37),31(36),32,34-nonadecaene Chemical compound N1=C(N=C2[C]3C=C(C)C(C)=CC3=C(N=C3C4=CC(C)=C(C)C=C4C(=N4)N3)N2)[C](C=C(C(C)=C2)C)C2=C1N=C1C2=CC(C)=C(C)C=C2C4=N1 WPYMZALMVVFPJZ-UHFFFAOYSA-N 0.000 description 1
- CFNMUZCFSDMZPQ-GHXNOFRVSA-N 7-[(z)-3-methyl-4-(4-methyl-5-oxo-2h-furan-2-yl)but-2-enoxy]chromen-2-one Chemical compound C=1C=C2C=CC(=O)OC2=CC=1OC/C=C(/C)CC1OC(=O)C(C)=C1 CFNMUZCFSDMZPQ-GHXNOFRVSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OQFCTJNGGQEMMF-UHFFFAOYSA-M CC(C=CC1=CC=C2)=NC1=C2[O-].CC(C=CC1=CC=C2)=NC1=C2O.[O-2].[Al+3] Chemical compound CC(C=CC1=CC=C2)=NC1=C2[O-].CC(C=CC1=CC=C2)=NC1=C2O.[O-2].[Al+3] OQFCTJNGGQEMMF-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- SBAUTRQODRAAMY-UHFFFAOYSA-N calcium;5-chloroquinolin-8-ol Chemical compound [Ca].C1=CN=C2C(O)=CC=C(Cl)C2=C1.C1=CN=C2C(O)=CC=C(Cl)C2=C1 SBAUTRQODRAAMY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- CTQMJYWDVABFRZ-UHFFFAOYSA-N cloxiquine Chemical compound C1=CN=C2C(O)=CC=C(Cl)C2=C1 CTQMJYWDVABFRZ-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- BQWXRCGBXCQIAB-UHFFFAOYSA-N copper 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin Chemical compound [Cu+2].C1(=CC=CC=C1)C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)C5=CC=CC=C5)N4)C4=CC=CC=C4)N3)C3=CC=CC=C3)=N2 BQWXRCGBXCQIAB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001352 cyclobutyloxy group Chemical group C1(CCC1)O* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001887 cyclopentyloxy group Chemical group C1(CCCC1)O* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000000131 cyclopropyloxy group Chemical group C1(CC1)O* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- HQQKMOJOCZFMSV-UHFFFAOYSA-N dilithium phthalocyanine Chemical compound [Li+].[Li+].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 HQQKMOJOCZFMSV-UHFFFAOYSA-N 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- LBAIJNRSTQHDMR-UHFFFAOYSA-N magnesium phthalocyanine Chemical compound [Mg].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 LBAIJNRSTQHDMR-UHFFFAOYSA-N 0.000 description 1
- MOOHXQFFIPDLNX-UHFFFAOYSA-N magnesium;quinolin-8-ol Chemical compound [Mg].C1=CN=C2C(O)=CC=CC2=C1.C1=CN=C2C(O)=CC=CC2=C1 MOOHXQFFIPDLNX-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical group C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- SRPIEPRXRTXWAD-UHFFFAOYSA-N n-acetyl-n-[4-(4-aminophenyl)phenyl]acetamide Chemical compound C1=CC(N(C(C)=O)C(=O)C)=CC=C1C1=CC=C(N)C=C1 SRPIEPRXRTXWAD-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- JACPFCQFVIAGDN-UHFFFAOYSA-M sipc iv Chemical compound [OH-].[Si+4].CN(C)CCC[Si](C)(C)[O-].C=1C=CC=C(C(N=C2[N-]C(C3=CC=CC=C32)=N2)=N3)C=1C3=CC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 JACPFCQFVIAGDN-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical compound C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は有機エレクトロルミ
ネッセンス素子（以下、有機ＥＬ素子と略称する）及び
これに適するジアミン誘導体に関し、さらに詳しくは、
精製が容易で、各種溶媒に対し極めて良好な溶解性を示
す特定のジアミン化合物及び、これを含有する、極めて
長寿命の有機ＥＬ素子に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescence device (hereinafter abbreviated as organic EL device) and a diamine derivative suitable for the device, and more specifically,
The present invention relates to a specific diamine compound which can be easily purified and has extremely good solubility in various solvents, and an organic EL device containing the same, which has an extremely long life.
【０００２】[0002]
【従来の技術】電界発光を利用したＥＬ素子は、自己発
光のため視認性が高く、かつ完全固体素子であるため、
耐衝撃性に優れるなどの特徴を有することから、各種表
示装置における発光素子としての利用が注目されてい
る。このＥＬ素子には、発光材料に無機化合物を用いて
なる無機ＥＬ素子と有機化合物を用いてなる有機ＥＬ素
子とがあり、このうち、有機ＥＬ素子は、印加電圧を大
幅に低くしうる小型化が容易であるために、次世代の表
示素子としてその実用化研究が積極的になされている。
この有機ＥＬ素子の構成については、陽極／有機発光層
／陰極の構成を基本とし、これに正孔輸送層や電子注入
層を適宜設けたもの、例えば陽極／正孔輸送層／有機発
光層／陰極や、陽極／正孔輸送層／有機発光層／電子注
入層／陰極などの構成のものが知られている。該正孔輸
送層は、陽極より注入された正孔を発光層に伝達する機
能を有し、また、電子注入層は陰極より注入された電子
を有機発光層に伝達する機能を有している。そして、該
正孔輸送層を有機発光層と陽極との間に介在させること
によって、より低い電界で多くの正孔が有機発光層に注
入され、さらに、有機発光層に陰極又は電子注入層より
注入された電子は、正孔輸送層が電子を輸送しないの
で、正孔輸送層と有機発光層との界面に蓄積され発光効
率が上がることが知られている。このような有機ＥＬ素
子の正孔輸送材料として、ナフチル基を有するジアミン
誘導体が優れていることが米国特許第5,０６1,５６９号
明細書に開示されている。また、電子写真感光体の分野
においては電荷輸送材料として、ナフチル基を有するジ
アミン誘導体を使用することが特開平１−１４２６５７
号公報に開示されている。2. Description of the Related Art An EL element utilizing electroluminescence has high visibility because it is self-luminous and is a completely solid-state element.
Due to its characteristics such as excellent impact resistance, attention has been paid to its use as a light emitting element in various display devices. This EL element includes an inorganic EL element that uses an inorganic compound as a light-emitting material and an organic EL element that uses an organic compound. Among these, the organic EL element is a miniaturized one in which an applied voltage can be significantly lowered. Since it is easy to manufacture, practical studies are being actively conducted as a next-generation display element.
The structure of this organic EL element is based on the structure of anode / organic light emitting layer / cathode, and a hole transport layer or electron injection layer is appropriately provided on it, for example, anode / hole transport layer / organic light emitting layer / There are known cathodes and anodes / hole transport layers / organic light-emitting layers / electron injection layers / cathodes. The hole transport layer has a function of transmitting holes injected from the anode to the light emitting layer, and the electron injection layer has a function of transmitting electrons injected from the cathode to the organic light emitting layer. . By interposing the hole transport layer between the organic light emitting layer and the anode, a large number of holes are injected into the organic light emitting layer at a lower electric field, and further, the organic light emitting layer is injected from the cathode or the electron injecting layer. It is known that the injected electrons are accumulated at the interface between the hole transport layer and the organic light emitting layer because the hole transport layer does not transport the electrons, and the luminous efficiency is improved. It is disclosed in US Pat. No. 5,061,569 that a diamine derivative having a naphthyl group is excellent as a hole transport material for such an organic EL device. Further, in the field of electrophotographic photoreceptors, it is preferable to use a diamine derivative having a naphthyl group as a charge transport material.
No. 6,086,045.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、これら
のナフチル基を有するジアミン誘導体はいずれも各種溶
媒に対する溶解度が低いものであり、このため精製が極
めて困難なものであった。更に、このような化合物を正
孔輸送層などに用いた有機ＥＬ素子においては、長時間
連続駆動させると発光輝度が低下する等の問題があり、
実用化の大きな障害となっていた。本発明はこのような
状況下でなされたものである。すなわち、本発明は、各
種溶媒に対して極めて溶解性が高く、精製が容易であ
り、有機ＥＬ素子あるいは電子写真感光体に用いた場
合、安定性に優れた長寿命の素子あるいは感光体を与え
る新規なジアミン誘導体を提供すること、及び該ジアミ
ン誘導体を用いることにより長時間連続駆動においても
優れた発光安定性を示す長寿命な有機ＥＬ素子を提供す
ることを目的とするものである。However, all of these diamine derivatives having a naphthyl group have low solubility in various solvents, and therefore purification was extremely difficult. Furthermore, in an organic EL device using such a compound in a hole transport layer or the like, there is a problem that the emission luminance is lowered when continuously driven for a long time,
It was a big obstacle to practical use. The present invention has been made under such circumstances. That is, the present invention provides an element or a photoconductor that has a very high solubility in various solvents, is easy to purify, and has excellent stability when used for an organic EL device or an electrophotographic photoconductor. It is an object of the present invention to provide a novel diamine derivative, and to provide a long-life organic EL device that exhibits excellent emission stability even when continuously driven for a long time by using the diamine derivative.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意研究を重ねた結果、特定の構造を有
するナフチル基を有するジアミン誘導体が、各種溶媒に
対して極めて高い溶解性を示し、精製が容易であり、こ
れを、特に、正孔輸送層材料あるいは電荷輸送材料など
として用いることにより、長寿命な有機ＥＬ素子あるい
は電子写真感光体が得られ、前記目的を達成しうること
を見出した。本発明は、かかる知見に基づいて完成した
ものである。すなわち、本発明は、下記一般式（Ｉ）で
表されるジアミン誘導体、及び該ジアミン誘導体を用い
ることを特徴とする有機エレクトロルミネッセンス素子
を提供するものである。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that diamine derivatives having a naphthyl group having a specific structure have extremely high solubility in various solvents. It is easy to purify, and by using this as a hole transport layer material or a charge transport material, a long-life organic EL device or electrophotographic photoreceptor can be obtained, and the above object can be achieved. I found that. The present invention has been completed based on such findings. That is, the present invention provides a diamine derivative represented by the following general formula (I), and an organic electroluminescence device characterized by using the diamine derivative.
【０００５】[0005]
【化２】 （式中、Ｘ1 〜Ｘ10はそれぞれ水素，炭素数２〜６のア
ルキル基，炭素数２〜６のアルコキシ基又はフェニル基
であり、Ｘ1 〜Ｘ5 の少なくともひとつ及びＸ6〜Ｘ10
の少なくともひとつは炭素数２〜６のアルキル基，炭素
数２〜６のアルコキシ基又はフェニル基である。また、
Ｘ1 〜Ｘ10はそれぞれ互いに同一でも異なっていてもよ
い。）Embedded image (In the formula, X 1 to X 10 are each hydrogen, an alkyl group having 2 to 6 carbon atoms, an alkoxy group having 2 to 6 carbon atoms, or a phenyl group, and at least one of X 1 to X 5 and X 6 to X 10;
At least one of them is an alkyl group having 2 to 6 carbon atoms, an alkoxy group having 2 to 6 carbon atoms, or a phenyl group. Also,
X 1 to X 10 may be the same or different from each other. )
【０００６】以下に、本発明を更に詳細に説明する。本
発明のジアミン誘導体は、上記一般式（Ｉ）で表される
もの（以下、「本発明のジアミン誘導体」ということが
ある）である。一般式（Ｉ）において、Ｘ1 〜Ｘ10のそ
れぞれで表される炭素数２〜６のアルキル基としては、
例えば、エチル基，ｎ−プロピル基，イソプロピル基，
ｎ−ブチル基，ｓｅｃ−ブチル基，ｔｅｒｔ−ブチル
基，ｎ−ペンチル基，ｎ−ヘキシル基，シクロプロピル
基，シクロブチル基，シクロペンチル基，シクロヘキシ
ル基等が挙げられる。また、Ｘ1 〜Ｘ10のそれぞれで表
される炭素数２〜６のアルコキシ基の例としては、エト
キシ基，ｎ−プロポキシ基，イソプロポキシ基，ｎ−ブ
トキシ基，ｓｅｃ−ブトキシ基，ｔｅｒｔ−ブトキシ
基，ｎ−ペントキシ基，ｎ−ヘキソキシ基，シクロプロ
ポキシ基，シクロブトキシ基，シクロペントキシ基，シ
クロヘキソキシ基等が挙げられる。Hereinafter, the present invention will be described in more detail. The diamine derivative of the present invention is represented by the above general formula (I) (hereinafter, may be referred to as “diamine derivative of the present invention”). In the general formula (I), the alkyl group having 2 to 6 carbon atoms represented by each of X 1 to X 10 is
For example, ethyl group, n-propyl group, isopropyl group,
Examples thereof include n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group. Further, examples of the alkoxy group having 2 to 6 carbon atoms represented by each of X 1 to X 10 include ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert- Examples thereof include butoxy group, n-pentoxy group, n-hexoxy group, cyclopropoxy group, cyclobutoxy group, cyclopentoxy group and cyclohexoxy group.
【０００７】上記アルキル基あるいはアルコキシ基の炭
素数が２より少ない場合は溶媒に対する溶解度が小さく
精製が困難であり、また６を超える場合は昇華性が悪く
なり、蒸着による薄膜形成が困難となり好ましくない。
従って、本発明においては上記アルキル基あるいはアル
コキシ基の炭素数は２〜４であることが更に好ましい。
本発明においては、上記Ｘ1 〜Ｘ10のそれぞれで表され
る基として、ＥＬ素子などに用いた場合、初期性能に優
れること，長寿命であること等の点から好ましくは、エ
チル基，イソプロピル基，ｔｅｒｔ−ブチル基，エトキ
シ基，フェニル基を挙げることができる。When the number of carbon atoms of the alkyl group or alkoxy group is less than 2, solubility in a solvent is small and purification is difficult, and when it exceeds 6, sublimability deteriorates and it is difficult to form a thin film by vapor deposition, which is not preferable. .
Therefore, in the present invention, it is more preferable that the alkyl group or the alkoxy group has 2 to 4 carbon atoms.
In the present invention, when the group represented by each of the above X 1 to X 10 is used in an EL device or the like, it is preferably an ethyl group or an isopropyl group from the viewpoint of excellent initial performance and long life. Group, tert-butyl group, ethoxy group, phenyl group.
【０００８】本発明においては、一般式（Ｉ）において
Ｘ1 〜Ｘ5 の少なくとも一つ及びＸ 6 〜Ｘ10の少なくと
も一つ、好ましくはＸ1 〜Ｘ5 の一つ及びＸ6 〜Ｘ10の
一つが上記炭素数２〜６のアルキル基，炭素数２〜６の
アルコキシ基又はフェニル基である。上記置換基を有す
ることにより、本発明の化合物は各種溶媒に対し高い溶
解度を示すことができ、また精製が容易なものとなる。
本発明のジアミン誘導体としては、具体的には下記の化
合物が挙げられる。In the present invention, in the general formula (I)
X1~ XFiveAt least one of and X 6~ XTenAt least
Also one, preferably X1~ XFiveOne and X6~ XTenof
One is an alkyl group having 2 to 6 carbon atoms, or 2 to 6 carbon atoms
It is an alkoxy group or a phenyl group. Has the above substituents
Therefore, the compound of the present invention is highly soluble in various solvents.
The degree of resolution can be shown and the purification is easy.
As the diamine derivative of the present invention, specifically,
Compounds.
【０００９】[0009]
【化３】 Embedded image
【００１０】[0010]
【化４】 Embedded image
【００１１】[0011]
【化５】 Embedded image
【００１２】[0012]
【化６】 ここで、ｎ−Ｃ3 Ｈ7 −，ｎ−Ｃ4 Ｈ9 −，ｎ−Ｃ5 Ｈ
11−，ｎ−Ｃ6 Ｈ13−の各基は各々ｎ−プロピル基，ｎ
−ブチル基，ｎ−ペンチル基，ｎ−ヘキシルを示し、ｉ
−Ｃ3 Ｈ7 −はイソプロピル基を、ｓ−Ｃ4 Ｈ9 −はｓ
ｅｃ−ブチル基を、ｔ−Ｃ4 Ｈ9 −はｔｅｒｔ−ブチル
基を示す。また、−ＯＣ3 Ｈ7 （ｎ），−ＯＣ4 Ｈ
9 （ｎ），−ＯＣ5 Ｈ11（ｎ），−ＯＣ6 Ｈ13（ｎ）の
各基は各々ｎ−プロポキシ基，ｎ−ブトキシ基，ｎ−ペ
ントキシ基，ｎ−ヘキソキシ基を示し、−ＯＣ3 Ｈ
7 （ｉ）はイソプロポキシ基を、−ＯＣ4 Ｈ9 （ｓ）は
ｓｅｃ−ブトキシ基を、−ＯＣ4 Ｈ9 （ｔ）はｔｅｒｔ
−ブトキシ基を示す。これらは一種用いてもよく、二種
以上を組み合わせて用いてもよい。[Chemical 6] Here, n-C 3 H 7 - , n-C 4 H 9 -, n-C 5 H
11 -, n-C 6 H 13 - Each group of each n- propyl radical, n
-Butyl group, n-pentyl group, n-hexyl, i
-C 3 H 7 - an isopropyl group, s-C 4 H 9 - is s
The ec- butyl group, t-C 4 H 9 - shows a tert- butyl group. Further, -OC 3 H 7 (n) , - OC 4 H
Each group of 9 (n), -OC 5 H 11 (n), -OC 6 H 13 (n) represents an n-propoxy group, an n-butoxy group, an n-pentoxy group, an n-hexoxy group, OC 3 H
7 (i) is an isopropoxy group, -OC 4 H 9 (s) is a sec-butoxy group, and -OC 4 H 9 (t) is tert.
Represents a butoxy group. These may be used alone or in combination of two or more.
【００１３】有機ＥＬ素子の構造としては、陽極／有
機発光層／陰極、陽極／正孔輸送層／有機発光層／陰
極、陽極／有機発光層／電子注入層／陰極、陽極／
正孔輸送層／有機発光層／電子注入層／陰極などがある
が、本発明の有機ＥＬ素子は、一対の電極（陽極と陰
極）により挾持された化合物層（上記の構成の素子に
おいては有機発光層、の構成の素子においては正孔輸
送層及び有機発光層、の構成の素子においては有機発
光層及び電子注入層、の構成の素子においては正孔輸
送層，有機発光層及び電子注入層）の少なくとも一層
が、上記一般式（Ｉ）で表されるジアミン誘導体を含ん
でいれば、上記〜のいずれの構成であってもよい。
なお、これらの構成の有機ＥＬ素子は、いずれも基板に
より支持されることが好ましい。この基板については特
に制限はなく、従来の有機ＥＬ素子に慣用されているも
の、例えばガラス，透明プラスチック，石英などからな
るものを用いることができる。The structure of the organic EL device is as follows: anode / organic light emitting layer / cathode, anode / hole transport layer / organic light emitting layer / cathode, anode / organic light emitting layer / electron injection layer / cathode, anode /
There is a hole transport layer / organic light emitting layer / electron injection layer / cathode, etc., but the organic EL device of the present invention is a compound layer sandwiched by a pair of electrodes (anode and cathode) A light emitting layer, a hole transport layer and an organic light emitting layer in the element, and a light emitting layer, an organic light emitting layer and an electron injection layer in the element, and a hole transport layer, an organic light emitting layer and an electron injection layer in the element If at least one layer of the above) contains the diamine derivative represented by the above general formula (I), any of the above configurations may be adopted.
In addition, it is preferable that the organic EL elements having these configurations are all supported by the substrate. The substrate is not particularly limited, and those commonly used in conventional organic EL devices, for example, those made of glass, transparent plastic, quartz or the like can be used.
【００１４】本発明の有機ＥＬ素子の特徴部分である本
発明のジアミン誘導体を含む層は、正孔輸送層又は有機
発光層であることが望ましく、特に正孔輸送層であるこ
とが好ましい。上記ジアミン誘導体を含む正孔輸送層
は、該ジアミン誘導体のみからなる単層構造でもよい
し、該ジアミン誘導体と、有機ＥＬ素子の正孔輸送層材
料として従来より使用されている物質の層との複層構造
であってもよい。さらには、該ジアミン誘導体と有機Ｅ
Ｌ素子の正孔輸送層材料として従来より使用されている
物質との混合物からなる層を含む単層構造又は複層構造
であってもよい。The layer containing the diamine derivative of the present invention, which is a characteristic part of the organic EL device of the present invention, is preferably a hole transport layer or an organic light emitting layer, and particularly preferably a hole transport layer. The hole-transporting layer containing the diamine derivative may have a single-layer structure consisting of only the diamine derivative, or a layer of the diamine derivative and a substance conventionally used as a hole-transporting layer material for an organic EL device. It may have a multilayer structure. Furthermore, the diamine derivative and organic E
It may have a single-layer structure or a multi-layer structure including a layer made of a mixture with a substance conventionally used as a hole transport layer material of an L element.
【００１５】本発明のジアミン誘導体を含む正孔輸送層
は、該ジアミン誘導体と、必要に応じて他の正孔輸送層
材料とを用いて、真空蒸着法，キャスト法，塗布法，ス
ピンコート法などにより形成することができる。さらに
は、ポリカーボネート，ポリウレタン，ポリスチレン，
ポリアリレート，ポリエステルなどの透明ポリマーに、
該ジアミン誘導体を分散させた溶液を用いたキャスト
法、塗布法あるいはスピンコート法などや、透明ポリマ
ーとの同時蒸着などによっても形成することができる。
また、本発明のジアミン誘導体を含む有機発光層は、該
ジアミン誘導体のみからなる単層構造であってもよい
し、該ジアミン誘導体と、有機ＥＬ素子の有機発光層材
料として従来より使用されている物質の層との複層構造
であっもよい。さらには、該ジアミン誘導体と有機ＥＬ
素子の有機発光層材料として従来より使用されている物
質との混合物からなる層を含む単層構造又は複層構造で
あってもよい。該ジアミン誘導体を含む有機発光層は、
該ジアミン誘導体と、必要に応じて他の有機発光層材料
とを用いて、真空蒸着法，キャスト法，塗布法，スピン
コート法などにより形成することができる。The hole transporting layer containing the diamine derivative of the present invention is prepared by using the diamine derivative and, if necessary, another hole transporting layer material, in vacuum deposition method, casting method, coating method, spin coating method. And the like. Furthermore, polycarbonate, polyurethane, polystyrene,
For transparent polymers such as polyarylate and polyester,
It can also be formed by a casting method using a solution in which the diamine derivative is dispersed, a coating method, a spin coating method, or the like, or simultaneous vapor deposition with a transparent polymer.
Further, the organic light emitting layer containing the diamine derivative of the present invention may have a single-layer structure composed of only the diamine derivative, or has been conventionally used as the organic light emitting layer material of the diamine derivative and the organic EL device. It may be a multi-layer structure with a layer of material. Furthermore, the diamine derivative and organic EL
It may have a single-layer structure or a multi-layer structure including a layer composed of a mixture with a substance conventionally used as a material for an organic light-emitting layer of the device. The organic light emitting layer containing the diamine derivative,
The diamine derivative and, if necessary, other organic light emitting layer material can be formed by a vacuum deposition method, a casting method, a coating method, a spin coating method or the like.
【００１６】本発明の有機ＥＬ素子において、本発明の
ジアミン誘導体を含む層以外は、従来の有機ＥＬ素子と
同様の材料を用いて形成するこができる。例えば、陽極
の材料としては、仕事関数の大きい（４ｅＶ以上）金
属，合金，電気伝導性化合物又はこれらの混合物が好ま
しく用いられる。具体例としては、Ａｕなどの金属，Ｃ
ｕＩ，ＩＴＯ，ＳｎＯ2 ，ＺｎＯなどの誘電性透明材料
が挙げられる。この陽極は、例えば蒸着法やスパッタリ
ング法などの方法で、上記材料の薄膜を形成することに
より作製することができる。有機発光層からの発光を陽
極より取り出す場合、該陽極の透過率は１０％より大き
いことが望ましい。また、陽極のシート抵抗は数百Ω／
□以下が好ましい。この陽極の膜厚は材料にもよるが、
通常１０ｎｍ〜１μｍ、好ましくは１０〜２００ｎｍの
範囲で選択される。The organic EL device of the present invention can be formed by using the same material as that of the conventional organic EL device except the layer containing the diamine derivative of the present invention. For example, as the material of the anode, a metal, an alloy, an electrically conductive compound having a large work function (4 eV or more), or a mixture thereof is preferably used. As a specific example, a metal such as Au, C
Dielectric transparent materials such as uI, ITO, SnO 2 and ZnO can be used. The anode can be manufactured by forming a thin film of the above material by a method such as a vapor deposition method or a sputtering method. When light emitted from the organic light emitting layer is taken out from the anode, the transmittance of the anode is desirably greater than 10%. The sheet resistance of the anode is several hundred Ω /
□ The following is preferable. The thickness of this anode depends on the material,
Usually, it is selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm.
【００１７】一方、陰極の材料としては、仕事関数の小
さい（４ｅＶ以下）金属，合金，電気伝導性化合物又は
これらの混合物が好ましく用いられる。該陰極材料の具
体例としては、ナトリウム，リチウム，マグネシウム／
銅混合物，Ａｌ／Ａｌ2 Ｏ3，インジウムなどが挙げら
れる。この陰極は、蒸着法やスパッタリング法などの方
法で、上記材料の薄膜を形成することにより作製するこ
とができる。有機発光層からの発光を陰極より取り出す
場合、該陰極の透過率は１０％より大きいことが望まし
い。また、この陰極のシート抵抗は数百Ω／□以下が好
ましい。該陰極の膜厚は材料にもよるが、通常１０ｎｍ
〜１μｍ、好ましくは５０〜２００ｎｍの範囲で選択さ
れる。なお、有機発光層からの発光を効率よく取り出す
観点からは、上記陽極及び陰極の少なくとも一方を透明
又は半透明物質により形成するのが好ましい。On the other hand, as a material of the cathode, a metal, an alloy, an electrically conductive compound having a small work function (4 eV or less), or a mixture thereof is preferably used. Specific examples of the cathode material include sodium, lithium and magnesium.
Copper mixture, Al / Al 2 O 3 , indium and the like can be mentioned. This cathode can be manufactured by forming a thin film of the above material by a method such as an evaporation method or a sputtering method. When light emitted from the organic light emitting layer is taken out from the cathode, it is desirable that the transmittance of the cathode is greater than 10%. The sheet resistance of the cathode is preferably several hundred Ω / □ or less. The thickness of the cathode depends on the material, but is usually 10 nm.
˜1 μm, preferably 50 to 200 nm. From the viewpoint of efficiently extracting the light emitted from the organic light emitting layer, at least one of the anode and the cathode is preferably formed of a transparent or semitransparent substance.
【００１８】また、本発明の有機ＥＬ素子における有機
発光層を、本発明のジアミン誘導体と他の物質とにより
形成する場合、ジアミン誘導体以外の他の有機発光層材
料としては、例えば多環縮合芳香族化合物や、ベンゾオ
キサゾール系，ベンジチアゾール系，ベンゾイミダゾー
ル系などの蛍光増白剤，金属キレート化オキサノイド化
合物、ジスチリルベンゼン系化合物などの薄膜形成性の
良い化合物を用いることができる。ここで、上記多環縮
合芳香族化合物の具体例としては、アセトラセン，ナフ
タレン，フェナントレン，ピレン，クリセン，ペリレン
骨格などを含む縮合環発光物質や、８〜２０個、好まし
くは８個の縮合環を含む他の縮合環発光物質などが挙げ
られる。When the organic light emitting layer in the organic EL device of the present invention is formed of the diamine derivative of the present invention and another substance, examples of the organic light emitting layer material other than the diamine derivative include polycyclic condensed aromatic compounds. Group compounds, fluorescent brightening agents such as benzoxazole-based, benzthiazole-based, and benzimidazole-based compounds, metal chelated oxanoide compounds, and distyrylbenzene-based compounds that can form thin films can be used. Here, specific examples of the polycyclic fused aromatic compound include a fused ring light-emitting substance containing an acetracene, naphthalene, phenanthrene, pyrene, chrysene, and perylene skeleton, and 8 to 20, preferably 8 fused rings. Other fused ring light-emitting substances are included.
【００１９】また、上記ベンゾオキサゾール系，ベンゾ
チアゾール系，ベンゾイミダゾール系などの蛍光増白剤
としては、例えば、特開昭５９−１９４３９３号公報に
開示されているものが挙げられる。その代表例として
は、２，５−ビス（５，７−ジ−ｔ−ペンチル−２−ベ
ンゾオキサゾリル）−１，３，４−チアジアゾール；
４，４’−ビス（５，７−ｔ−ペンチル−２−ベンゾオ
キサゾリル）スチルベン；４，４’−ビス（５，７−ジ
−（２−メチル−２−ブチル）−２−ベンゾオキサゾリ
ル）スチルベン；２，５−ビス（５，７−ジ−ｔ−ペン
チル−２−ベンゾオキサゾリル）チオフェン；２，５−
ビス（５−（α，α−ジメチルベンジル）−２−ベンゾ
オキサゾリル）チオフェン；２，５−ビス（５，７−ジ
−（２−メチル−２−ブチル）−２−ベンゾオキサゾリ
ル）−３，４−ジフェニルチオフェン；２，５−ビス
（５−メチル−２−ベンゾオキサゾリル）チオフェン；
４，４’−ビス（２−ベンゾオキサゾリル）ビフェニ
ル；５−メチル−２−（２−（４−（５−メチル−２−
ベンゾオキサゾリル）フェニル）ビニル）ベンゾオキサ
ゾール；２−（２−（４−クロロフェニル）ビニル）ナ
フト（１，２−ｄ）オキサゾールなどのベンゾオキサゾ
ール系、２，２’−（ｐ−フェニレンジビニレン）−ビ
スベンゾチアゾールなどのベンゾチアゾール系、２−
（２−（４−カルボキシフェニル）ビニル）ベンゾイミ
ダゾールなどのベンゾイミダゾール系などの蛍光増白剤
が挙げられる。Examples of the above-mentioned benzoxazole-based, benzothiazole-based, benzimidazole-based fluorescent whitening agents include those disclosed in JP-A-59-194393. Typical examples thereof include 2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl) -1,3,4-thiadiazole;
4,4'-bis (5,7-t-pentyl-2-benzoxazolyl) stilbene; 4,4'-bis (5,7-di- (2-methyl-2-butyl) -2-benzo Oxazolyl) stilbene; 2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl) thiophene; 2,5-
Bis (5- (α, α-dimethylbenzyl) -2-benzoxazolyl) thiophene; 2,5-bis (5,7-di- (2-methyl-2-butyl) -2-benzoxazolyl ) -3,4-Diphenylthiophene; 2,5-bis (5-methyl-2-benzoxazolyl) thiophene;
4,4'-bis (2-benzoxazolyl) biphenyl; 5-methyl-2- (2- (4- (5-methyl-2-
Benzoxazolyl) phenyl) vinyl) benzoxazole; benzoxazoles such as 2- (2- (4-chlorophenyl) vinyl) naphtho (1,2-d) oxazole, 2,2 ′-(p-phenylenedivinylene) ) -Bisbenzothiazole and other benzothiazoles, 2-
Fluorescent brighteners such as benzimidazole based ones such as (2- (4-carboxyphenyl) vinyl) benzimidazole can be mentioned.
【００２０】上記金属キレート化オキサノイド化合物と
しては、例えば特開昭６３−２９５６９５号公報に開示
されているものを用いることができる。その代表例とし
ては、トリス（８−キノリノール）アルミニウム，ビス
（８−キノリノール）マグネシウム，ビス（ベンゾ
（ｆ）−８−キノリノール）亜鉛，ビス（２−メチル−
８−キノリノラート）アルミニウムオキシド，トリス
（８−キノリノール）インジウム，トリス（５−メチル
−８−キノリノール）アルミニウム，８−キノリノール
リチウム，トリス（５−クロロ−８−キノリノール）ガ
リウム，ビス（５−クロロ−８−キノリノール）カルシ
ウム，ポリ（亜鉛（II) −ビス（８−ヒドロキシ−５−
キノリノニル）メタン）などの８−ヒドロキシキノリン
系金属錯体やジリチウムエピンドリジオンなどが挙げら
れる。また、上記ジスチリルベンゼン系化合物として
は、例えば欧州特許第０３７３５８２号明細書に開示さ
れているものを用いることができる。その代表例として
は、１，４−ビス（２−メチルスチリル）ベンゼン；
１，４−ビス（３−メチルスチリル）ベンゼン；１，４
−ビス（４−メチルスチリル）ベンゼン；ジスチリルベ
ンゼン；１，４−ビス（２−エチルスチリル）ベンゼ
ン；１，４−ビス（３−エチルスチリル）ベンゼン；
１，４−ビス（２−メチルスチリル）−２−メチルベン
ゼン；１，４−ビス（２−メチルスチリル）−２−エチ
ルベンゼンなどが挙げられる。As the metal chelated oxanoide compound, for example, those disclosed in JP-A-63-295695 can be used. Representative examples are tris (8-quinolinol) aluminum, bis (8-quinolinol) magnesium, bis (benzo (f) -8-quinolinol) zinc, bis (2-methyl-
8-quinolinolate) aluminum oxide, tris (8-quinolinol) indium, tris (5-methyl-8-quinolinol) aluminum, lithium 8-quinolinol, tris (5-chloro-8-quinolinol) gallium, bis (5-chloro- 8-quinolinol) calcium, poly (zinc (II) -bis (8-hydroxy-5-
Examples thereof include 8-hydroxyquinoline-based metal complexes such as quinolinonyl) methane) and dilithium epindridione. As the distyrylbenzene compound, for example, those disclosed in European Patent No. 0373582 can be used. As a typical example thereof, 1,4-bis (2-methylstyryl) benzene;
1,4-bis (3-methylstyryl) benzene; 1,4
-Bis (4-methylstyryl) benzene; distyrylbenzene; 1,4-bis (2-ethylstyryl) benzene; 1,4-bis (3-ethylstyryl) benzene;
1,4-bis (2-methylstyryl) -2-methylbenzene; 1,4-bis (2-methylstyryl) -2-ethylbenzene and the like.
【００２１】また、特開平２−２５２７９３号公報に開
示されているジスチリルピラジン誘導体も有機発光層の
材料として用いることができる。その代表例としては、
２，５−ビス（４−メチルスチリル）ピラジン；２，５
−ビス（４−エチルスチリル）ピラジン；２，５−ビス
〔２−（１−ナフチル）ビニル〕ピラジン；２，５−ビ
ス（４−メトキシスチリル）ピラジン；２，５−ビス
〔２−（４−ビフェニル）ビニル〕ピラジン；２，５−
ビス〔２−（１−ピレニル）ビニル〕ピラジンなどが挙
げられる。その他、欧州特許第０３８８７６８号明細書
や特開平３−２３１９７０号公報に開示されているジメ
チリデン誘導体を有機発光層の材料として用いることも
できる。その代表例としては、１，４−フェニレンジメ
チリディン；４，４’−ビフェニレンジメチリディン；
２，５−キシリレンジメチリディン；２，６−ナフチレ
ンジメチリディン；１，４−ビフェニレンジメチリディ
ン；１，４−ｐ−テレフェニレンジメチリディン；９，
１０−アントラセンジイルジメチリディン；４，４’−
（２，２−ジ−ｔ−ブチルフェニルビニル）ビフェニ
ル；４，４’−（２，２−ジフェニルビニル）ビフェニ
ルなど、及びこれらの誘導体が挙げられる。The distyrylpyrazine derivative disclosed in JP-A-2-252793 can also be used as a material for the organic light emitting layer. As a typical example,
2,5-bis (4-methylstyryl) pyrazine; 2,5
-Bis (4-ethylstyryl) pyrazine; 2,5-bis [2- (1-naphthyl) vinyl] pyrazine; 2,5-bis (4-methoxystyryl) pyrazine; 2,5-bis [2- (4 -Biphenyl) vinyl] pyrazine; 2,5-
Bis [2- (1-pyrenyl) vinyl] pyrazine and the like can be mentioned. In addition, the dimethylidene derivative disclosed in European Patent No. 0388768 or JP-A-3-231970 can be used as a material for the organic light emitting layer. Typical examples thereof are 1,4-phenylenedimethyridin; 4,4'-biphenylenedimethyridin;
2,5-xylylene dimethylidene; 2,6-naphthylene dimethylidene; 1,4-biphenylene dimethylidene; 1,4-p-terephenylene dimethylidene;
10-anthracene diyl dimethylidin; 4,4'-
(2,2-di-t-butylphenylvinyl) biphenyl; 4,4 ′-(2,2-diphenylvinyl) biphenyl and the like, and derivatives thereof.
【００２２】さらには、特開平２−１９１６９４号公報
に開示されているクマリン誘導体、特開平２−１９６８
８５号公報に開示されているペリレン誘導体、特開平２
−２５５７８９公報に開示されているナフタレン誘導
体、特開平２−２８９６７６号公報及び同２−８８６８
９号公報に開示されているフタロペリノン誘導体、特開
平２−２５０２９２号公報に開示されているスチリルア
ミン誘導体も、有機発光層の材料として用いることがで
きる。これらの有機発光層材料は、所望の発光色や性能
などに応じて適宜選ばれる。なお、本発明の有機ＥＬ素
子における有機発光層は、米国特許第４，７６９，２９
２号明細書に開示されているように、蛍光物質を加えて
形成してもよい。この場合のベースとなる物質は、該ジ
アミン誘導体であってもよいし、該ジアミン誘導体以外
の有機発光層材料であってもよい。さらには、該ジアミ
ン誘導体と有機発光層材料との混合物であってもよい。
蛍光物質を加えて有機発光層を形成する場合、蛍光物質
の添加量は数モル％以下が好ましい。該蛍光物質は電子
と正孔との再結合に応答して発光するため、発光機能の
一部を担うことになる。Furthermore, the coumarin derivative disclosed in Japanese Patent Application Laid-Open No. 2-191694, and Japanese Patent Application Laid-Open No. 2-1968.
Patent No. 85,853, discloses a perylene derivative;
Naphthalene derivatives disclosed in JP-A-255789, JP-A-2-289676 and JP-A-2-8868.
The phthaloperinone derivative disclosed in JP-A No. 9 and the styrylamine derivative disclosed in JP-A-2-250292 can also be used as a material for the organic light emitting layer. These organic light emitting layer materials are appropriately selected according to the desired emission color and performance. The organic light emitting layer in the organic EL device of the present invention is described in US Pat. No. 4,769,29.
It may be formed by adding a fluorescent substance as disclosed in the specification of No. 2. In this case, the base substance may be the diamine derivative or an organic light emitting layer material other than the diamine derivative. Further, it may be a mixture of the diamine derivative and an organic light emitting layer material.
When the organic light emitting layer is formed by adding a fluorescent substance, the amount of the fluorescent substance added is preferably several mol% or less. Since the fluorescent substance emits light in response to recombination of electrons and holes, it plays a part in the light emitting function.
【００２３】また、有機発光層材料としては、薄膜形成
性を有していない化合物を用いることもできる。具体例
としては、１，４−ジフェニル−１，３−ブタジエン；
１，１，４，４−テトラフェニル−１，３−ブタジエ
ン；テトラフェニルシクロペンタジエンなどが挙げられ
る。しかし、薄膜形成性を有しないこれらの材料を用い
た有機ＥＬ素子は、素子の寿命が短いという欠点を有す
る。本発明の有機ＥＬ素子における正孔輸送層は、有機
発光層が本発明のジアミン誘導体を含んでいれば、該ジ
アミン誘導体を含む層であってもよいし、該ジアミン誘
導体を含まない層であってもよい。本発明のジアミン誘
導体以外の正孔輸送層材料としては、有機ＥＬ素子の正
孔輸送層材料として従来より使用されている種々の物質
を用いることができる。As the organic light emitting layer material, a compound having no thin film forming property can be used. Specific examples include 1,4-diphenyl-1,3-butadiene;
1,1,4,4-tetraphenyl-1,3-butadiene; tetraphenylcyclopentadiene and the like. However, the organic EL device using these materials having no thin film forming property has a shortcoming that the life of the device is short. The hole transport layer in the organic EL device of the present invention may be a layer containing the diamine derivative of the present invention, or a layer not containing the diamine derivative, as long as the organic light emitting layer contains the diamine derivative of the present invention. May be. As the hole transport layer material other than the diamine derivative of the present invention, various substances conventionally used as the hole transport layer material of the organic EL device can be used.
【００２４】また、正孔輸送層として、本発明のジアミ
ン誘導体を含む層を設ける場合、この正孔輸送層は、前
記したように該ジアミン誘導体のみからなる単層構造、
該ジアミン誘導体と有機ＥＬ素子の正孔輸送層材料とし
て従来より使用されている物質の層との複層構造、ある
いは該ジアミン誘導体と有機ＥＬ素子の正孔輸送層材料
として従来より使用されている物質との混合物からなる
層を含む単層構造又は複層構造のいずれであってもよ
い。この場合の好ましい層構造は、該ジアミン誘導体の
みからなる単層構造又は該ジアミン誘導体層と、ポルフ
ィリン化合物（特開昭６３−２９５６９５号公報などに
開示されているもの）の層又は有機半導体性オリゴマー
の層との複層構造である。When a layer containing the diamine derivative of the present invention is provided as the hole transport layer, the hole transport layer has a single-layer structure consisting of the diamine derivative alone, as described above.
Conventionally used as a multilayer structure of the diamine derivative and a layer of a substance conventionally used as a hole transport layer material for an organic EL device, or as a hole transport layer material for the diamine derivative and an organic EL device. It may have either a single-layer structure or a multi-layer structure including a layer composed of a mixture with a substance. In this case, the preferred layer structure is a single layer structure consisting of the diamine derivative alone or the diamine derivative layer and a layer of a porphyrin compound (disclosed in JP-A-63-295695) or an organic semiconductor oligomer. It is a multi-layer structure with layers.
【００２５】上記ポリフィリン化合物の代表例として
は、ポリフィン，５，１０，１５，２０−テトラフェニ
ル−２１Ｈ−，２３Ｈ−ポルフィン銅（II) ；５，１
０，１５，２０−テトラフェニル−２１Ｈ−，２３Ｈ−
ポルフィン亜鉛（II) ；５，１０，１５，２０−テトラ
キス（ペルフルオロフェニル）−２１Ｈ−，２３Ｈ−ポ
ルフィン；シリコンフタロシアニンオキシド；アルミニ
ウムフタロシアニンクロリド；フタロシアニン（無金
属）；ジリチウムフタロシアニン；銅テトラメチルフタ
ロシアニン；銅フタロシアニン；クロムフタロシアニ
ン；亜鉛フタロシアニン；鉛フタロシアニン；チタニウ
ムフタロシアニンオキシド；マグネシウムフタロシアニ
ン；銅オクタメチルフタロシアニンンなどが挙げられ
る。また、上記有機半導体性オリゴマーとしては、特に
一般式（II)Typical examples of the above porphyrin compound include polyfin, 5,10,15,20-tetraphenyl-21H-, 23H-porphine copper (II); 5,1
0,15,20-tetraphenyl-21H-, 23H-
Porphin zinc (II); 5,10,15,20-tetrakis (perfluorophenyl) -21H-, 23H-porphine; silicon phthalocyanine oxide; aluminum phthalocyanine chloride; phthalocyanine (metal-free); dilithium phthalocyanine; copper tetramethyl phthalocyanine; Copper phthalocyanine; chromium phthalocyanine; zinc phthalocyanine; lead phthalocyanine; titanium phthalocyanine oxide; magnesium phthalocyanine; copper octamethylphthalocyanine. In addition, as the above-mentioned organic semiconducting oligomer, a compound represented by the general formula (II)
【００２６】[0026]
【化７】 Embedded image
【００２７】（式中、Ｒ1 〜Ｒ5 はそれぞれ炭素数１〜
６のアルキル基，炭素数１〜６のアルコキシ基又はフェ
ニル基であり、それらはたがいに同一でも異なっていて
もよい。）で表される化合物が好適である。本発明の有
機ＥＬ素子において必要に応じて設けられる電子注入層
（電子注入輸送層）は、陰極より注入された電子を有機
発光層に伝達する機能を有していればよく、その材料と
しては、従来公知の電子伝達化合物の中から任意のもの
を選択して用いることができる。この電子伝達化合物の
好ましいものとしては、例えば(In the formula, R 1 to R 5 are each 1 to 1 carbon atoms.
An alkyl group having 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group, which may be the same or different. The compound represented by the formula (1) is preferable. The electron injection layer (electron injection / transport layer) provided as necessary in the organic EL device of the present invention may have a function of transmitting the electrons injected from the cathode to the organic light emitting layer, and its material is Any of the conventionally known electron transfer compounds can be selected and used. Preferred examples of this electron transfer compound include, for example,
【００２８】[0028]
【化８】 Embedded image
【００２９】で表される化合物が挙げられる。なお、電
子注入層は電子の注入性，輸送性，障害性のいずれかを
有する層であり、上記の化合物の他に、Ｓｉ系，ＳｉＣ
系，ＣｄＳ系などの結晶性ないし非結晶性材料を用いる
こともできる。本発明の有機ＥＬ素子は、前記の陽極，
陰極，有機発光層，必要に応じて設けられる正孔輸送層
及び電子注入層以外に、層間の付着性を改善するための
層を有していてもよい。このような層、例えば有機発光
層と陰極との付着性を改善するための層の材料の具体例
としては、トリス（８−キノリノール）アルミニウム，
トリス（８−キノリノール）インジウムなどのキノリノ
ール金属錯体系化合物を挙げることができる。Examples include compounds represented by: Note that the electron injection layer is a layer having any of an electron injection property, a transport property, and a hindrance property.
It is also possible to use crystalline or non-crystalline materials such as those based on CdS and CdS. The organic EL device of the present invention comprises the above-mentioned anode,
In addition to the cathode, the organic light emitting layer, the hole transport layer and the electron injection layer which are provided as necessary, a layer for improving the adhesion between the layers may be included. Specific examples of the material of such a layer, for example, a layer for improving the adhesion between the organic light emitting layer and the cathode, include tris (8-quinolinol) aluminum,
Examples include quinolinol metal complex compounds such as tris (8-quinolinol) indium.
【００３０】以上説明した本発明の有機ＥＬ素子は、そ
の構成に応じて、例えば以下のようにして製造すること
ができる。 （ａ）陽極／有機発光層（本発明のジアミン誘導体を含
む）／陰極の構成を有する有機ＥＬ素子の製造−１− まず、適当な基板上に、所望の電極物質、例えば陽極物
質からなる薄膜を、１μｍ以下、好ましくは１０〜２０
０ｎｍの範囲の膜厚になるように、蒸着やスパッタリン
グなどの方法により形成して陽極を作製する。次に、こ
の陽極上に本発明のジアミン誘導体の薄膜を形成するこ
とにより、有機発光層を設ける。このジアミン誘導体の
薄膜化は真空蒸着法，スピンコート法，キャスト法など
の方法により行うことができるが、均質な膜が得られや
すく、かつピンホールが生成しにくいなどの点から、真
空蒸着法が好ましい。該ジアミン誘導体を薄膜化するに
当たって真空蒸着法を適用する場合、その蒸着条件は、
使用するジアミン誘導体の種類、目的とする有機発光層
の結晶構造や会合構造などにより異なるが、一般にボー
ト加熱温度５０〜４００℃、真空度１０-6〜１０-3Ｐ
ａ、蒸着速度0.０１〜５０ｎｍ／ｓｅｃ、基板温度−５
０〜＋３００℃、膜厚５ｎｍ〜５μｍの範囲で適宜選択
することが好ましい。The organic EL device of the present invention described above can be manufactured, for example, as follows, depending on its structure. (A) Manufacture of organic EL device having constitution of anode / organic light emitting layer (including diamine derivative of the present invention) / cathode-1-First, a thin film made of a desired electrode substance, for example, an anode substance, on a suitable substrate. Is 1 μm or less, preferably 10 to 20
An anode is formed by a method such as vapor deposition or sputtering so as to have a thickness in a range of 0 nm. Next, an organic light emitting layer is provided by forming a thin film of the diamine derivative of the present invention on this anode. The diamine derivative can be formed into a thin film by a method such as a vacuum deposition method, a spin coating method, or a casting method, but a vacuum deposition method is preferred because a uniform film is easily obtained and pinholes are less likely to be formed. Is preferred. When applying a vacuum vapor deposition method to form a thin film of the diamine derivative, the vapor deposition conditions are as follows:
Generally, the boat heating temperature is 50 to 400 ° C., and the vacuum degree is 10 −6 to 10 −3 P although it depends on the type of the diamine derivative used, the crystal structure or the association structure of the target organic light emitting layer, and the like.
a, evaporation rate 0.01 to 50 nm / sec, substrate temperature -5
It is preferable to appropriately select in the range of 0 to + 300 ° C. and the film thickness of 5 nm to 5 μm.
【００３１】このようにして有機発光層を形成したの
ち、この有機発光層上に陰極物質からなる薄膜を１μｍ
以下、好ましくは１０〜２００ｎｍの範囲の膜厚になる
ように、蒸着やスパッタリングなどの方法により形成し
て陰極を作製する。これにより目的とする有機ＥＬ素子
が得られる。なお、この有機ＥＬ素子の製造において
は、製造順を逆にして、基板上に陰極／有機発光層／陽
極の順に作製することも可能である。 （ｂ）陽極／有機発光層（本発明のジアミン誘導体を含
む）／陰極の構成を有する有機ＥＬ素子の製造−２− まず、適当な基板上に、上記（ａ）の場合と同様にして
陽極を作製する。次いで、この陽極上に正孔輸送層材
料，有機発光層材料，電子注入層材料，結着剤（ポリビ
ニルカルバゾールなど）などを含む溶液を塗布すること
により、有機発光層を設ける。After the organic light emitting layer is formed in this manner, a thin film of cathode material having a thickness of 1 μm is formed on the organic light emitting layer.
Hereinafter, the cathode is formed by a method such as vapor deposition or sputtering so as to have a thickness preferably in the range of 10 to 200 nm. As a result, the target organic EL device is obtained. In the production of this organic EL element, it is also possible to reverse the production order and produce it on the substrate in the order of cathode / organic light emitting layer / anode. (B) Production of Organic EL Element Having Anode / Organic Light-Emitting Layer (Including Diamine Derivative of the Present Invention) / Cathode-2-First, an anode is formed on a suitable substrate in the same manner as in the case (a). To make. Next, an organic light emitting layer is provided by applying a solution containing a hole transport layer material, an organic light emitting layer material, an electron injection layer material, a binder (such as polyvinyl carbazole), etc. on the anode.
【００３２】次に、陰極物質からなる薄膜を、上記
（ａ）の場合と同様にして有機発光層上に形成して陰極
を作製する。これにより目的とする有機ＥＬ素子が得ら
れる。なお、有機発光層は、上記のようにして形成した
層の上に、所望の有機発光層材料の薄膜を真空蒸着法な
どにより形成して複層構造としてもよい。あるいは、正
孔輸送層材料や電子注入層材料と共に、有機発光層材料
を同時蒸着させることにより、有機発光層を形成しても
よい。 （ｃ）陽極／正孔輸送層（本発明のジアミン誘導体を含
む）／有機発光層／陰極の構成を有する有機ＥＬ素子の
製造 まず、適当な基板上に、上記（ａ）の場合と同様にして
陽極を作製する。次いで、この陽極上に本発明のジアミ
ン誘導体の薄膜を形成することにより正孔輸送層を設け
る。この正孔輸送層の形成は、上記（ａ）における有機
発光層（本発明のジアミン誘導体を含む）の形成と同様
にして行うことができる。Then, a thin film made of a cathode material is formed on the organic light emitting layer in the same manner as in the case of the above (a) to produce a cathode. As a result, the target organic EL device is obtained. The organic light emitting layer may have a multilayer structure by forming a thin film of a desired organic light emitting layer material on the layer formed as described above by a vacuum deposition method or the like. Alternatively, the organic light emitting layer material may be formed by co-evaporating the organic light emitting layer material together with the hole transport layer material and the electron injection layer material. (C) Production of Organic EL Element Having Anode / Hole Transport Layer (Containing Diamine Derivative of the Present Invention) / Organic Emissive Layer / Cathode First, on a suitable substrate, in the same manner as in the case of (a) above. To produce an anode. Next, a hole transport layer is provided by forming a thin film of the diamine derivative of the present invention on this anode. The hole transport layer can be formed in the same manner as the organic light emitting layer (including the diamine derivative of the present invention) in (a) above.
【００３３】次に、正孔輸送層上に、所望の有機発光層
材料を用いて有機発光層を設ける。有機発光層は、真空
蒸着法，スピンコート法，キャスト法などの方法により
有機発光層材料を薄膜化することにより形成することが
できるが、均質な膜が得られやすく、かつピンホールが
生成しにくいなどの点から、真空蒸着法が好ましい。こ
の後、陰極物質からなる薄膜を上記（ａ）の場合と同様
にして有機発光層上に形成して陰極を作製する。これに
より目的とする有機ＥＬ素子が得られる。なお、この有
機ＥＬ素子の製造においても、製造順を逆にして、基板
上に陰極／有機発光層／正孔輸送層／陰極の順に作製す
ることが可能である。Next, an organic light emitting layer is provided on the hole transport layer by using a desired organic light emitting layer material. The organic light emitting layer can be formed by thinning the organic light emitting layer material by a method such as a vacuum deposition method, a spin coating method, a casting method, etc. However, a uniform film is easily obtained and pinholes are generated. A vacuum deposition method is preferable because it is difficult. Thereafter, a thin film made of a cathode material is formed on the organic light-emitting layer in the same manner as in the above (a) to produce a cathode. As a result, the target organic EL device is obtained. Also in the production of this organic EL element, it is possible to reverse the production order and produce the order of cathode / organic light emitting layer / hole transport layer / cathode on the substrate.
【００３４】（ｄ）陽極／正孔輸送層（本発明のジアミ
ン誘導体を含む）／有機発光層／電子注入層／陰極の構
成を有する有機ＥＬ素子の製造 まず、適当な基板上に、上記（ｃ）の場合と同様にして
陽極，正孔輸送層（本発明のジアミン誘導体を含む）及
び有機発光層を形成する。有機発光層の形成後、この有
機発光層上に電子伝達化合物からなる薄膜を、１μｍ以
下、好ましくは５〜１００ｎｍの範囲の膜厚になるよう
に、蒸着やスパッタリングなどの方法により形成して、
電子注入層を形成する。この後、陰極物質からなる薄膜
を上記（ｃ）の場合と同様にして電子注入層上に形成し
て、陰極を作成する。これにより目的とする有機ＥＬ素
子が得られる。なお、この有機ＥＬ素子の製造において
も、製造順を逆にして、基極上に陰極／電子注入層／有
機発光層／正孔輸送層／陽極の順に作成することが可能
である。このようにして製造することができる本発明の
有機ＥＬ素子は、陽極を＋、陰極を−の極性にして５〜
４０Ｖの直流電圧を印加することにより、発光を生じ
る。逆の極性で電圧を印加しても電流は流れず、発光は
全く生じない。また、交流電圧を印加した場合には、陽
極が＋、陰極が−の極性になったときにのみ発光が生じ
る。なお、交流電圧を印加する場合、交流の波形は任意
でよい。(D) Production of Organic EL Element Having Anode / Hole Transport Layer (Including Diamine Derivative of the Present Invention) / Organic Light Emitting Layer / Electron Injection Layer / Cathode First, on a suitable substrate, the above ( An anode, a hole transport layer (including the diamine derivative of the present invention) and an organic light emitting layer are formed in the same manner as in the case of c). After forming the organic light emitting layer, a thin film made of an electron transfer compound is formed on the organic light emitting layer by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 5 to 100 nm,
An electron injection layer is formed. After that, a thin film made of a cathode material is formed on the electron injection layer in the same manner as in the case of (c) above to form a cathode. As a result, the target organic EL device is obtained. Also in the production of this organic EL element, it is possible to reverse the production order to form cathode / electron injection layer / organic light emitting layer / hole transport layer / anode on the base electrode in this order. The organic EL device of the present invention which can be manufactured in this manner has an anode of + and a cathode of −5
Light emission is generated by applying a DC voltage of 40V. Even if a voltage is applied with the opposite polarity, no current flows and no light emission occurs. When an AC voltage is applied, light emission occurs only when the anode has a positive polarity and the cathode has a negative polarity. When an AC voltage is applied, the waveform of the AC may be arbitrary.
【００３５】[0035]
【実施例】次に、実施例により本発明をさらに具体的に
説明するが、本発明はこれらの例によってなんら限定さ
れるものではない。 参考例１ Ｎ，Ｎ’−ジ−（１−ナフチル）−４，
４’−ベンジジンの合成 １０ｇのＮ，Ｎ−ジアセチル−４，４’−ベンジジン
（東京化成社製），１０ｇの１−ヨードナフタレン（東
京化成社製），１０ｇの無水炭酸カリウム，１ｇの銅粉
および３００ミリリットルのジメチルスホキシド（ＤＭ
ＳＯ）を５００ミリリットルのナスフラスコに入れ、２
００℃で４８時間加熱攪拌した。無機物を濾別し、母液
を減圧下で溶媒留去し、得られた残渣を１リットルのテ
トラヒドロフラン（ＴＨＦ）に溶解し、５０ミリリット
ルのメタノールに溶解させた１０ｇの水酸化カリウム溶
液を加え、８０℃で２４時間加熱攪拌した。反応溶液を
１０リットルの水に注ぎ、生成した沈殿を濾過して集
め、6.７ｇの茶白色粉末を得た。これを原料Ａとして以
下の実施例に用いた。EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Reference Example 1 N, N'-di- (1-naphthyl) -4,
Synthesis of 4′-benzidine 10 g of N, N-diacetyl-4,4′-benzidine (manufactured by Tokyo Chemical Industry Co., Ltd.), 10 g of 1-iodonaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 10 g of anhydrous potassium carbonate, 1 g of copper powder. And 300 ml of dimethyl sulphoxide (DM
(SO) into a 500 ml eggplant flask, 2
The mixture was heated and stirred at 00 ° C for 48 hours. Inorganic substances were filtered off, the mother liquor was distilled off under reduced pressure, the resulting residue was dissolved in 1 liter of tetrahydrofuran (THF), and 10 g of potassium hydroxide solution dissolved in 50 ml of methanol was added. The mixture was heated and stirred at ℃ for 24 hours. The reaction solution was poured into 10 liters of water, and the produced precipitate was collected by filtration to obtain 6.7 g of a brown-white powder. This was used as a raw material A in the following examples.
【００３６】実施例１ ＤＡ−１の合成 原料Ａ１ｇと４−エチル−ヨードベンゼン５ｇ（ランカ
スター社製），５ｇの無水炭酸カリウム，１ｇの銅粉お
よび２００ミリリットルのＤＭＳＯを３００ミリリット
ルのナスフラスコに入れ、２００℃で３０時間加熱攪拌
した。無機物を濾別し、母液を減圧下で溶媒留去し、得
られた残渣をワコーゲルＣ−２００（広島和光社製）を
担持したカラムを用い、トルエンを溶媒にして精製した
ところ0.９１ｇの淡黄色粉末を得た（収率４８％，融点
１９８℃）。この化合物の 1Ｈ−ＮＭＲを図１に示す。Example 1 Synthesis of DA-1 1 g of raw material A, 5 g of 4-ethyl-iodobenzene (manufactured by Lancaster), 5 g of anhydrous potassium carbonate, 1 g of copper powder and 200 ml of DMSO were placed in a 300 ml eggplant flask. The mixture was heated and stirred at 200 ° C. for 30 hours. Inorganic substances were filtered off, the mother liquor was evaporated under reduced pressure, and the resulting residue was purified using toluene as a solvent using a column carrying Wakogel C-200 (manufactured by Hiroshima Wako) to give 0.91 g of A pale yellow powder was obtained (yield 48%, melting point 198 ° C). 1 H-NMR of this compound is shown in FIG.
【００３７】実施例２ ＤＡ−３の合成 実施例１において、４−エチル−ヨードベンゼンに代え
て４−ｉ−プロピル−ヨードベンゼン（ランカスター社
製）５ｇを用いた以外は同様に反応を行ったところ0.６
６ｇの淡黄色粉末を得た（収率５４％，融点１４４
℃）。この化合物の 1Ｈ−ＮＭＲを図２に示す。Example 2 Synthesis of DA-3 In Example 1, instead of 4-ethyl-iodobenzene
4-i-propyl-iodobenzene (Lancaster
The same reaction was carried out except that 5 g was used.
6 g of a pale yellow powder was obtained (yield 54%, melting point 144
° C). This compound 1H-NMR is shown in FIG.
【００３８】実施例３ ＤＡ−６の合成 実施例１において４−エチル−ヨードベンゼンに代えて
４−ｔ−ブチル−ヨードベンゼン（ランカスター社製）
５ｇを用いた以外は同様に反応を行ったところ、0.５８
ｇの淡黄色粉末を得た（収率３６％，融点１７３℃）。
この化合物の 1Ｈ−ＮＭＲを図３に示す。Example 3 Synthesis of DA-6 4-t-butyl-iodobenzene (manufactured by Lancaster) in place of 4-ethyl-iodobenzene in Example 1
When the reaction was performed in the same manner except that 5 g was used, it was 0.58.
g of a pale yellow powder was obtained (yield 36%, melting point 173 ° C.).
1 H-NMR of this compound is shown in FIG.
【００３９】実施例４ ＤＡ−１３の合成 実施例１において４−エチル−ヨードベンゼンに代えて
４−ブロモフェネトン（アルドリッチ社製）５ｇを用い
た以外は同様に反応を行ったところ、0.７０ｇの淡黄色
粉末を得た（収率４７％，融点１８８℃）。この化合物
の 1Ｈ−ＮＭＲを測定した結果、δ 7.９６〜7.９２
（ｄ，２Ｈ），7.８８〜7.８４（ｄ，２Ｈ），7.７４〜
7.７０（ｄ，２Ｈ），7.４７〜7.４２（ｔ，２Ｈ），7.
４４〜7.４０（ｔ，２Ｈ），7.３７〜7.２７（ｍ，８
Ｈ），7.０８〜7.０３（ｍ，４Ｈ），6.８５〜6.７６
（ｍ，８Ｈ），4.０８〜3.７０（ｑ，４Ｈ），1.４８〜
1.２０（ｔ，６Ｈ）ｐｐｍであった。Example 4 Synthesis of DA-13 A reaction was carried out in the same manner as in Example 1 except that 5 g of 4-bromophenetone (manufactured by Aldrich) was used instead of 4-ethyl-iodobenzene. 70 g of a pale yellow powder was obtained (yield 47%, melting point 188 ° C.). As a result of 1 H-NMR measurement of this compound, δ 7.96 to 7.92 was obtained.
(D, 2H), 7.88 ~ 7.84 (d, 2H), 7.74 ~
7.70 (d, 2H), 7.47 to 7.42 (t, 2H), 7.
44 to 7.40 (t, 2H), 7.37 to 7.27 (m, 8
H), 7.08 to 7.03 (m, 4H), 6.85 to 6.76
(M, 8H), 4.08 to 3.70 (q, 4H), 1.48 to
It was 1.20 (t, 6H) ppm.
【００４０】実施例５ ＤＡ−２５の合成 実施例１において４−エチル−ヨードベンゼンに代えて
ヨードビフェニル（アルドリッチ社製）５ｇを用いた以
外は同様に反応を行ったところ、0.４３ｇの淡黄色粉末
を得た（収率２５％，融点１７２℃）。この化合物の 1
Ｈ−ＮＭＲを図４に示す。Example 5 Synthesis of DA-25 When the same reaction as in Example 1 was carried out except that 5 g of iodobiphenyl (manufactured by Aldrich) was used in place of 4-ethyl-iodobenzene, 0.43 g of light was obtained. A yellow powder was obtained (yield 25%, melting point 172 ° C.). 1 of this compound
1 H-NMR is shown in FIG.
【００４１】実施例６ 実施例１で合成した化合物ＤＡ−１を用いて以下のよう
にして有機ＥＬ素子を作製した。２５ｍｍ×７５ｍｍ×
1.１ｍｍのサイズのガラス基板上にＩＴＯ電極を１００
ｎｍの厚さで成膜したものを透明支持基板とした。これ
をイソプロピルアルコールで５分間超音波洗浄した後、
純水で５分間洗浄し最後に再びイソプロピルアルコール
で５分間超音波洗浄した。この透明支持基板を真空蒸着
装置（日本真空技術（株）製）の基板ホルダーに固定
し、モリブデン製の抵抗加熱ボート５つを用意してそれ
ぞれに４，４’，４" −トリス（３−メチルフェニルフ
ェニルアミノ）トリフェニルアミン（ＭＴＤＡＴＡ）を
５００ｍｇ、ＤＡ−１を２００ｍｇ、４，４’−ビス
（２，２−ジフェニルビニル）ビフェニル（ＤＰＶＢ
ｉ）を２００ｍｇ、４，４’−ビス〔２−（４−（Ｎ，
Ｎ−ジフェニルアミノ）フェニル）ビニル〕ビフェニル
（ＤＰＡＶＢｉ）を２００ｍｇ、最後にトリス（８−ヒ
ドロキシキノリン）アルミニウム（Ａｌｑ）を１００ｍ
ｇ入れ、真空チャンバー内を１×１０-4Ｐａまで減圧し
た。Example 6 Using the compound DA-1 synthesized in Example 1, an organic EL device was prepared as follows. 25 mm x 75 mm x
100 ITO electrodes on a glass substrate of 1.1 mm size
A film having a thickness of nm was used as a transparent support substrate. After ultrasonically cleaning this with isopropyl alcohol for 5 minutes,
It was washed with pure water for 5 minutes, and finally ultrasonically washed again with isopropyl alcohol for 5 minutes. This transparent support substrate was fixed to a substrate holder of a vacuum vapor deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.), and 5 resistance heating boats made of molybdenum were prepared, and 4, 4 ', 4 "-Tris (3- Methylphenylphenylamino) triphenylamine (MTDATA) 500 mg, DA-1 200 mg, 4,4′-bis (2,2-diphenylvinyl) biphenyl (DPVB
i) 200 mg, 4,4'-bis [2- (4- (N,
200 mg of N-diphenylamino) phenyl) vinyl] biphenyl (DPAVBi) and finally 100 m of tris (8-hydroxyquinoline) aluminum (Alq).
Then, the inside of the vacuum chamber was depressurized to 1 × 10 −4 Pa.
【００４２】そして、まずＭＴＤＡＴＡ入りのボートを
加熱してＭＴＤＡＴＡを基板上に堆積させ、膜厚６０ｎ
ｍの正孔注入層を成膜した。次にＤＡ−１入りの前記ボ
ートを加熱しＤＡ−１を蒸発させて、膜厚２０ｎｍの正
孔輸送層を成膜した。続いて、ＤＰＶＢｉ入りのボート
とＤＰＡＶＢｉ入りのボートを同時に加熱蒸発させ正孔
輸送層の上に、混合発光層として４０ｎｍ積層蒸着した
（混合比は重量比でＤＰＶＢｉ：ＤＰＡＶＢｉ＝４０：
１）。さらに最後のボートからＡｌｑ（電子注入層）を
２０ｎｍ堆積させた。最後に、これを真空槽から取り出
して、上記発光層の上にステンレススチール製マスクを
設置し、再び基板ホルダーに固定した。さらに、タング
ステン製バスケットにＡｇワイヤー0.５ｇ入れ、また別
のモリブリテン製ボートにＭｇリボン１ｇを入れた。真
空槽内を１×１０-4Ｐａまで減圧して、Ｍｇを1.８ｎｍ
／ｓ，同時にＡｇを0.１ｎｍ／ｓの蒸発速度で蒸着して
陰電極を作製した。得られた素子に、ＩＴＯを陽極、Ｍ
ｇ：Ａｇを陰極として８Ｖの電圧を印加すると、青色に
均一発光した。初期性能は８Ｖで電流密度4.０ｍＡ／ｃ
ｍ2 、輝度１６３ｃｄ／ｍ2 、効率1.６１ルーメン／Ｗ
であった。初期１００ｃｄ／ｍ2 で乾燥窒素中で定電流
連続駆動すると半減寿命（輝度が半分になる時間）が１
５００時間であった。Then, first, a boat containing MTDATA is heated to deposit MTDATA on the substrate, and a film thickness of 60 n is obtained.
m of the hole injection layer was formed. Next, the boat containing DA-1 was heated to evaporate DA-1 to form a hole transport layer having a film thickness of 20 nm. Subsequently, the boat containing DPVBi and the boat containing DPAVBi were simultaneously heated and vaporized to be laminated and vapor-deposited by 40 nm as a mixed emission layer on the hole transport layer (mixing ratio is DPVBi: DPAVBi = 40: by weight ratio).
1). Further, Alq (electron injection layer) was deposited to a thickness of 20 nm from the last boat. Finally, this was taken out of the vacuum chamber, a stainless steel mask was placed on the above light emitting layer, and again fixed to the substrate holder. Further, 0.5 g of Ag wire was placed in a tungsten basket, and 1 g of Mg ribbon was placed in another molyburiten boat. The pressure inside the vacuum chamber was reduced to 1 × 10 -4 Pa and Mg was reduced to 1.8 nm.
/ S, and at the same time Ag was vapor-deposited at an evaporation rate of 0.1 nm / s to prepare a negative electrode. The obtained device was treated with ITO as an anode, M
When a voltage of 8 V was applied using g: Ag as a cathode, blue light was uniformly emitted. Initial performance is 8V and current density is 4.0mA / c
m 2 , brightness 163 cd / m 2 , efficiency 1.61 lumen / W
Met. Half-life (time when brightness is halved) is 1 when continuously driven with constant current in dry nitrogen at initial 100 cd / m 2.
It was 500 hours.
【００４３】実施例７ 実施例６においてＤＡ−１に代えて実施例２で合成した
ＤＡ−３を用いた以外は同様にして有機ＥＬ素子を作製
し評価した。 実施例８ 実施例６においてＤＡ−１に代えて実施例３で合成した
ＤＡ−６を用いた以外は同様にして有機ＥＬ素子を作製
し評価した。 実施例９ 実施例６においてＤＡ−１に代えて実施例４で合成した
ＤＡ−１３を用いた以外は同様にして有機ＥＬ素子を作
製し評価した。Example 7 An organic EL device was prepared and evaluated in the same manner as in Example 6 except that DA-3 synthesized in Example 2 was used instead of DA-1. Example 8 An organic EL device was prepared and evaluated in the same manner as in Example 6 except that DA-6 synthesized in Example 3 was used instead of DA-1. Example 9 An organic EL device was prepared and evaluated in the same manner as in Example 6 except that DA-13 synthesized in Example 4 was used instead of DA-1.
【００４４】実施例１０ 実施例６においてＤＡ−１に代えて実施例５で合成した
ＤＡ−２５を用いた以外は同様にして有機ＥＬ素子を作
製し評価した。Example 10 An organic EL device was prepared and evaluated in the same manner as in Example 6 except that DA-25 synthesized in Example 5 was used instead of DA-1.
【００４５】比較例１ 正孔輸送層としてＤＡ−１に代えてＮ，Ｎ’−ジナフチ
ル−Ｎ，Ｎ’−ジフェニル−４，４’−ジアミノビフェ
ニル（ＮＰＤ）を用いた以外は実施例６と同様にして有
機ＥＬ素子を作製した。得られた素子にＩＴＯを陽極、
Ｍｇ：Ａｇを陰極として８Ｖの電圧を印加すると、青色
に均一発光した。初期性能は８Ｖで電流密度4.０ｍＡ／
ｃｍ2 、輝度１４０ｃｄ／ｍ2 、効率1.３７ルーメン／
ｗであった。初期１００ｃｄ／ｍ3 で乾燥窒素中で定電
流連続駆動すると半減寿命は９５０時間であり、明らか
に実施例６のものより劣っていた。 比較例２ 実施例６においてＤＡ−１に代えて、特開平１−１４２
６５７号公報明細書の第１２頁に記載の化合物Ｎｏ．１
８１と同一の化合物である下記ＤＡ−０を用いた以外は
同様にして有機ＥＬ素子を作製し評価した。Comparative Example 1 As Example 6 except that N, N'-dinaphthyl-N, N'-diphenyl-4,4'-diaminobiphenyl (NPD) was used as the hole transport layer in place of DA-1. Similarly, an organic EL device was produced. ITO is added to the obtained element as an anode,
When a voltage of 8 V was applied using Mg: Ag as a cathode, blue light was uniformly emitted. Initial performance is 8V and current density is 4.0mA /
cm 2 , brightness 140 cd / m 2 , efficiency 1.37 lumen /
It was w. When driven at a constant current continuously in dry nitrogen at an initial stage of 100 cd / m 3 , the half life was 950 hours, which was clearly inferior to that of Example 6. Comparative Example 2 Instead of DA-1 in Example 6, JP-A-1-142
No. 657, the compound No. described on page 12 of the specification. 1
An organic EL device was prepared and evaluated in the same manner except that the following DA-0, which was the same compound as 81, was used.
【００４６】[0046]
【化９】 Embedded image
【００４７】比較例３ 実施例６においてＤＡ−１に代えて、特開平１−１４２
６５７号公報明細書の第１４頁に記載の化合物Ｎｏ．２
４０と同一の化合物である下記構造を有するＤＡ−００
を用いた以外は同様にしてＥＬ素子を作製し評価した。Comparative Example 3 Instead of DA-1 in Example 6, JP-A-1-142 was used.
No. 657, the compound No. described on page 14 of the specification. 2
DA-00 having the following structure, which is the same compound as 40
EL devices were prepared and evaluated in the same manner except that was used.
【００４８】[0048]
【化１０】 実施例６〜１０および比較例１〜３の結果を第１表に示
す。Embedded image The results of Examples 6 to 10 and Comparative Examples 1 to 3 are shown in Table 1.
【００４９】[0049]
【表１】 [Table 1]
【００５０】[0050]
【発明の効果】本発明の新規なジアミン誘導体は、各種
溶媒に対して極めて溶解性が高く、精製が容易であり、
有機ＥＬ素子あるいは電子写真感光体に用いた場合、安
定性に優れ極めて長寿命の素子あるいは感光体を得るこ
とができる。また、本発明のジアミン誘導体を用いるこ
とにより長時間連続駆動においても優れた発光安定性を
示す長寿命な有機ＥＬ素子を提供するができる。INDUSTRIAL APPLICABILITY The novel diamine derivative of the present invention has extremely high solubility in various solvents and is easy to purify,
When used in an organic EL device or an electrophotographic photoreceptor, it is possible to obtain an element or a photoreceptor having excellent stability and a very long life. Further, by using the diamine derivative of the present invention, it is possible to provide a long-life organic EL device which exhibits excellent luminescence stability even when continuously driven for a long time.
【図面の簡単な説明】[Brief description of the drawings]
【図１】 実施例１で得られた本発明のジアミン誘導体
の 1Ｈ−ＮＭＲを示す図である。FIG. 1 is a diagram showing 1 H-NMR of a diamine derivative of the present invention obtained in Example 1.
【図２】 実施例２で得られた本発明のジアミン誘導体
の 1Ｈ−ＮＭＲを示す図である。FIG. 2 is a chart showing 1 H-NMR of the diamine derivative of the present invention obtained in Example 2.
【図３】 実施例３で得られた本発明のジアミン誘導体
の 1Ｈ−ＮＭＲを示す図である。FIG. 3 is a chart showing 1 H-NMR of the diamine derivative of the present invention obtained in Example 3.
【図４】 実施例５で得られた本発明のジアミン誘導体
の 1Ｈ−ＮＭＲを示す図である。FIG. 4 is a chart showing 1 H-NMR of the diamine derivative of the present invention obtained in Example 5.
Claims (3)
導体。 【化１】 式中、Ｘ1 〜Ｘ10はそれぞれ水素，炭素数２〜６のアル
キル基，炭素数２〜６のアルコキシ基又はフェニル基で
あり、Ｘ1 〜Ｘ5 の少なくともひとつ及びＸ6 〜Ｘ10の
少なくともひとつは炭素数２〜６のアルキル基，炭素数
２〜６のアルコキシ基又はフェニル基である。1. A diamine derivative represented by the following general formula (I). Embedded image In the formula, X 1 to X 10 are each hydrogen, an alkyl group having 2 to 6 carbon atoms, an alkoxy group having 2 to 6 carbon atoms or a phenyl group, and at least one of X 1 to X 5 and X 6 to X 10 At least one is an alkyl group having 2 to 6 carbon atoms, an alkoxy group having 2 to 6 carbon atoms, or a phenyl group.
ことを特徴とする有機エレクトロルミネッセンス素子。2. An organic electroluminescence device comprising the diamine derivative according to claim 1.
送層として用いることを特徴とする有機エレクトロルミ
ネッセンス素子。3. An organic electroluminescence device comprising the diamine derivative according to claim 1 as a hole transport layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00358596A JP3168897B2 (en) | 1996-01-12 | 1996-01-12 | Diamine derivative having naphthyl group and organic electroluminescence device using the derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00358596A JP3168897B2 (en) | 1996-01-12 | 1996-01-12 | Diamine derivative having naphthyl group and organic electroluminescence device using the derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09194441A true JPH09194441A (en) | 1997-07-29 |
| JP3168897B2 JP3168897B2 (en) | 2001-05-21 |
Family
ID=11561540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00358596A Expired - Fee Related JP3168897B2 (en) | 1996-01-12 | 1996-01-12 | Diamine derivative having naphthyl group and organic electroluminescence device using the derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3168897B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1088119A (en) * | 1996-09-11 | 1998-04-07 | Sharp Corp | Organic electroluminescent element |
| EP0924192A1 (en) * | 1997-12-16 | 1999-06-23 | Chisso Corporation | Diaminonaphthalene derivatives and organic electroluminescent device using the same |
| WO2002094965A1 (en) * | 2001-05-24 | 2002-11-28 | Idemitsu Kosan Co., Ltd. | Organic electroluminescence element |
| US6583583B1 (en) | 1999-09-02 | 2003-06-24 | Nippon Steel Chemical Co., Ltd. | Organic el material |
| US6617053B2 (en) | 2000-08-04 | 2003-09-09 | Chisso Corporation | Organic electroluminescent device containing dithiafulvene derivative |
| US6761981B2 (en) | 2000-09-28 | 2004-07-13 | Chisso Corporation | Cyclic tertiary amine compound and organic electroluminescent device containing the compound |
| US7605277B2 (en) | 2004-02-09 | 2009-10-20 | Nippon Steel Chemical Co., Ltd. | Aminodibenzodioxin derivative and organic electroluminescent using the same |
| US7700251B2 (en) * | 2005-10-19 | 2010-04-20 | Kyocera Mita Corporation | Electrophotographic photoconductor and image-forming apparatus |
| EP2696383A1 (en) * | 2012-08-10 | 2014-02-12 | Solvay Sa | Multilayered organic electronic devices |
| JPWO2016006673A1 (en) * | 2014-07-11 | 2017-04-27 | 日産化学工業株式会社 | Charge transport varnish |
| CN113461548A (en) * | 2020-03-31 | 2021-10-01 | 江苏三月光电科技有限公司 | Aromatic amine derivative and application thereof |
-
1996
- 1996-01-12 JP JP00358596A patent/JP3168897B2/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1088119A (en) * | 1996-09-11 | 1998-04-07 | Sharp Corp | Organic electroluminescent element |
| EP0924192A1 (en) * | 1997-12-16 | 1999-06-23 | Chisso Corporation | Diaminonaphthalene derivatives and organic electroluminescent device using the same |
| US6376106B1 (en) | 1997-12-16 | 2002-04-23 | Chisso Corporation | Diaminonaphthalene derivative and organic electroluminescent device using the same |
| US6583583B1 (en) | 1999-09-02 | 2003-06-24 | Nippon Steel Chemical Co., Ltd. | Organic el material |
| US6617053B2 (en) | 2000-08-04 | 2003-09-09 | Chisso Corporation | Organic electroluminescent device containing dithiafulvene derivative |
| US6761981B2 (en) | 2000-09-28 | 2004-07-13 | Chisso Corporation | Cyclic tertiary amine compound and organic electroluminescent device containing the compound |
| CN100377382C (en) * | 2001-05-24 | 2008-03-26 | 出光兴产株式会社 | Organic electroluminescent device |
| JPWO2002094965A1 (en) * | 2001-05-24 | 2004-09-09 | 出光興産株式会社 | Organic electroluminescence device |
| WO2002094965A1 (en) * | 2001-05-24 | 2002-11-28 | Idemitsu Kosan Co., Ltd. | Organic electroluminescence element |
| US7605277B2 (en) | 2004-02-09 | 2009-10-20 | Nippon Steel Chemical Co., Ltd. | Aminodibenzodioxin derivative and organic electroluminescent using the same |
| US7700251B2 (en) * | 2005-10-19 | 2010-04-20 | Kyocera Mita Corporation | Electrophotographic photoconductor and image-forming apparatus |
| EP2696383A1 (en) * | 2012-08-10 | 2014-02-12 | Solvay Sa | Multilayered organic electronic devices |
| JPWO2016006673A1 (en) * | 2014-07-11 | 2017-04-27 | 日産化学工業株式会社 | Charge transport varnish |
| CN106537629B (en) * | 2014-07-11 | 2019-03-29 | 日产化学工业株式会社 | Charge-transporting varnish |
| CN113461548A (en) * | 2020-03-31 | 2021-10-01 | 江苏三月光电科技有限公司 | Aromatic amine derivative and application thereof |
| CN113461548B (en) * | 2020-03-31 | 2023-12-12 | 江苏三月科技股份有限公司 | Aromatic amine derivative and application thereof |
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|---|---|
| JP3168897B2 (en) | 2001-05-21 |
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