JPH11144875A - Organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element having a long electroluminescent life and excellent durability. SOLUTION: This electroluminescent element comprises at least one layer containing at least one compound represented by the formula sandwiched between a pair of electrodes, and has the layer containing the compound represented by the formula as an positive hole injection and transportation layer. In the formula, Ar is a substituted or unsubstituted aryl group, R1 -R4 independently are hydrogen atom, a straight chain, branched, or cyclic alkyl group, a substituted or unsubstituted aralkyl, or a substituted or unsubstituted aryl group, and X1 -X4 are hydrogen atom, a halogen atom, a straight chain, branched, or cyclic alkyl group, a straight chain, branched, or cyclic alkoxyl group or a substituted or unsubstituted aryl group.

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 device has been used as a panel-type light source such as a backlight. However, driving the light emitting device 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 devices have disadvantages such as poor stability and durability. 4,4 'as hole injection transport material
-Bis [N-phenyl-N- (3 "-methylphenyl)
It has been proposed to use [amino] biphenyl [Jp
n. J. Appl. Phys., 27 , L269 (1988)]. Further, as a hole injection transport material, for example, 9,9-dialkyl-
It has been proposed to use a 2,7-bis (N, N-diphenylamino) fluorene derivative [for example, 9,9-dimethyl-2,7-bis (N, N-diphenylamino) fluorene] (JP-A-Hei. No. 5-25473).
However, these organic electroluminescent elements also have stability,
There are difficulties such as poor durability. At present, further improved organic electroluminescent devices are desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electroluminescent device having improved stability and durability.

[0004]

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 device comprising at least one layer containing at least one compound represented by the general formula (1) (formula 2) between a pair of electrodes,

[0005]

Embedded image (In the formula, Ar represents a substituted or unsubstituted aryl group,
R _{1 to} R ₄ represent a hydrogen atom, a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and X _{1 to} X ₄ represent a hydrogen atom, a halogen atom, Represents a straight-chain, branched or cyclic alkyl group, a straight-chain, branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group.) The layer containing the compound represented by the general formula (1) has a hole injection property. The organic electroluminescent device described as a transport layer, the layer containing the compound represented by the general formula (1) is an organic electroluminescent device described as a light emitting layer, and a light emitting layer is further provided between a pair of electrodes. The present invention also relates to the organic electroluminescent device according to any one of the above, wherein the organic electroluminescent device further comprises an electron injection / transport layer between the pair of electrodes.

[0006]

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,
At least one compound represented by the general formula (1)
At least one layer containing the seeds is sandwiched.

[0007]

Embedded image (In the formula, Ar represents a substituted or unsubstituted aryl group,
R _{1 to} R ₄ represent a hydrogen atom, a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and X _{1 to} X ₄ represent a hydrogen atom, a halogen atom, Represents a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group)

In the compound represented by the general formula (1),
Ar represents a substituted or unsubstituted aryl group. Note that the aryl group represents a carbocyclic aromatic group such as a phenyl group, a naphthyl group, and an anthryl group, and a heterocyclic aromatic group such as a furyl group, a thienyl group, and a pyridyl group.
Ar is preferably unsubstituted or, as a substituent, for example, a carbocyclic group having a total carbon number of 6 to 20, which may be mono- or polysubstituted by a halogen atom, an alkyl group, an alkoxy group, or an aryl group. An aromatic group or a heterocyclic aromatic group having a total of 3 to 20 carbon atoms, more preferably an unsubstituted or halogen atom or a carbon atom of 1 to 1;
An alkyl group having 4 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, or a carbocyclic aromatic group having 6 to 20 carbon atoms, which may be mono- or polysubstituted with an aryl group having 6 to 10 carbon atoms; More preferably, it may be unsubstituted or mono- or polysubstituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms. It is a carbocyclic aromatic group having 6 to 16 carbon atoms in total.

Specific examples of Ar include, for example, phenyl, 1-naphthyl, 2-naphthyl, 2-anthryl, 9-anthryl, 4-quinolyl, 4-pyridyl, 3-pyridyl, 2-pyridyl group, 3-furyl group,
2-furyl group, 3-thienyl group, 2-thienyl group, 2-
Oxazolyl group, 2-thiazolyl group, 2-benzoxazolyl 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-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4- (4′-methyl Cyclohexyl) 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,
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-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-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl 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-methoxy-2-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),
R _{1 to} R ₄ represent a hydrogen atom, a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, preferably a hydrogen atom, having 1 to 16 carbon atoms. A straight-chain, branched or cyclic alkyl group, a substituted or unsubstituted aryl group having 4 to 16 carbon atoms,
Alternatively, it represents a substituted or unsubstituted aralkyl group having 5 to 16 carbon atoms, more preferably a hydrogen atom, and 1 to 8 carbon atoms.
Linear, branched or cyclic alkyl group having 6 to 12 carbon atoms
A substituted or unsubstituted aryl group, or having 7 to 7 carbon atoms
Represents 12 substituted or unsubstituted aralkyl groups. More preferably, R _{1 to} R ₄ are a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a carbocyclic aromatic group having 6 to 10 carbon atoms, or a carbocyclic aralkyl having 7 to 10 carbon atoms. Represents a group.

Specific examples of the substituted or unsubstituted aryl group of R _{1 to} R ₄ include, for example, the substituted or unsubstituted aryl groups mentioned as specific examples of Ar. Specific examples of the linear, branched or cyclic alkyl group and substituted or unsubstituted aralkyl group of R _{1 to} R ₄ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 2-ethylbutyl group, 3,3
-Dimethylbutyl group, cyclohexyl group, n-heptyl group, cyclohexylmethyl group, n-octyl group, tert-
Octyl group, 2-ethylhexyl group, n-nonyl group, n
-Decyl group, n-dodecyl group, n-tetradecyl group, n
Alkyl groups such as -hexadecyl group, for example, benzyl group, phenethyl group, α-methylbenzyl group, α, α-dimethylbenzyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, furfuryl group, 2-methylbenzyl group , 3
-Methylbenzyl group, 4-methylbenzyl group, 4-ethylbenzyl group, 4-isopropylbenzyl group, 4-tert
-Butylbenzyl group, 4-n-hexylbenzyl group, 4
-N-nonylbenzyl group, 3,4-dimethylbenzyl group, 3-methoxybenzyl group, 4-methoxybenzyl group, 4-ethoxybenzyl group, 4-n-butoxybenzyl group, 4-n-hexyloxybenzyl group, 4-n-nonyloxybenzyl group, 4-fluorobenzyl group, 3-
An aralkyl group such as a fluorobenzyl group, a 2-chlorobenzyl group, and a 4-chlorobenzyl group can be given.

X _{1 to} X ₄ 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. Atom, halogen atom, C1-C16 linear, branched or cyclic alkyl group, C1-C16 linear, branched or cyclic alkoxy group,
Alternatively, it represents a substituted or unsubstituted aryl group having 4 to 20 carbon atoms, more preferably a hydrogen atom, a halogen atom,
Represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; Preferably, a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms,
A linear or branched alkoxy group of 4 or 6 carbon atoms
Represents 10 to 10 carbocyclic aromatic groups.

Specific examples of the linear, branched or cyclic alkyl group of X _{1 to} X ₄ include, for example, the linear, branched or cyclic alkyl groups exemplified as specific examples of R _{1 to} R _4. can do. Further, specific examples of the substituted or unsubstituted aryl group of X _{1 to} X ₄ include, for example, the substituted or unsubstituted aryl groups mentioned as specific examples of Ar.

Specific examples of halogen atoms of X _{1 to} X ₄ , linear, branched or cyclic alkoxy groups include halogen atoms such as fluorine atom, chlorine atom and bromine atom, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, se
c-butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, cyclopentyloxy group, n-hexyloxy group, 2-ethylbutoxy group,
3,3-dimethylbutoxy group, cyclohexyloxy group, n-heptyloxy group, cyclohexylmethyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-
Examples include an alkoxy group such as a dodecyloxy group, an n-tetradecyloxy group, and an n-hexadecyloxy group.

Specific examples of the compound represented by formula (1) according to the present invention include, for example, the following compounds, but the present invention is not limited thereto. -Exemplified compound number 1. N- (9'H-fluoren-2'-yl) -N-phenyl-9H-fluoren-2-amine N- (9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -9H-fluoren-2-amine 3. N- (9'-methyl-9'H-fluoren-2 ' -Yl) -N- (4 "-methoxyphenyl) -9-methyl-9H-fluoren-2-amine 4. 4. N- (9 ', 9'-dimethyl-9'H-fluoren-2'-yl) -N-phenyl-9,9-dimethyl-9H-fluoren-2-amine. N- (9 ', 9'-Dimethyl-9'H-fluoren-2'-yl) -N- (3 "-methylphenyl) -9,9-dimethyl-9H-fluoren-2-amine 6.N -(9 ', 9'-Dimethyl-9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -9,9-dimethyl-9H-fluoren-2-amine7. N- (9 ', 9'-Dimethyl-9'H-fluoren-2'-yl) -N- (4 "-ethylphenyl) -9,9-dimethyl-9H-fluoren-2-amine 8.N -(9 ', 9'-Dimethyl-9'H-fluoren-2'-yl) -N- (4 "-tert-butylphenyl) -9,9-dimethyl-9H-fluoren-2-amine 9. N- (9 ', 9'-dimethyl-9'H-fluoren-2'-yl) -N- (3 ", 4" -dimethylphenyl) -9,9-dimethyl-9H-fluoren-2-amine 10 . N- (9 ', 9'-dimethyl-9'H-fluoren-2'-yl) -N- (3 ", 5" -dimethylphenyl) -9,9-dimethyl-9H-fluoren-2-amine

11. N- (9 ', 9'-Dimethyl-9'H-fluoren-2'-yl) -N- (3 "-methoxyphenyl) -9,9-dimethyl-9H-fluoren-2-amine 12.N -(9 ', 9'-dimethyl-9'H-fluoren-2'-yl) -N- (4 "-methoxyphenyl) -9,9-dimethyl-9H-fluoren-2-amine 13. 13. N- (9 ', 9'-dimethyl-9'H-fluoren-2'-yl) -N- (4 "-ethoxyphenyl) -9,9-dimethyl-9H-fluoren-2-amine 14.N -(9 ', 9'-dimethyl-9'H-fluoren-2'-yl)-N- (4 "-n-butoxyphenyl) -9,9-dimethyl-9H-fluoren-2-amine 15. N- (9 ', 9'-Dimethyl-9'H-fluoren-2'-yl) -N- (3 "-fluorophenyl) -9,9-dimethyl-9H-fluoren-2-amine 16.N -(9 ', 9'-Dimethyl-9'H-fluoren-2'-yl) -N- (4 "-chlorophenyl) -9,9-dimethyl-9H-fluoren-2-amine 17. N- (9 ', 9'-Dimethyl-9'H-fluoren-2'-yl) -N- (4 "-phenylphenyl) -9,9-dimethyl-9H-fluoren-2-amine 18.N -(9 ', 9'-Dimethyl-9'H-fluoren-2'-yl)-N- (2 "-naphthyl) -9,9-dimethyl-9H-fluoren-2-amine 19. N- (9 ', 9'-Dimethyl-9'H-fluoren-2'-yl) -N- (2 "-furyl) -9,9-dimethyl-9H-fluoren-2-amine 20. N- ( 9 ', 9'-Dimethyl-9'H-fluoren-2'-yl) -N- (2 "-thienyl) -9,9-dimethyl-9H-fluoren-2-amine N- (9 ', 9'-Dimethyl-9'H-fluoren-2'-yl) -N- (2 "-pyridyl) -9,9-dimethyl-9H-fluoren-2-amine 22.N- ( 4'-fluoro-9 ', 9'-dimethyl-9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -4-fluoro-9,9-dimethyl-9H-fluorene-2 -Amine 23. N- (7'-n-butyl-9 ', 9'-dimethyl-9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -7-n-butyl-9,9 -Dimethyl-9H-fluoren-2-amine 24. N- (7'-methoxy-9 ', 9'-dimethyl-9'H-fluoren-2'-yl) -N-phenyl-7-methoxy-9, 9-dimethyl-9H-fluoren-2-amine 25. N- (7'-phenyl-9 ', 9'-dimethyl-9'H-fluoren-2'-yl) -N-phenyl-7-phenyl-9 , 9-Dimethyl-9H-fluoren-2-amine

26. N- (9 ', 9'-Diethyl-9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -9,9-diethyl-9H-fluoren-2-amine 27.N 28.-(9 ', 9'-Diethyl-9'H-fluoren-2'-yl) -N- (4 "-methoxyphenyl) -9,9-diethyl-9H-fluoren-2-amine N- (4'-methyl-9 ', 9'-diethyl-9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -4-methyl-9,9-diethyl-9H- Fluoren-2-amine 29. N- (9'-isopropyl-9'H-fluoren-2'-yl) -N- (4 "-methoxyphenyl) -9-isopropyl-9H-fluoren-2-amine 30 . N- (9 ', 9'-Di-n-propyl-9'H-fluoren-2'-yl) -N-phenyl-9,9-di-n-propyl-9H-fluoren-2-amine 31 . N- (9 ', 9'-di-n-propyl-9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -9,9-di-n-propyl-9H-fluorene -2-amine 32. N- (9 ', 9'-di-n-propyl-9'H-fluoren-2'-yl) -N- (4 "-methoxyphenyl) -9,9-di-n -Propyl-9H-fluoren-2-amine 33. N- (9 ', 9'-Di-n-butyl-9'H-fluoren-2'-yl) -N-phenyl-9,9-di-n-butyl-9H-fluoren-2-amine 34 . N- (9 ', 9'-di-n-butyl-9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -9,9-di-n-butyl-9H -Fluoren-2-amine 35. N- (9 ', 9'-di-n-pentyl-9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -9,9-di 36. -n-pentyl-9H-fluoren-2-amine N- (9 ', 9'-di-n-hexyl-9'H-fluoren-2'-yl) -N- (4 "-methoxyphenyl) -9,9-di-n-hexyl-9H- Fluoren-2-amine 37. N- (9 ', 9'-di-n-hexyl-9'H-fluoren-2'-yl) -N- (4 "-phenylphenyl) -9,9-di- n-hexyl-9H-fluoren-2-amine 38. N- (9 ', 9'-di-n-hexyl-9'H-fluoren-2'-yl) -N- (2 "-naphthyl) -9,9-di-n-hexyl-9H-fluorene- 2-amine 39. N- (9'-cyclohexyl-9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -9-cyclohexyl-9H-fluoren-2-amine 40. N- (7'-phenyl-9 ', 9'-di-n-octyl-9'H-fluoren-2'-yl) -N- (2 "-naphthyl) -7-phenyl-9,9- Di-n-octyl-9H-fluoren-2-amine 41. N- (9'-methyl-9'-ethyl-9'H-fluoren-2'-yl) -N- (4 "-methoxyphenyl) -9-methyl-9-ethyl-9H-fluoren-2-amine 42. N- (9'-methyl-9'-n-propyl-9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -9-methyl-9-n-propyl-9H-fluorene -2-amine 43. N- (9'-ethyl-9'-n-hexyl-9'H-fluoren-2'-yl) -N- (4 "-ethylphenyl) -9-methyl-9-n -Hexyl-9H-fluoren-2-amine 44. N- (9'-ethyl-9'-cyclohexyl-9'H-fluoren-2'-yl) -N- (4 "-ethylphenyl) -9-ethyl-9-cyclohexyl-9H-fluorene-2- Amine 45. N- (9 ', 9'-Dimethyl-9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -9H-fluoren-2-amine 46. N- (9 ', 9'-dimethyl-9'H-fluoren-2'-yl) -N- (4 "-ethylphenyl) -9,9-diethyl-9H-fluoren-2-amine

47. N- (9'-benzyl-9'H-fluoren-2'-yl) -N- (4 "-ethylphenyl) -9-benzyl-9H-fluoren-2-amine 48. N- (9 ', 9 '-Dibenzyl-9'H-fluoren-2'-yl) -N-phenyl-9,9-dibenzyl-9H-fluoren-2-amine 49. N- (9', 9'-dibenzyl-9'H -Fluoren-2'-yl) -N- (4 "-methoxyphenyl) -9,9-dibenzyl-9H-fluoren-2-amine 50. N- (9 ', 9'-Dibenzyl-9'H-fluoren-2'-yl) -N- (4 "-phenylphenyl) -9,9-dibenzyl-9H-fluoren-2-amine 51.N 52.-(9 ', 9'-Dibenzyl-9'H-fluoren-2'-yl) -N- (2 "-naphthyl) -9,9-dibenzyl-9H-fluoren-2-amine 52. N- (9'-methyl-9'-benzyl-9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -9-methyl-9-benzyl-9H-fluoren-2-amine 53. N- (9 ', 9'-dibenzyl-9'H-fluoren-2'-yl) -N- (4 "-ethylphenyl) -9,9-dimethyl-9H-fluoren-2-amine 54 . N- [9 '-(4 "-methylphenyl) -9'H-fluoren-2'-yl] -N-phenyl-9- (4"'-methylphenyl) -9H-fluoren-2-amine 55 . N- (9 ', 9'-diphenyl-9'H-fluoren-2'-yl) -N-phenyl-9,9-diphenyl-9H-fluoren-2-amine 56. N- (9 ', 9'-Diphenyl-9'H-fluoren-2'-yl) -N- (3 "-methylphenyl) -9,9-diphenyl-9H-fluoren-2-amine 57.N -[9 ', 9'-di (4 "-methylphenyl) -9'H-fluoren-2'-yl] -N-phenyl-9,9-di (4"'-methylphenyl) -9H- Fluoren-2-amine 58. N- [9 ', 9'-di (4 "-methoxyphenyl) -9H-fluoren-2'-yl] -N-phenyl-9,9-di (4"'- Methoxyphenyl) -9H-fluoren-2-amine 59. N- (9'-methyl-9'-phenyl-9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -9- Methyl-9-phenyl-9H-fluoren-2-amine 60. N- (9'-ethyl-9'-phenyl-9'H-fluoren-2'-yl) -N- (4 "-methylphenyl) -9-ethyl-9-phenyl-9H-fluoren-2-amine 61. N- (9 ', 9'-diphenyl-9'H-fluoren-2'-yl) -N-phenyl-9,9-dimethyl-9H-fluoren-2-amine

The compound represented by the general formula (1) is described in, for example, JP-A-3-78756, EP-A-6
It can be produced by the method described in No. 33507. That is, for example, a compound represented by the general formula (2-A) (formula 4), a compound represented by the general formula (2-B) (formula 4) and a compound represented by the general formula (2-C) (formula 4) The compound represented is
It can be produced by a reaction (Ullman reaction) in the presence of a copper compound.

[0022]

Embedded image (Wherein, Z ₁ and Z ₂ represent a halogen atom, and Ar,
R _{1 to} R ₄ and X _{1 to} X ₄ represent the same meaning as in the general formula (1))

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 injection function, a hole transport function and / or an electron injection function, and an electron transport function, the light emitting layer is formed of the hole injection transport layer and / or the electron injection transport layer. The element can also be configured to serve as Needless to say, depending on the case, a structure of a device (single-layer device) in which both the hole injection transport layer and the electron injection transport layer are not provided 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 a mixed layer of the hole injecting and transporting component and the light emitting component and / or between the light emitting layer and the electron injecting and transporting layer. 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 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, N, N'-bis [4- (diphenylamino)
Phenyl] -N, N'-diphenyl-1,3-diaminobenzene, N, N'-bis [4- (diphenylamino)
Phenyl] -N, N'-diphenyl-1,4-diaminobenzene, 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), polythiophene and its derivatives, poly-N-
Vinyl carbazole derivatives are more preferred. When the compound represented by the general formula (1) and another compound having a hole injecting and transporting function are used in combination, the proportion of the compound represented by the general formula (1) in the hole injecting and transporting layer 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, it is adjusted to about 5 to 95% by weight.

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-
Hydroxyacridine zinc salt, 3-hydroxyflavone zinc salt, 5-hydroxyflavone beryllium salt,
Aluminum salt of 5-hydroxyflavone], stilbene derivative [for example, 1,1,4,4-tetraphenyl-
1,3-butadiene, 4,4′-bis (2,2-diphenylvinyl) biphenyl], a coumarin derivative [for example,
Coumarin 1, Coumarin 6, Coumarin 7, Coumarin 30,
Coumarin 106, Coumarin 138, Coumarin 151, Coumarin 152, Coumarin 153, Coumarin 307, Coumarin 311, Coumarin 314, Coumarin 334, Coumarin 338, Coumarin 343, Coumarin 500], Pyran derivative [eg DCM1, DCM2], Oxazone derivative [ For example, Nile Red], benzothiazole derivative, benzoxazole derivative, benzimidazole derivative, pyrazine derivative, cinnamate derivative, poly-N-vinylcarbazole and its derivatives, polythiophene and its derivatives, polyphenylene and its derivatives, polyfluorene and Derivatives thereof, polyphenylene vinylene and its derivatives, polybiphenylene vinylene and its derivatives, polyterphenylene vinylene and its derivatives, Naphthylene vinylene and derivatives thereof, poly (thienylene vinylene) and derivatives thereof) can be formed using at least one kind of.

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 the other compound having a light emitting function used in the present invention, a polycyclic aromatic compound and a light emitting organometallic complex are more preferable. For example, J. Appl. Phys., 65 , 36
10 (1989) and JP-A-5-214332, the light-emitting layer can be composed of a host compound and a guest compound (dopant). The compound represented by the general formula (1) can form a light-emitting layer as a host compound, and can also form a light-emitting layer as a guest compound. When the compound represented by the general formula (1) is used as a host compound to form a light-emitting layer, examples of the guest compound include the above compounds having other light-emitting functions, and among them, a polycyclic aromatic compound Is preferred. In this case, a compound having another light emitting function is added to the compound represented by the general formula (1) in an amount of 0.001 to 40.
% By weight, preferably, more preferably, 0.1 to 2%.
Use about 0% by weight. Examples of the polycyclic aromatic compound used in combination with the compound represented by the general formula (1) include, but are not limited to, 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 forming a light emitting layer using the compound to be used as a guest compound,
As the host compound, a luminescent organometallic complex is preferable. In this case, the compound represented by the general formula (1) is preferably added to the luminescent organometallic complex by 0.001 to 0.001.
About 40% by weight, more preferably 0.1 to 20% by weight
Use to the extent. 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) (where 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-butylphenolato) aluminum, bis (2-methyl-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-8-quinolinolate) aluminum, bis (2,4 −
Dimethyl-8-quinolinolate) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolate)
Aluminum, bis (2-methyl-4-ethyl-8-quinolinolate) 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-quinolinolate) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolate) aluminum, bis (2- Methyl-5-trifluoromethyl-8-quinolinolate)
Aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolate) aluminum and the like can be mentioned. 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 [for example, tris (8-quinolinolate) aluminum, bis (10-benzo [h] quinolinolate) beryllium, -Beryllium salt of hydroxyflavone, aluminum salt of 5-hydroxyflavone], oxadiazole derivative, triazole derivative, triazine derivative, perylene derivative, quinoline derivative, quinoxaline derivative, diphenylquinone derivative, nitro-substituted fluorenone derivative, thiopyrandioxide derivative And the like. 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 the 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 the emitted light is generally 70% or more. It is more preferable to set the material and thickness of the anode.

Further, in the organic electroluminescent device of the present invention, at least one of the layers may contain a singlet oxygen quencher. 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.
For example, when a singlet oxygen quencher is contained in the hole injecting and transporting layer, the singlet oxygen quencher may be contained uniformly in the hole injecting and transporting 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 of 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 of about 50 to 400 ° C. (evaporation source temperature), 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 each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer continuously under a vacuum, an organic electroluminescent element having more excellent 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, dimethylsulfoxide) 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 by a coating method to be performed. Preferably, the solution concentration is about 1 to 30% by weight. When a binder resin is used, the amount of the binder resin used is not particularly limited. 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, 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), furthermore, a photocurable resin, and the like. 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.

Also, a metal oxide film (for example, 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.

[0047]

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- (9 ', 9'-dimethyl-9'H-fluoren-2'-yl) -N-phenyl- was placed on the ITO transparent electrode.
9,9-Dimethyl-9H-fluoren-2-amine (compound of Exemplified Compound No. 4) was deposited at a deposition rate of 0.2 nm / se.
By evaporating to a thickness of 75 nm with c, a hole injection transport layer was obtained.
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 were co-deposited thereon as a cathode at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to produce 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 produced organic electroluminescent device, and
The device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at 0 ° C. Initially, 6.5 V, luminance 450 cd /
Green light emission of m ² was confirmed. Brightness half-life is 550
It was time.

Examples 2 to 15 In Example 1, instead of using the compound of Exemplified Compound No. 4 in forming the hole injecting and transporting layer, the compound of Exemplified Compound No. 6 (Example 2) and Exemplified Compound No. 10 were used. (Example 3), the compound of Exemplified Compound No. 13 (Example 4), the compound of Exemplified Compound No. 15 (Example 5),
Compound of Exemplified Compound No. 17 (Example 6), Compound of Exemplified Compound No. 18 (Example 7), Compound of Exemplified Compound No. 22 (Example 8), Compound of Exemplified Compound No. 24 (Example 9), Exemplified Compound Compound No. 25 (Example 1
0), compound of Exemplified Compound No. 27 (Example 11), compound of Exemplified Compound No. 41 (Example 12), compound of Exemplified Compound No. 50 (Example 13), Exemplified Compound No. 52
(Example 14), the compound of Exemplified Compound No. 55 (Example 15), and the compound of Exemplified Compound No. 58 (Example 16) were used to prepare an organic electroluminescent device according to the method described in Example 1. Produced. Green light emission was confirmed from each element. The characteristics were further examined, and the results are shown in Table 1 (Table 1).

Comparative Examples 1 and 2 In Example 1, when forming the hole injecting and transporting layer, the compound of Exemplified Compound No. 4 was used instead of 4,4 ′.
-Bis [N-phenyl-N- (3 "-methylphenyl)
Amino] biphenyl (Comparative Example 1), 9,9-dimethyl-
An organic electroluminescent device was manufactured by the method described in Example 1 except that 2,7-bis (N, N-diphenylamino) fluorene (Comparative Example 2) was used. Green light emission was confirmed from each element. The characteristics were further examined, and the results are shown in Table 1 (Table 1).

[0050]

[Table 1]

Example 17 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-
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. 5 was deposited at a deposition rate of 0.2 nm / sec to a thickness of 55 nm to form a second hole injection / transport layer.
Next, tris (8-quinolinolanote) 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 were further deposited thereon at a deposition rate of 0.2.
at 200 nm / sec to a thickness of 200 nm (weight ratio: 10:
1) The resultant was used as a cathode to produce an organic electroluminescent device. still,
The 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 450 cd / m ² was confirmed. The half life of the luminance was 1200 hours.

Example 18 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 at a deposition rate of 0.1 nm / sec.
The first hole injection transport layer was deposited to a thickness of nm. Next, the compound of Exemplified Compound No. 7 and rubrene were co-evaporated from different evaporation sources at a deposition rate of 0.2 nm / sec to a thickness of 20 nm (weight ratio: 10: 1), and also served as the second hole injection / transport layer. Light emitting layer. Then, Tris (8-
Quinolinolate) aluminum at a deposition rate of 0.2 nm /
The film was deposited to a thickness of 50 nm in sec to form an electron injection / transport 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 470 cd / m ² was confirmed. The half life of the luminance was 1300 hours.

Example 19 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-
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 atmospheric pressure, the pressure of the vapor deposition tank was reduced again to 3 × 10 ⁻⁶ Torr. Next, the compound of Exemplified Compound No. 26 and rubrene were separated from different evaporation sources at a deposition rate of 0.2 nm / sec for 5 minutes.
A co-evaporation (weight ratio: 10: 1) was performed to a thickness of 5 nm to obtain a light emitting layer also serving as a second hole injection / transport layer. While maintaining the reduced pressure state, tris (8-quinolinolate) was further placed thereon.
Aluminum was deposited at a deposition rate of 0.2 nm / sec to a thickness of 50 nm 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 to produce an organic electroluminescent device. did. 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 450 cd / m ² was confirmed. The half life of the luminance was 1500 hours.

Example 20 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, the compound of Exemplified Compound No. 12 was deposited on the ITO transparent electrode 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. 4 and rubrene were co-deposited 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. Furthermore, on top of this, tris (8-quinolinolate)
Aluminum was deposited at a deposition rate of 0.2 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 direct current voltage is applied to the produced organic electroluminescent device, and a dry current of 10 mA is applied.
/ Cm ^{2 at} a constant current density. Initially, 6.
Yellow light emission of 1 V and a luminance of 440 cd / m ² was confirmed. The half life of the luminance was 1600 hours.

Example 21 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. 18 was vapor-deposited on the ITO transparent electrode to a thickness of 55 nm at a vapor deposition rate of 0.2 nm / sec to form a hole injection transport layer. Next, tris (8-quinolinolato) aluminum and the compound of Exemplified Compound No. 16 were deposited thereon at a deposition rate of 0.2 nm / sec at a thickness of 40 nm.
Was co-evaporated (weight ratio 10: 1) to obtain a light emitting layer.
Further, tris (8-quinolinolato) aluminum was deposited at a deposition rate of 0.2 nm / sec to a thickness of 30 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, 6.2V, brightness 4
Green light emission of 60 cd / m ² was confirmed. The half life of the luminance was 1500 hours.

Example 22 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 and further washed with UV / ozone. Next, on the ITO transparent electrode, polycarbonate (weight average molecular weight: 50,000),
And a compound of Exemplified Compound No. 8 in a 3% by weight dichloroethane solution containing 100: 50 by weight,
By a dip coating method, a 40 nm hole injection / transport layer was formed. Next, after fixing the glass substrate having the hole injecting and transporting layer to the substrate holder of the vapor deposition apparatus, the vapor deposition tank was moved to 3 mm.
The pressure was reduced to × 10 ⁻⁶ Torr. Then tris (8-quinolinolato) aluminum was deposited thereon with a deposition rate of 0,1.
Vapor deposition was performed at 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 were deposited on the light emitting layer at a deposition rate of 0.2 nm / sec for 200 n.
An organic electroluminescent device was prepared by co-evaporating the resultant to a thickness of 10 m (weight ratio: 10: 1) to form a cathode. 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 1030cd
/ M ² green light emission was confirmed. Brightness half-life is 25
It was 0 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 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. 36, 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 a substrate holder of a vapor deposition device, 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 300 hours.

[0058]

According to the present invention, it has become possible to provide an organic electroluminescent device having a long light-emitting 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]

 Reference Signs List 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 (5)

[Claims] A compound represented by the general formula (1) between a pair of electrodes:
An organic electroluminescent device comprising at least one layer sandwiching at least one compound containing at least one compound represented by the formula: Embedded image (In the formula, Ar represents a substituted or unsubstituted aryl group,
R _{1 to} R ₄ represent a hydrogen atom, a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and X _{1 to} X ₄ represent a hydrogen atom, a halogen atom, Represents a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy 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, wherein the layer containing the compound represented by the general formula (1) is a light emitting layer. 4. The organic electroluminescent device according to claim 1, further comprising a light emitting layer between the pair of electrodes. 5. The organic electroluminescent device according to claim 1, further comprising an electron injection / transport layer between the pair of electrodes.