JPH1092581A - Organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element having a long light emitting life and excellent durability by providing an organic electroluminescent element having a layer containing a compound having a specified formula between a pair of electrodes. SOLUTION: An organic electroluminescent element having at least one layer containing at least one of compounds between a pair of electrodes is installed and the compounds have a formula (1) wherein Ar1 -Ar6 stand for substituted or unsubstituted aryl group; x1 -x6 for hydrogen atom, halogen atom, linear, branched, or cyclic alkoxy group, or substituted or unsubstituted aryl group. In this case, Ar1 -Ar6 as substituents are preferably, for example, halogen atom, linear, branched, or cyclic alkoxy group with 1-10 carbons, cyclic aromatic group with total carbons 6-20 or hetero-cyclic aromatic group with total carbons 4 20, which may be substituted with aryl group with 6-10 carbons or multi- substituted with aryl groups with 6-10 carbons and more preferably Ar1 -Ar6 are halogen atom and cycling aromatic group with total carbons 6-20 which may by substituted with alkoxy group with 1-6 carbons.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an organic electroluminescent device.

[0002]

2. Description of the Related Art Conventionally, an inorganic electroluminescent element has been used as a panel-type light source such as a backlight. However, driving the light emitting element requires a high AC voltage. Recently, an organic electroluminescent device (organic electroluminescent device: organic EL device) using an organic material as a light emitting material has been developed [Appl. Phys. Lett., 51 ,
913 (1987)]. The organic electroluminescent element has a structure in which a thin film containing a fluorescent organic compound is sandwiched between an anode and a cathode,
An exciton is generated by injecting electrons and holes into the thin film and recombining them, and emits light using light emitted when the exciton is deactivated. is there. The organic electroluminescent element can emit light at a low DC voltage of about several volts to several tens of volts, and various colors (for example, red, blue, and green) can be obtained by selecting the type of the fluorescent organic compound. ) Is possible. Organic electroluminescent devices having such features include various light emitting devices,
Application to display elements and the like is expected. However,
In general, organic electroluminescent elements have disadvantages such as a short luminescent life and poor durability.

It has been proposed to use 1,1-bis [4 '-[N, N-di (4 "-methylphenyl) amino] phenyl] cyclohexane as a hole injection / transport material [Appl. Phys. Lett., 51 , 913 (1987)] It has been proposed to use 4,4'-bis [N-phenyl-N- (3 "-methylphenyl) amino] biphenyl as a hole injecting and transporting material. Jpn. J. Appl. Phy
s., 27 , L269 (1988)]. N, N'-bis [4 '-(N ", N" -diphenylamino) phenyl] -N, N'-diphenyl is used as a material of an organic semiconductor layer for assisting hole injection or electron injection used in an organic electroluminescent device. -1, 4
-Diaminobenzene has been shown to be useful (JP-A-7-240277, JP-A-8-1991).
No. 62). However, these light-emitting elements also have disadvantages such as a short light-emitting life and poor durability. At present, further improved organic electroluminescent devices are desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electroluminescent device having an improved light emission lifetime.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on the organic electroluminescent device, and as a result, completed the present invention. That is, the present invention provides an organic electroluminescent element comprising at least one layer containing at least one compound containing at least one compound represented by the following general formula (1) (formula 2) between a pair of electrodes. The organic electroluminescent device according to the above, wherein the layer containing the compound represented by 1) is a hole injecting and transporting layer; the organic electroluminescent device according to the above or the above, further comprising a light emitting layer between a pair of electrodes; The present invention relates to the organic electroluminescent device according to any one of the above items, further comprising an electron injection / transport layer between a pair of electrodes.

[0006]

Embedded image (In the formula, Ar _{1 to} Ar ₆ represent a substituted or unsubstituted aryl group, and X _{1 to} X ₆ represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. Represents a group or a substituted or unsubstituted aryl group)

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The organic electroluminescent device of the present invention, between a pair of electrodes,
It comprises at least one layer containing at least one layer containing at least one compound represented by the following general formula (1).

[0008]

Embedded image (In the formula, Ar _{1 to} Ar ₆ represent a substituted or unsubstituted aryl group, and X _{1 to} X ₆ represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. Represents a group or a substituted or unsubstituted aryl group)

In the compound represented by the general formula (1),
Ar _{1 to} Ar ₆ represent a substituted or unsubstituted aryl group.
Note that the aryl group represents a carbocyclic aromatic group such as a phenyl group and a naphthyl group, for example, a heterocyclic aromatic group such as a furyl group, a thienyl group, and a pyridyl group. Ar ₁ ~
Ar ₆ is preferably a substituent such as a halogen atom, a straight-chain, branched or cyclic alkyl group having 1 to 10 carbon atoms, a straight-chain, branched or cyclic alkoxy group having 1 to 10 carbon atoms, or a carbon atom. A carbocyclic aromatic group having a total of 6 to 20 carbon atoms or a heterocyclic aromatic group having a total of 4 to 20 carbon atoms, which may be monosubstituted or polysubstituted with an aryl group having 6 to 10 carbon atoms, more preferably Is a halogen atom, carbon number 1
An alkyl group having 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a carbocyclic aromatic group having a total of 6 to 20 carbon atoms which may be mono- or polysubstituted with an aryl group having 6 to 10 carbon atoms, Particularly preferably, a total of 6 to 6 carbon atoms which may be mono- or polysubstituted by a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. A phenyl group having 20 or a naphthyl group having 10 to 20 carbon atoms in total.

Specific examples of Ar _{1 to} Ar ₆ include, for example, phenyl, 1-naphthyl, 2-naphthyl, 2-anthryl, 9-anthryl, 4-quinolyl, 4-pyridyl, 3 -Pyridyl group, 2-pyridyl group, 3-furyl group, 2-furyl group, 3-thienyl group, 2-thienyl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzooxazolyl group, 2-benzothiazolyl Group, 2-benzimidazolyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group,
4-n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec-butylphenyl group, 2-sec-butylphenyl group, 4-tert
-Butylphenyl group, 3-tert-butylphenyl group, 2
-Tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 2-neopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group, 4- (2 ′ -Ethylbutyl) phenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4- (2'-ethylhexyl) phenyl group, 4-tert-octylphenyl group, 4-n-decylphenyl group, 4 -Cyclopentylphenyl group, 4-cyclohexylphenyl group, 4- (4'-methylcyclohexyl) phenyl group, 4- (4'-tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2
-Cyclohexylphenyl group, 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4
-Dimethylphenyl group, 3,5-dimethylphenyl group,
2,6-dimethylphenyl group, 2,4-diethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6
-Trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,6-diethylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisobutylphenyl group, 2,4-di-tert-butylphenyl group 2,5-di-tert-butylphenyl group, 4,6-di-tert-butyl-2-methylphenyl group, 5-tert-butyl-2-methylphenyl group, 4-tert-butyl-2,6 A dimethylphenyl group,

4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 3-ethoxyphenyl, 2-ethoxyphenyl, 4-n-propoxyphenyl, 3-n -Propoxyphenyl group, 4-isopropoxyphenyl group, 2-
Isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-
Isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 4-neopentyloxyphenyl group, 2
-Neopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2- (2'-ethylbutyl) oxyphenyl group, 4-n-octyloxyphenyl group, 4-n
-Decyloxyphenyl group, 4-cyclohexyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2
-Methoxy-1-naphthyl group, 4-methoxy-1-naphthyl group, 4-n-butoxy-1-naphthyl group, 5-ethoxy-1-naphthyl group, 6-ethoxy-2-naphthyl group, 6-n- Butoxy-2-naphthyl group, 6-n-hexyloxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 7-n-butoxy-2-naphthyl group, 2-methyl-4-methoxyphenyl group, 2 -Methyl-5-methoxyphenyl group, 3-methyl-5-methoxyphenyl group,
3-ethyl-5-methoxyphenyl group, 2-methoxy-
4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group,
3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2-methoxy -6-ethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4'-methylphenyl) phenyl group, 4- (3′-methylphenyl) phenyl group, 4-
(4′-methoxyphenyl) phenyl group, 4- (4′-
n-butoxyphenyl) phenyl group, 2- (2′-methoxyphenyl) phenyl group, 4- (4′-chlorophenyl) phenyl group, 3-methyl-4-phenylphenyl group, 3-methoxy-4-phenylphenyl group ,

4-fluorophenyl, 3-fluorophenyl, 2-fluorophenyl, 4-chlorophenyl, 3-chlorophenyl, 2-chlorophenyl,
4-bromophenyl group, 2-bromophenyl group, 4-chloro-1-naphthyl group, 4-chloro-2-naphthyl group,
6-bromo-2-naphthyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group,
3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4
-Dichlorophenyl group, 3,5-dichlorophenyl group,
2,5-dibromophenyl group, 2,4,6-trichlorophenyl group, 2,4-dichloro-1-naphthyl group,
6-dichloro-2-naphthyl group, 2-fluoro-4-methylphenyl group, 2-fluoro-5-methylphenyl group, 3-fluoro-2-methylphenyl group, 3-fluoro-4-methylphenyl group, 2 -Methyl-4-fluorophenyl group, 2-methyl-5-fluorophenyl group, 3
-Methyl-4-fluorophenyl group, 2-chloro-4-
Methylphenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2-methyl-
3-chlorophenyl group, 2-methyl-4-chlorophenyl group, 3-methyl-4-chlorophenyl group, 2-chloro-4,6-dimethylphenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4 -Methoxyphenyl group, 2-fluoro-4-ethoxyphenyl group, 2-fluoro-6-methoxyphenyl group, 3-fluoro-4-
Examples thereof include an ethoxyphenyl group, a 3-chloro-4-methoxyphenyl group, a 2-methoxy-5-chlorophenyl group, a 3-methoxy-6-chlorophenyl group, and a 5-chloro-2,4-dimethoxyphenyl group. However, the present invention is not limited to these.

In the compound represented by the general formula (1),
X _{1 to} X ₆ represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group, preferably a hydrogen atom; A halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom); a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms (e.g., a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, cyclohexyl group, n- Heptyl group, cyclohexylmethyl group, n-octyl group, tert-
Octyl group, 2-ethylhexyl group, n-nonyl group, n
-Decyl group and the like); a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group) Group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group Such);
Alternatively, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms (for example, phenyl group, 2-methylphenyl group, 3
-Methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-n-propylphenyl group, 4-tert
-Butylphenyl group, 2-methoxyphenyl group, 4-methoxyphenyl group, 3-ethoxyphenyl group, 3-fluorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 1-naphthyl group, 2-naphthyl group, etc.) It is. More preferably, they are a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. It is a C1-4 alkyl group or a C1-4 alkoxy group.

Specific examples of the compound represented by the general formula (1) according to the present invention include, for example, the following compounds, but the present invention is not limited thereto. -Exemplified compound number N, N'-bis [4 '-(N ", N" -diphenylamino) phenyl] -N, N'-diphenyl-1,3
-Diaminobenzene2. N, N'-bis [4 '-(N ", N" -diphenylamino) phenyl] -N-phenyl-N'-(3 "-
2. methylphenyl) -1,3-diaminobenzene N, N'-bis [4 '-(N ", N" -diphenylamino) phenyl] -N-phenyl-N'-(4 "-
3. methylphenyl) -1,3-diaminobenzene N, N'-bis [4 '-(N ", N" -diphenylamino) phenyl] -N, N'-di (3 "-methylphenyl) -1,3-diaminobenzene 5. N, N'- 5. bis [4 '-(N ", N" -diphenylamino) phenyl] -N, N'-di (4 "-methylphenyl) -1,3-diaminobenzene N, N'-bis [4 '-(N ", N" -diphenylamino) phenyl] -N, N'-di (4 "-tert-butylphenyl) -1,3-diaminobenzene 7. N, N '-Bis [4'-(N ", N" -diphenylamino) phenyl] -N, N'-di (4'-isopentylphenyl) -1,3-diaminobenzene 8. N, N'-bis [ 4 '-(N ", N" -diphenylamino) phenyl] -N, N'-di (4'-n-octylphenyl) -1,3-diaminobenzene 9. N, N'-bis [4'- (N ", N" -diphenylamino) phenyl] -N-phenyl-N '-(3 "-
9. methoxyphenyl) -1,3-diaminobenzene N, N'-bis [4 '-(N ", N" -diphenylamino) phenyl] -N-phenyl-N'-(3 "
-Ethoxyphenyl) -1,3-diaminobenzene

11. N, N'-bis [4 '-(N ",
N "-diphenylamino) phenyl] -N, N'-di (4" -methoxyphenyl) -1,3-diaminobenzene N, N'-bis [4 '-(N ", N" -diphenylamino) phenyl] -N, N'-di (4 "-isopropoxyphenyl) -1,3-diaminobenzene 13. N, N' -Bis [4 '-(N ", N" -diphenylamino) phenyl] -N, N'-di (4 "-n-hexyloxyphenyl) -1,3-diaminobenzene 14. N, N'-bis [4 '-(N ", N" -diphenylamino) phenyl] -N, N'-di (3 "-fluorophenyl) -1,3-diaminobenzene 15. N, N'- Bis [4 '-(N ", N" -diphenylamino) phenyl] -N, N'-di (4 "-phenylphenyl) -1,3-diaminobenzene16. N, N'-bis [4 '-(N ", N" -diphenylamino) phenyl] -N, N'-di (1 "-naphthyl) -1,3-diaminobenzene 17. N, N'-bis 17. [4 '-(N ", N" -diphenylamino) phenyl] -N, N'-di (2 "-naphthyl) -1,3-diaminobenzene N, N'-bis [4 '-(N ", N" -diphenylamino) phenyl] -N, N'-di (2 "-furyl) -1,3-diaminobenzene 19. 4-chloro-N, N'-bis [4 '-(N ",
N "-diphenylamino) phenyl] -N, N'-diphenyl-1,3-diaminobenzene 20. 6-methyl-N, N'-bis [4 '-(N",
N "-diphenylamino) phenyl] -N, N'-diphenyl-1,3-diaminobenzene 21. 4-ethoxy-N, N'-bis [4'-
(N ", N" -diphenylamino) phenyl] -N,
N'-diphenyl-1,3-diaminobenzene 22. 5-phenyl-N, N'-bis [4'-
(N ", N" -diphenylamino) phenyl] -N,
N'-diphenyl-1,3-diaminobenzene 23. N, N'-bis [4 '-[N "-(3" -fluorophenyl) -N "-(phenyl) amino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene 24. N'-bis [4 '-[N "-(3" -chlorophenyl) -N "-(phenyl) amino] phenyl]
-N, N'-diphenyl-1,3-diaminobenzene 25. N, N'-bis [4 '-[N ", N" -di (3 "-fluorophenyl) amino] phenyl] -N,
N'-diphenyl-1,3-diaminobenzene 26. N, N'-bis [4 '-[N "-(3" -fluorophenyl) -N "-phenylamino] phenyl]-
N, N'-di (4 "'-methylphenyl) -1,3-diaminobenzene 27. N, N'-bis [4'-[N"-(2 "-methylphenyl) -N"-(phenyl ) Amino] phenyl]
-N, N'-diphenyl-1,3-diaminobenzene 28. N, N'-bis [4 '-[N "-(3" -methylphenyl) -N "-phenylamino] phenyl]-
N, N'-diphenyl-1,3-diaminobenzene 29. N, N'-bis [4 '-[N "-(4" -methylphenyl) -N "-phenylamino] phenyl]-
N, N'-diphenyl-1,3-diaminobenzene 30. N, N'-bis [4 '-[N "-(4" -ethylphenyl) -N "-phenylamino] phenyl]-
N, N'-diphenyl-1,3-diaminobenzene

31. N, N'-bis [4 '-[N "-
(4 "-tert-butylphenyl) -N" -phenylamino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene N, N'-bis [4 '-[N "-(4" -n-
Octylphenyl) -N "-phenylamino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene 33. N, N'-bis [4 '-[N"-(2 ", 4"
-Dimethylphenyl) -N "-phenylamino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene 34. N, N'-bis [4 '-[N"-(2 ", 6"
-Dimethylphenyl) -N "-phenylamino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene 35. N, N'-bis [4 '-[N"-(3 ", 4"
-Dimethylphenyl) -N "-phenylamino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene 36. N, N'-bis [4 '-[N"-(1 "-naphthyl)- N "-phenylamino] phenyl] -N, N '
-Diphenyl-1,3-diaminobenzene 37. N, N'-bis [4 '-[N "-(2" -naphthyl) -N "-phenylamino] phenyl] -N, N'
-Diphenyl-1,3-diaminobenzene 38. N, N'-bis [4 '-[N "-(4" -pyridyl) -N "-phenylamino] phenyl] -N, N'
-Diphenyl-1,3-diaminobenzene 39. N, N'-bis [4 '-[N "-(2" -thienyl) -N "-phenylamino] phenyl] -N, N'
-Diphenyl-1,3-diaminobenzene 40. N, N'-bis [4 '-[N ", N" -di (2 "-methylphenyl) amino] phenyl] -N,
N'-diphenyl-1,3-diaminobenzene

41. N, N'-bis [4 '-[N ",
N "-di (3" -methylphenyl) amino] phenyl]
-N, N'-diphenyl-1,3-diaminobenzene 42. N, N'-bis [4 '-[N ", N" -di (4 "-methylphenyl) amino] phenyl] -N,
N'-diphenyl-1,3-diaminobenzene 43. N, N'-bis [4 '-[N ", N" -di (4 "-tert-butylphenyl) amino] phenyl]-
N, N'-diphenyl-1,3-diaminobenzene 44. N, N'-bis [4 '-[N ", N" -di (4 "-cyclohexylphenyl) amino] phenyl]
—N, N′-diphenyl-1,3-diaminobenzene 45. N, N'-bis [4 '-[N ", N" -di (2 ", 5" -diisopropylphenyl) amino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene N, N'-bis [4 '-[N ", N" -di (3 ", 5" -dimethylphenyl) amino] phenyl]
—N, N′-diphenyl-1,3-diaminobenzene 47. N, N'-bis [4 '-[N "-(3" -methylphenyl) -N "-(4""-ethylphenyl) amino] phenyl] -N, N'-diphenyl-1,3-diamino Benzene 48. N, N'-bis [4 '-[N "-(3" -methylphenyl) -N "-phenylamino] phenyl]-
N, N'-Di (3 "'-methylphenyl) -1,3-diaminobenzene 49. N, N'-bis [4'-[N"-(4 "-methylphenyl) -N" -phenylamino ] Phenyl]-
N, N'-di (3 "'-methylphenyl) -1,3-diaminobenzene 50. N, N'-bis [4'-[N"-(4 "-methylphenyl) -N" -phenylamino ] Phenyl]-
N, N'-di (4 "'-methylphenyl) -1,3-diaminobenzene

51. N, N'-bis [4 '-[N "-
(4 "-tert-butylphenyl) -N" -phenylamino] phenyl] -N, N'-di (4 "'-methylphenyl) -1,3-diaminobenzene 52. N, N'-bis [4 '-[N "-(3" -methylphenyl) -N "-phenylamino] phenyl]-
N, N'-di (4 "'-phenylphenyl) -1,3-diaminobenzene 53. N, N'-bis [4'-[N", N "-di (2" -methylphenyl) amino] Phenyl] -N,
N'-di (4 "'-phenylphenyl) -1,3-diaminobenzene 54. N, N'-bis [4'-[N"-(3 "-methylphenyl) -N" -phenylamino] phenyl ]-
N, N'-di (1 "'-naphthyl) -1,3-diaminobenzene 55. N, N'-bis [4'-[N"-(2 "-methoxyphenyl) -N" -phenylamino] Phenyl]-
N, N'-diphenyl-1,3-diaminobenzene 56. N, N'-bis [4 '-[N "-(3" -ethoxyphenyl) -N "-phenylamino] phenyl]-
N, N'-diphenyl-1,3-diaminobenzene 57. N, N'-bis [4 '-[N "-(4" -methoxyphenyl) -N "-phenylamino] phenyl]-
N, N'-diphenyl-1,3-diaminobenzene 58. N, N'-bis [4 '-[N "-(4" -n-
Butoxyphenyl) -N "-phenylamino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene 59. N, N'-bis [4 '-[N"-(3 ", 4"
-Dimethoxyphenyl) -N "-phenylamino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene 60. N, N'-bis [4 '-[N", N "-di (3" -Methoxyphenyl) amino] phenyl] -N,
N'-diphenyl-1,3-diaminobenzene

61. N, N'-bis [4 '-[N ",
N "-di (4" -methoxyphenyl) amino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene N, N'-bis [4 '-[N ", N" -di (4 "-ethoxyphenyl) amino] phenyl] -N,
N'-diphenyl-1,3-diaminobenzene 63. N, N'-bis [4 '-[N "-(4" -methoxyphenyl) -N "-phenylamino] phenyl]-
N, N'-di (4 "'-methylphenyl) -1,3-diaminobenzene 64. N, N'-bis [4'-[N"-(4 "-methoxyphenyl) -N" -phenylamino ] Phenyl]-
N, N'-di (4 "'-phenylphenyl) -1,3-diaminobenzene 65. N, N'-bis [4'-[N"-(2 "-methyl-4" -methoxyphenyl)- N "-phenylamino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene 66. N, N'-bis [4 '-[N"-(3 "-methyl-5" -methoxyphenyl) -N "-phenylamino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene 67. N, N'-bis [4 '-[N"-(4 "-methoxyphenyl) -N"- (3 "'-methylphenyl) amino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene 68. N, N'-bis [4'-[N"-(4 "-ethoxyphenyl)- N "-(2"', 4 "'-dimethylphenyl) amino] phenyl] -N, N'-diphenyl-1
3-diaminobenzene 69. N, N'-bis [4 '-[N "-(2" -methyl-4 "-methoxyphenyl) -N"-(3 "'-methylphenyl) amino] phenyl] -N, N'-diphenyl- 1,3-diaminobenzene 70. N, N'-bis [4 '-[N "-(2" -methyl-4 "-methoxyphenyl) -N"-(2 "', 5"'-
Dimethylphenylamino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene

71. N, N'-bis [4 '-[N "-
(4 "-phenylphenyl) -N" -phenylamino]
Phenyl] -N, N'-diphenyl-1,3-diaminobenzene N, N'-bis [4 '-[N "-(4" -phenylphenyl) -N "-(4""-methylphenyl) amino] phenyl] -N, N'-diphenyl-1,3-diamino Benzene 73. N, N'-bis [4 '-[N "-(4" -m-
Tolylphenyl) -N "-phenylamino] phenyl]
-N, N'-diphenyl-1,3-diaminobenzene 74. N, N'-bis [4 '-[N "-(4" -p-
Tolylphenyl) -N "-phenylamino] phenyl]
—N, N′-diphenyl-1,3-diaminobenzene 75. N, N'-bis [4 '-[N ", N" -di (4 "-phenylphenyl) amino] phenyl] -N,
N'-diphenyl-1,3-diaminobenzene 76. N- [4 '-[N "-(3" -methylphenyl) -N "-phenylamino] phenyl] -N'-
[4 "'-(N"', N "'-diphenylamino) phenyl]
—N, N′-diphenyl-1,3-diaminobenzene 77. N- [4 '-[N "-(4" -methylphenyl) -N "-phenylamino] phenyl] -N'-
[4 "'-(N"', N "'-diphenylamino) phenyl]
-N, N'-diphenyl-1,3-diaminobenzene 78. N- [4 '-[N "-(4" -tert-butylphenyl) -N "-phenylamino] phenyl] -N'-
[4 "'-(N"', N "'-diphenylamino) phenyl]
—N, N′-diphenyl-1,3-diaminobenzene 79. N- [4 '-[N ", N" -di (4 "-methylphenyl) amino] phenyl] -N'-[4"'-
(N "', N"'-diphenylamino) phenyl] -N,
N'-diphenyl-1,3-diaminobenzene N- [4 '-[N ", N" -di (4 "-methylphenyl) amino] phenyl] -N'-[4"'-[
N "', N"'-di (3 "'-methylphenyl) amino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene

81. N- [4 '-[N "-(4" -methoxyphenyl) -N "-phenylamino] phenyl]
-N '-[4 "'-(N"', N "'-diphenylamino) phenyl] -N, N'-diphenyl-1,3-diaminobenzene 82. N- [4 '-[N", N "-Di (4" -methoxyphenyl) amino] phenyl] -N '-[4 "'-[
N "', N"'-di (3 "'-ethylphenyl) amino] phenyl] -N, N'-diphenyl-1,3-diaminobenzene 83. N, N'-bis [2'-chloro-4 '-
(N ", N" -diphenylamino) phenyl] -N,
N'-diphenyl-1,3-diaminobenzene 84. N, N'-bis [2'-methyl-4'-
(N ", N" -diphenylamino) phenyl] -N,
N'-diphenyl-1,3-diaminobenzene 85. N, N'-bis [3'-ethyl-4'-
(N ", N" -diphenylamino) phenyl] -N,
N'-diphenyl-1,3-diaminobenzene 86. N, N'-bis [2'-methoxy-4'-
(N ", N" -diphenylamino) phenyl] -N,
N'-diphenyl-1,3-diaminobenzene 87. N, N'-bis [2'-phenyl-4'-
(N ", N" -diphenylamino) phenyl] -N,
N'-diphenyl-1,3-diaminobenzene

The compound represented by the general formula (1) can be produced by a method known per se. For example,
It can be produced by reacting an N, N′-diaryl-1,3-diaminobenzene derivative with a 4-halogeno-N, N-diarylaminobenzene derivative in the presence of a copper compound (Ullman reaction). Also, for example, N, N'-
Diaryl-N, N'-di (4'-halogenophenyl)
It can also be produced by reacting a -1,3-diaminobenzene derivative with an N, N-diarylamine derivative in the presence of a copper compound.

The organic electroluminescent element usually has at least one light-emitting layer containing at least one light-emitting component sandwiched between a pair of electrodes. In consideration of the functional levels of hole injection and hole transport, electron injection and electron transport of the compound used in the light-emitting layer, a hole injection transport layer containing a hole injection transport component and / or An electron injection / transport layer containing an injection / transport component can also be provided. For example, when the compound used for the light emitting layer has a good hole injecting function, a hole transporting function or / and an electron injecting function, and an electron transporting function, the light emitting layer is preferably a hole injecting / transporting layer or / and an electron injecting / transporting layer. The element can also be configured to serve as Of course, depending on the case, a structure of a device (single-layer device) without both the hole injection transport layer and the electron injection transport layer may be employed. Further, each of the hole injection transport layer, the electron injection transport layer and the light emitting layer may have a single-layer structure or a multilayer structure,
The hole injecting and transporting layer and the electron injecting and transporting layer can be formed by separately providing a layer having an injection function and a layer having a transport function in each layer.

In the organic electroluminescent device of the present invention, the compound represented by the general formula (1) is preferably used for a hole injection / transport component and / or a light emitting component, and more preferably used for a hole injection / transport component. preferable. In the organic electroluminescent device of the present invention, the compound represented by the general formula (1) may be used alone or in combination.

The structure of the organic electroluminescent device of the present invention is not particularly limited.
Hole injection / transport layer / emission layer / electron injection / transport layer / cathode device (FIG. 1), (B) anode / hole injection / transport layer / emission layer / cathode device (FIG. 2), (C) anode / emission Layer / electron injection / transport layer / cathode type device (FIG. 3), (D) anode / light emitting layer / cathode type device (FIG. 4) and the like. Further, the device is of a type in which a light emitting layer is sandwiched between electron injection and transport layers (E).
Anode / hole injection / transport layer / electron injection / transport layer / emission layer / electron injection / transport layer / cathode type device (FIG. 5).
The element configuration of the (D) type is, of course, an element of a type in which a light emitting component is sandwiched between a pair of electrodes in a single layer form, and further, for example, (F) a hole injection / transport component, a light emitting component, An element of a type in which an electron injection / transport component is mixed and sandwiched between a pair of electrodes (FIG. 6), and (G) a layer in which a hole injection / transport component and a light emitting component are mixed, between a pair of electrodes. There is an element of the sandwiched type (FIG. 7) and an element of the type (H) sandwiched between a pair of electrodes in the form of a single layer in which a light emitting component and an electron injection / transport component are mixed (FIG. 8).

The organic electroluminescent device of the present invention is not limited to these device configurations, and each type of device may be provided with a plurality of hole injection / transport layers, light emitting layers, and electron injection / transport layers. it can. In each type of device, a light emitting component is provided between the hole injecting and transporting layer and the light emitting layer, and / or between the hole injecting and transporting component and the light emitting component. And a mixed layer of an electron injection and transport component. More preferred configurations of the organic electroluminescent device are (A) type device, (B) type device, (E)
Type element, (F) type element or (G) type element, and more preferably (A) type element, (B) type element, (F) type element or (G) type element.

As the organic electroluminescent device of the present invention, for example, (A) anode / hole injection / transport layer / emission layer / electron injection / transport layer / cathode type device shown in FIG. 1 will be described.
In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection / transport layer, 4 is a light emitting layer, 5 is an electron injection / transport layer, 6 is a cathode,
Reference numeral 7 denotes a power supply.

The organic electroluminescent device of the present invention is preferably supported on a substrate 1. The substrate is not particularly limited, but is preferably transparent or translucent. Transparent plastic sheet (for example, polyester, polycarbonate, polysulfone, polymethyl methacrylate, polypropylene,
A sheet made of polyethylene or the like), a translucent plastic sheet, quartz, a transparent ceramic, or a composite sheet combining these. Further, the luminescent color can be controlled by combining, for example, a color filter film, a color conversion film, and a dielectric reflection film on the substrate.

As the anode 2, it is preferable to use a metal, an alloy or an electrically conductive compound having a relatively large work function as an electrode material. As the electrode material used for the anode, for example, gold, platinum, silver, copper, cobalt, nickel,
Palladium, vanadium, tungsten, tin oxide, zinc oxide, ITO (indium tin oxide), polythiophene, polypyrrole, and the like can be given. These electrode substances may be used alone or in combination of two or more. The anode can be formed on the substrate by using such an electrode material by a method such as a vapor deposition method and a sputtering method. Further, the anode may have a single-layer structure or a multilayer structure. The sheet electric resistance of the anode is preferably several hundred Ω / □.
Hereinafter, more preferably, it is set to about 5 to 50 Ω / □. The thickness of the anode depends on the material of the electrode substance to be used, but is generally about 5 to 1000 nm, more preferably,
It is set to about 10 to 500 nm.

The hole injecting / transporting layer 3 is a layer containing a compound having a function of facilitating the injection of holes (holes) from the anode and a function of transporting the injected holes. The hole injecting and transporting layer includes a compound represented by the general formula (1) and / or another compound having a hole injecting and transporting function (for example, a phthalocyanine derivative, a triarylmethane derivative, a triarylamine derivative, an oxazole derivative,
Hydrazone derivative, stilbene derivative, pyrazoline derivative, polysilane derivative, polyphenylenevinylene and its derivative, polythiophene and its derivative, poly-
N-vinylcarbazole derivative). The compounds having a hole injection / transport function may be used alone or in combination. In the organic electroluminescent device of the present invention, the hole injecting and transporting layer preferably contains the compound represented by the general formula (1).

Other compounds having a hole injection / transport function used in the present invention include triarylamine derivatives (for example, 4,4′-bis [N-phenyl-N- (4 ″)).
-Methylphenyl) amino] biphenyl, 4,4'-bis [N-phenyl-N- (3 "-methylphenyl) amino] biphenyl, 4,4'-bis [N-phenyl-N-
(3 "-methoxyphenyl) amino] biphenyl, 4,
4'-bis [N-phenyl-N- (1 "-naphthyl) amino] biphenyl, 3,3'-dimethyl-4,4'-bis [N-phenyl-N- (3" -methylphenyl) amino] Biphenyl, 1,1-bis [4 ′-[N, N-di (4 ″ -methylphenyl) amino] phenyl] cyclohexane, 9,10-bis [N- (4′-methylphenyl) -N- (4 "-N-butylphenyl) amino] phenanthrene, 3,8-bis (N, N-diphenylamino) -6-phenylphenanthridine, 4-methyl-
N, N-bis [4 ", 4"'-bis[N',N'-di (4
-Methylphenyl) amino] biphenyl-4'-yl]
Aniline, 5,5 "-bis [4- (bis [4-methylphenyl] amino) phenyl] -2,2 ': 5', 2"-
Terthiophene, 1,3,5-tris (diphenylamino) benzene, 4,4 ′, 4 ″ -tris (N-carbazolyl) triphenylamine, 4,4 ′, 4 ″ -tris [N- (3 ″ ″ -Methylphenyl) -N-phenylamino] triphenylamine, 1,3,5-tris [4-diphenylaminophenyl) phenylamino] benzene, etc., polythiophene and derivatives thereof, and poly-N-vinylcarbazole derivatives are more preferable. , A triarylamine derivative and a poly-N-vinylcarbazole derivative are more preferable.When the compound represented by the general formula (1) is used in combination with another compound having a hole injecting and transporting function, The proportion of the compound represented by the general formula (1) occupying is preferably 0.1% by weight or more, more preferably 0.1 to 99.9% by weight. %, More preferably,
About 1 to 99% by weight, particularly preferably 5 to 95% by weight
Prepare to about.

The light emitting layer 4 has a function of injecting holes and electrons,
This is a layer containing a compound having a transport function thereof and a function of generating excitons by recombination of holes and electrons. The light-emitting layer includes a compound represented by the general formula (1) and / or a compound having another light-emitting function (eg, an acridone derivative, a quinacridone derivative, a polycyclic aromatic compound [eg,
Rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, 9,10-diphenylanthracene, 9,10-
Bis (phenylethynyl) anthracene, 1,4-bis (9′-ethynylanthracenyl) benzene, 4,4 ′
-Bis (9 "-ethynylanthracenyl) biphenyl], a triarylamine derivative (for example, the compounds described above as compounds having a hole injecting and transporting function), and an organometallic complex [for example, tris (8- Quinolinolate) aluminum, bis (10-benzo [h]
Quinolinolate) beryllium, zinc salt of 2- (2'-hydroxyphenyl) benzoxazole, 2- (2'-
4-hydroxyphenyl) benzothiazole zinc salt, 4-
Zinc salts of hydroxyacridine], stilbene derivatives [eg, 1,1,4,4-tetraphenyl-1,3-
Butadiene, 4,4'-bis (2,2-diphenylvinyl) biphenyl], coumarin derivative [for example, coumarin 1, coumarin 6, coumarin 7, coumarin 30, coumarin 106, coumarin 138, coumarin 151, coumarin 1
52, coumarin 153, coumarin 307, coumarin 31
1. Coumarin 314, Coumarin 334, Coumarin 33
8, coumarin 343, coumarin 500], pyran derivatives [eg, DCM1, DCM2], oxazone derivatives [eg, Nile Red], benzothiazole derivatives,
Benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamate derivatives, poly-
N-vinyl carbazole and its derivatives, polythiophene and its derivatives, polyphenylene and its derivatives, polyfluorene and its derivatives, polyphenylene vinylene and its derivatives, polybiphenylene vinylene and its derivatives, polyterphenylene vinylene and its derivatives, polynaphthylene vinylene and And at least one of its derivatives, polythienylenevinylene and derivatives thereof).

In the organic electroluminescent device of the present invention, the light emitting layer preferably contains a compound represented by the general formula (1). When the compound represented by the general formula (1) and the compound having another light emitting function are used in combination, the ratio of the compound represented by the general formula (1) in the light emitting layer is preferably 0.001 to 99. It is adjusted to about .999% by weight.
As other compounds having a light-emitting function used in the present invention, polycyclic aromatic compounds and light-emitting organometallic complexes are more preferable. For example, J. Appl. Phys., 65 , 3610 (1989),
As described in JP-A-5-214332, the light-emitting layer can be composed of a host compound and a guest compound (dopant). A light emitting layer can be formed by using the compound represented by the general formula (1) as a host compound,
Further, a light-emitting layer can be formed as a guest compound. When forming a light emitting layer using the compound represented by the general formula (1) as a host compound, the guest compound
For example, the above compounds having other light emitting functions can be mentioned, and among them, a polycyclic aromatic compound is preferable. In this case, a compound having another light emitting function is added in an amount of about 0.001 to 40% by weight based on the compound represented by the general formula (1),
Preferably, it is more preferably used in an amount of about 0.1 to 20% by weight.

The polycyclic aromatic compound used in combination with the compound represented by the general formula (1) is not particularly limited. For example, rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene,
Tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, 9,10-diphenylanthracene, 9,10-bis (phenylethynyl) anthracene, 1,4-bis (9′-ethynylanthracenyl) benzene, 4,4′-bis (9 "-ethynylanthracenyl) biphenyl, etc. Of course, the polycyclic aromatic compound may be used alone or in combination of two or more.

When the compound represented by the general formula (1) is used as a guest compound to form a light emitting layer, the host compound is preferably a light emitting organometallic complex. In this case, the compound represented by the general formula (1) is preferably used in an amount of about 0.001 to 40% by weight, more preferably about 0.1 to 20% by weight, based on the luminescent organic metal complex. . The luminescent organometallic complex used in combination with the compound represented by the general formula (1) is not particularly limited, but a luminescent organoaluminum complex is preferable and has a substituted or unsubstituted 8-quinolinolate ligand. Luminescent organoaluminum complexes are more preferred. Preferred luminescent organic metal complexes include, for example, luminescent organic aluminum complexes represented by general formulas (a) to (c). (Q) _3- Al (a) (wherein Q represents a substituted or unsubstituted 8-quinolinolate ligand) (Q) _2- Al-OL (b) (wherein Q represents substituted 8 -Represents a quinolinolate ligand, O
-L is a phenolate ligand, and L represents a hydrocarbon group having 6 to 24 carbon atoms including a phenyl moiety.) (Q) _2- Al-O-Al- (Q) ₂ (c) Q represents a substituted 8-quinolinolate ligand)

Specific examples of the luminescent organometallic complex include, for example, tris (8-quinolinolate) aluminum, tris (4-methyl-8-quinolinolate) aluminum, tris (5-methyl-8-quinolinolate) aluminum, tris ( 3,4-dimethyl-8-quinolinolate) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, tris (4,6-dimethyl-8-quinolinolate) aluminum, bis (2-methyl-8-quinolinolate) (Phenolate) aluminum, bis (2-methyl-8-quinolinolate) (2-
Methylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-methylphenolate) aluminum, bis (2-methyl-8-quinolinolate)
(4-methylphenolate) aluminum, bis (2-
Methyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-phenylphenolate) aluminum,
Bis (2-methyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2-methyl-8
-Quinolinolate) (2,3-dimethylphenolate)
Aluminum, bis (2-methyl-8-quinolinolate) (2,6-dimethylphenolate) aluminum,
Bis (2-methyl-8-quinolinolate) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3,5-dimethylphenolate) aluminum, bis (2-methyl-8- Quinolinolate) (3,5-di-tert-butylphenolate) aluminum, bis (2-methyl-8-quinolinolate)
(2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,4,6-
Triphenylphenolate) aluminum, bis (2-
Methyl-8-quinolinolate) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl-8
-Quinolinolate) (2,4,5,6-tetramethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (1-naphtholate) aluminum, bis (2-methyl-8-quinolinolate) (2-naphtholate) ) Aluminum, bis (2,4-dimethyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate)
(3-phenylphenolato) aluminum, bis (2,4-dimethyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-dimethylphenolate) ) Aluminum, bis (2,4-dimethyl-8-)
Quinolinolate) (3,5-di-tert-butylphenolate) aluminum,

Bis (2-methyl-8-quinolinolate)
Aluminum-μ-oxo-bis (2-methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolato) aluminum, Bis (2-methyl-4-ethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-
4-ethyl-8-quinolinolate) aluminum, bis (2-methyl-4-methoxy-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8-quinolinolate) aluminum, bis (2-
Methyl-5-cyano-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-
Quinolinolate) aluminum, bis (2-methyl-5)
-Trifluoromethyl-8-quinolinolato) aluminum- [mu] -oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum. Of course, the luminescent organometallic complex may be used alone or in combination.

The electron injection / transport layer 5 is a layer containing a compound having a function of facilitating the injection of electrons from the cathode and a function of transporting the injected electrons. Examples of the compound having an electron injecting and transporting function used in the electron injecting and transporting layer include, for example, organometallic complexes [eg, tris (8-quinolinolate) aluminum, bis (10-benzo [h] quinolinolate) beryllium], oxadiazole Derivatives, triazole derivatives, triazine derivatives, perylene derivatives, quinoline derivatives, quinoxaline derivatives, diphenylquinone derivatives, nitro-substituted fluorenone derivatives, thiopyrandioxide derivatives and the like can be mentioned. The compounds having an electron injection / transport function may be used alone or in combination.

As the cathode 6, it is preferable to use a metal, an alloy or an electrically conductive compound having a relatively small work function as an electrode material. Examples of the electrode material used for the cathode include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, calcium, magnesium, magnesium-silver alloy, magnesium-indium alloy, indium, ruthenium, titanium,
Manganese, yttrium, aluminum, an aluminum-lithium alloy, an aluminum-calcium alloy, an aluminum-magnesium alloy, a graphite thin film and the like can be given. These electrode substances may be used alone or in combination of two or more. The cathode, these electrode substances, for example, a vapor deposition method, a sputtering method,
It can be formed on the electron injection transport layer by a method such as an ionization vapor deposition method, an ion plating method, and a cluster ion beam method. Further, the cathode may have a single-layer structure or a multilayer structure. The sheet electric resistance of the cathode is preferably set to several hundreds Ω / □ or less. The thickness of the cathode depends on the material of the electrode substance used, but is generally about 5 to 1000 nm, more preferably,
It is set to about 10 to 500 nm. In order to efficiently extract light emitted from the organic electroluminescent device, it is preferable that at least one of the anode and the cathode is transparent or translucent, and the transmittance of emitted light is generally 70% or more. It is more preferable to set the material and thickness of the anode.

The organic electroluminescent device of the present invention may contain a singlet oxygen quencher in at least one layer. The singlet oxygen quencher is not particularly limited and includes, for example, rubrene,
Nickel complexes, diphenylisobenzofuran and the like can be mentioned, and rubrene is particularly preferred. The layer containing the singlet oxygen quencher is not particularly limited, but is preferably a light emitting layer or a hole injection transport layer, and more preferably a hole injection transport layer.
When a singlet oxygen quencher is contained in the hole injecting and transporting layer, for example, the singlet oxygen quencher may be uniformly contained in the hole injecting and transporting layer, and a layer adjacent to the hole injecting and transporting layer (for example, a light emitting layer, (An electron injection / transport layer having a light emitting function). The content of the singlet oxygen quencher is from 0.01 to 50% by weight, preferably from 0.0 to 50% by weight of the total amount constituting the contained layer (for example, the hole injection / transport layer).
5 to 30% by weight, more preferably 0.1 to 20% by weight
It is.

The method for forming the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer is not particularly limited, and may be, for example, a vacuum evaporation method, an ionization evaporation method, a solution coating method (eg, a spin coating method, a casting method, or the like). Method, dip coating method,
It can be manufactured by forming a thin film by a bar coating method, a roll coating method, a Langmuir-Brosette method, or the like. When forming each layer by a vacuum deposition method, the conditions of the vacuum deposition are not particularly limited,
It is carried out under a vacuum of about 10 ^-5 Torr or less, a boat temperature (deposition source temperature) of about 50 to 400 ° C., a substrate temperature of about −50 to 300 ° C., and a deposition rate of about 0.005 to 50 nm / sec. Is preferred. In this case, by forming the layers such as the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer continuously under vacuum, an organic electroluminescent device having more excellent various characteristics can be manufactured. When each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer is formed using a plurality of compounds by a vacuum deposition method, each boat containing the compounds is individually temperature-controlled and co-deposited. Is preferred.

When each layer is formed by a solution coating method,
The components forming each layer or the components and a binder resin or the like are dissolved or dispersed in a solvent to form a coating liquid. Examples of the binder resin that can be used for each of the hole injection transport layer, the light emitting layer, and the electron injection transport layer include poly-N-vinylcarbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl acrylate, and the like.
Polymethyl methacrylate, polyether, polycarbonate, polyamide, polyimide, polyamide imide,
High molecular compounds such as polyparaxylene, polyethylene, polyphenylene oxide, polyethersulfone, polyaniline and its derivatives, polythiophene and its derivatives, polyphenylenevinylene and its derivatives, polyfluorene and its derivatives, and polythienylenevinylene and its derivatives. . The binder resin may be used alone or in combination.

When each layer is formed by a solution coating method,
The components forming each layer or the components and a binder resin are combined with a suitable organic solvent (for example, hexane, octane,
Decane, toluene, xylene, ethylbenzene, hydrocarbon solvents such as 1-methylnaphthalene, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, for example, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, Halogenated hydrocarbon solvents such as tetrachloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene, for example, ester solvents such as ethyl acetate, butyl acetate, and amyl acetate, for example, methanol, propanol, butanol, pentanol, hexanol, and cyclohexanol , Methyl cellosolve, ethyl cellosolve, alcohol solvents such as ethylene glycol, for example, dibutyl ether, tetrahydrofuran,
Dioxane, ether solvents such as anisole, for example,
Polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide) and / or dissolved in water Alternatively, a thin film can be formed by various coating methods by dispersing the mixture into a coating liquid.

The method of dispersion is not particularly limited. For example, the particles can be dispersed into fine particles using a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer or the like. The concentration of the coating solution is not particularly limited, and can be set to a concentration range suitable for producing a desired thickness depending on a coating method to be performed, and is generally about 0.1 to 50% by weight. Preferably, the solution concentration is about 1 to 30% by weight. When a binder resin is used, the amount of the binder resin is not particularly limited. However, in general, the amount of the binder resin is limited to the components forming each layer (when forming a single-layer element, the total 5) to 99.9% by weight
Level, preferably about 10 to 99% by weight, more preferably about 15 to 90% by weight.

The thicknesses of the hole injecting and transporting layer, the light emitting layer and the electron injecting and transporting layer are not particularly limited, but are generally preferably set to about 5 nm to 5 μm.
A protective layer (sealing layer) may be provided on the fabricated device for the purpose of preventing contact with oxygen, moisture, or the like, or the device may be formed of, for example, paraffin, liquid paraffin, silicon oil, fluorocarbon oil, zeolite, or the like. It can be protected by being enclosed in an inert substance such as a contained fluorocarbon oil. Examples of the material used for the protective layer include organic polymer materials (for example, fluorinated resin, epoxy resin, silicone resin, epoxy silicone resin, polystyrene, polyester, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene) , Polyphenylene oxide), inorganic materials (for example, diamond thin film, amorphous silica, electrically insulating glass, metal oxide, metal nitride, metal carbide,
Metal sulfide), and a photocurable resin. The material used for the protective layer may be used alone or in combination of two or more. The protective layer may have a single-layer structure or a multilayer structure.

Further, a metal oxide film (for example, an aluminum oxide film) or a metal fluoride film can be provided as a protective film on the electrode. Also, for example, on the surface of the anode,
For example, an interface layer (intermediate layer) composed of an organic phosphorus compound, polysilane, an aromatic amine derivative, and a phthalocyanine derivative
Can also be provided. Further, electrodes, eg, anodes, can be used by treating the surface with, eg, acid, ammonia / hydrogen peroxide, or plasma.

The organic electroluminescent device of the present invention is generally used as a DC-driven device, but can also be used as a pulse-driven or AC-driven device.
Incidentally, the applied voltage is generally about 2 to 30 V. The organic electroluminescent device of the present invention can be used for, for example, a panel light source, various light emitting devices, various display devices, various labels, various sensors, and the like.

[0048]

The present invention will be described in more detail with reference to the following examples, which, of course, are not intended to limit the scope of the present invention. Example 1 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr.
First, N, N'-bis [4'-
(N ", N" -diphenylamino) phenyl] -N,
N′-diphenyl-1,3-diaminobenzene (compound of Exemplified Compound No. 1) was deposited at a deposition rate of 0.2 nm / sec to a thickness of 75 nm to form a hole injection transport layer. Next, tris (8-quinolinolato) aluminum was deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form a light-emitting layer also serving as an electron injection / transport layer. Further, magnesium and silver are further deposited thereon at a deposition rate of 0.2 nm / se.
A co-evaporation (weight ratio 10: 1) was carried out to a thickness of 200 nm at c to obtain a cathode, thereby producing an organic electroluminescent device. In addition, evaporation is
The test was performed while maintaining the reduced pressure of the vapor deposition tank. A DC voltage is applied to the produced organic electroluminescent device, and a dry
The device was continuously driven at a constant current density of mA / cm ² . Initially,
Green light emission of 6.5 V and a luminance of 450 cd / m ² was confirmed. The half life of the luminance was 600 hours.

Examples 2 to 21 In Example 1, instead of using the compound of Exemplified Compound No. 1 in forming the hole injecting and transporting layer, the compound of Exemplified Compound No. 2 (Example 2) and Exemplified Compound No. 5 were used. (Example 3), compound of Exemplified Compound No. 11 (Example 4), compound of Exemplified Compound No. 14 (Example 5), compound of Exemplified Compound No. 17 (Example 6), compound of Exemplified Compound No. 20 (Example 7), a compound of Exemplified Compound No. 28 (Example 8), a compound of Exemplified Compound No. 30 (Example 9), a compound of Exemplified Compound No. 31 (Example 10),
Compound of Exemplified Compound No. 35 (Example 11), Compound of Exemplified Compound No. 36 (Example 12), Exemplified Compound No. 4
Compound No. 2 (Example 13), Compound No. 49 (Example 14), Compound No. 56 (Example 15), Compound No. 60 (Example 1)
6), compound of Exemplified Compound No. 65 (Example 17), compound of Exemplified Compound No. 67 (Example 18), compound of Exemplified Compound No. 73 (Example 19), Exemplified Compound No. 79
(Example 20) and the compound of Exemplified Compound No. 86 (Example 21) were used to produce an organic electroluminescent device by the method described in Example 1. Green light emission was confirmed from each element. The characteristics were further examined, and the results are shown in Table 1 (Tables 1 and 2).

Comparative Examples 1 to 3 In Example 1, instead of using the compound of Exemplified Compound No. 1 in forming the hole injecting and transporting layer,
-Bis [N-phenyl-N- (3 "-methylphenyl)
Amino] biphenyl (Comparative Example 1), 1,1-bis [4 ′
-[N, N-di (4 "-methylphenyl) amino] phenyl] cyclohexane (Comparative Example 2), N, N'-bis [4- (N", N "-diphenylamino) phenyl]-
An organic electroluminescent device was produced by the method described in Example 1 except that N, N'-diphenyl-1,4-diaminobenzene (Comparative Example 3) was used. Green light emission was confirmed from each element. The characteristics were further examined, and the results are shown in Table 1.

[0051]

[Table 1]

[0052]

[Table 2]

Example 22 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr.
First, poly (thiophene-2,5) was placed on the ITO transparent electrode.
-Diyl) was deposited at a deposition rate of 0.1 nm / sec to a thickness of 20 nm to form a first hole injection / transport layer. Next, the compound of Exemplified Compound No. 1 was deposited at a deposition rate of 0.2 nm / sec.
Was evaporated to a thickness of 55 nm to form a second hole injection / transport layer. Then, on top of this, tris (8-quinolinolate)
Aluminum is deposited at 50 nm at a deposition rate of 0.2 nm / sec.
To form a light-emitting layer also serving as an electron injection / transport layer. Further, magnesium and silver were further deposited thereon at a vapor deposition rate of 0.1 mm.
Co-deposition to a thickness of 200 nm at 2 nm / sec (weight ratio 1
0: 1) to form a cathode to produce an organic electroluminescent device.
In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank.
A DC voltage was applied to the produced organic electroluminescent device, and the device was continuously driven at a constant current density of 10 mA / cm ² in a dry atmosphere. Initially, green light emission of 6.4 V and luminance of 380 cd / m ² was confirmed. The half life of the luminance was 1600 hours.

Example 23 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr.
First, 4,4 ′, 4 ″ -tris [N- (3 ″ ′-methylphenyl) -N-phenylamino] triphenylamine was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / sec.
Then, it was deposited to a thickness of 50 nm to form a first hole injection transport layer. Next, the compound of Exemplified Compound No. 4 and rubrene were
20n from different evaporation sources at a deposition rate of 0.2nm / sec
m to give a light emitting layer also serving as a second hole injection / transport layer. Subsequently, tris (8-quinolinolato) aluminum was deposited thereon at a deposition rate of 0,1.
Vapor deposition was performed at 2 nm / sec to a thickness of 50 nm to form an electron injecting and transporting layer. Further, magnesium and silver were co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to form a cathode, thereby producing an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. A DC voltage was applied to the produced organic electroluminescent device, and the device was continuously driven at a constant current density of 10 mA / cm ² in a dry atmosphere. Initially, yellow light emission of 6.2 V and a luminance of 540 cd / m ² was confirmed. The half life of the luminance was 1500 hours.

Example 24 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr.
First, poly (thiophene-2,5) was placed on the ITO transparent electrode.
-Diyl) was deposited at a deposition rate of 0.1 nm / sec to a thickness of 20 nm to form a first hole injection / transport layer. After returning the vapor deposition tank to the atmospheric pressure, the pressure of the vapor deposition tank was again reduced to 3 × 10 ⁻⁶ Torr. Next, the compound of Exemplified Compound No. 28 and rubrene were co-evaporated from different evaporation sources at a deposition rate of 0.2 nm / sec to a thickness of 55 nm (weight ratio: 10: 1), and also served as the second hole injection / transport layer. Light emitting layer. While maintaining the reduced pressure state, tris (8-quinolinolate) aluminum was further deposited thereon at a deposition rate of 0.2 nm / sec for 50 n.
m to form an electron injecting and transporting layer. While maintaining the reduced pressure, magnesium and silver were further co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to form a cathode, thereby producing an organic electroluminescent device. . Apply a DC voltage to the produced organic electroluminescent device,
The device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere. Initially, yellow light emission of 6.2 V and a luminance of 450 cd / m ² was confirmed. The half life of the luminance was 2000 hours.

Example 25 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr.
First, the compound of Exemplified Compound No. 1 was deposited on the ITO transparent electrode to a thickness of 55 nm at a deposition rate of 0.2 nm / sec to form a hole injection transport layer. Next, tris (8-quinolinolate) aluminum and the compound of Exemplified Compound No. 5 were further deposited thereon from different evaporation sources at an evaporation rate of 0.2 nm.
/ Sec co-deposition to a thickness of 40 nm (weight ratio 10: 1)
Thus, a light emitting layer was obtained. Furthermore, tris (8-quinolinolate) aluminum was deposited at a deposition rate of 0.2 nm / sec for 30 minutes.
It was deposited to a thickness of nm to form an electron injection transport layer. Further, magnesium and silver are further deposited thereon at a deposition rate of 0.2 nm / sec.
Then, co-evaporation (weight ratio: 10: 1) was performed to a thickness of 200 nm to form a cathode, thereby producing an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. Apply a DC voltage to the organic electroluminescent device prepared, and in a dry atmosphere,
It was continuously driven at a constant current density of A / cm ² . Initially,
Green light emission of 6.2 V and luminance of 460 cd / m ² was confirmed. The half life of the luminance was 2000 hours.

Example 26 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas and further washed with UV / ozone. Next, on the ITO transparent electrode, polycarbonate (weight average molecular weight: 50,000),
And the compound of Exemplified Compound No. 31 in a weight ratio of 100: 50.
Was used as a hole injection transport layer having a thickness of 40 nm by a dip coating method using a 3% by weight dichloroethane solution. Next, after fixing the glass substrate having the hole injecting and transporting layer to the substrate holder of the vapor deposition apparatus, the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. Next, tris (8-quinolinolato) aluminum was deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form a light-emitting layer also serving as an electron injection / transport layer. Furthermore, on the light emitting layer,
Magnesium and silver are deposited at a deposition rate of 0.2 nm / sec.
A cathode was formed by co-evaporation (weight ratio: 10: 1) to a thickness of 0 nm to produce an organic electroluminescent device. When a DC voltage of 10 V was applied to the produced organic electroluminescent device in a dry atmosphere, a current of 95 mA / cm ² flowed. Brightness 1030
Green light emission of cd / m ² was confirmed. The half life of the luminance was 150 hours.

Example 27 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas and further washed with UV / ozone. Next, on the ITO transparent electrode, polymethyl methacrylate (weight average molecular weight 250
00), the compound of Exemplified Compound No. 46, and tris (8-quinolinolato) aluminum were each added at a weight ratio of 10
Using a 3% by weight dichloroethane solution containing 0: 50: 0.5 in a ratio of 100n by dip coating.
m light emitting layers were formed. Next, after fixing the glass substrate having the light emitting layer to the substrate holder of the vapor deposition apparatus, the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. Further, on the light emitting layer, magnesium and silver were co-deposited (weight ratio: 10: 1) to a thickness of 200 nm at a deposition rate of 0.2 nm / sec to form an organic electroluminescent device. When a DC voltage of 15 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 80 mA / cm ² flowed. Brightness 530
Green light emission of cd / m ² was confirmed. The half life of the luminance was 200 hours.

[0059]

According to the present invention, it has become possible to provide an organic electroluminescent device having a long emission life and excellent durability.

[Brief description of the drawings]

FIG. 1 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 2 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 3 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 4 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 5 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 6 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 7 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 8 is a schematic structural diagram of an example of an organic electroluminescent device.

[Explanation of symbols]

 1: substrate 2: anode 3: hole injection / transport layer 3a: hole injection / transport component 4: light emitting layer 4a: light emitting component 5: electron injection / transport layer 5 ″: electron injection / transport layer 5a: electron injection / transport component 6: cathode 7: Power supply

Claims (4)

[Claims] A compound represented by the general formula (1) between a pair of electrodes:
An organic electroluminescence device comprising at least one layer sandwiching at least one layer containing at least one compound represented by the formula: Embedded image (In the formula, Ar _{1 to} Ar ₆ represent a substituted or unsubstituted aryl group, and X _{1 to} X ₆ represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. Represents a group or a substituted or unsubstituted aryl group) 2. The organic electroluminescent device according to claim 1, wherein the layer containing the compound represented by the general formula (1) is a hole injection / transport layer. 3. The organic electroluminescent device according to claim 1, further comprising a light emitting layer between the pair of electrodes. 4. The organic electroluminescent device according to claim 1, further comprising an electron injection / transport layer between the pair of electrodes.