JP2001196177A - Organic electric field light emission element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To offer an organic electric field light emission element having along life and an excellent durability. SOLUTION: The organic electric field light emission element is comprises of at least one layer containing at least one sort of compounds expressed with formula (1) which is sandwiched between a pair of electrodes. In the formula, a naphthyl group of substitution or non-substitution is expressed by Ar1-Ar3 each independently. Ar4 expresses a phoenyl or naphthyl group of substitution or non-substitution and R1 and R2 independently and respectively express a hydrogen atom, a normal chain, branch, or cyclic alkyl group, an aryl group or an aralkyl group of substitution or non-substitution, and Z1 and Z2 express each independently a hydrogen atom, a halogen atom, a normal chain, branch or cyclic alkyl group, an alkoxy group, or an aryl group of substitution or non-substitution.

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 element that injects electrons and holes (holes) into the thin film and causes recombination to generate excitons (excitons), and emits light using light emitted when the excitons are 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.

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. Phys., 27 , L269 (1988)]. Further, as a hole injection transport material, for example, 9,9-dialkyl-2,
7-bis (N, N-diphenylamino) fluorene derivative [for example, 9,9-dimethyl-2,7-bis (N, N
-Diphenylamino) fluorene] (JP-A-5-25473). However, these organic electroluminescent elements also have disadvantages such as poor stability and 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 improved stability and durability.

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

[0006]

Embedded image (Wherein, Ar _{1 to} Ar ₃ each independently represent a substituted or unsubstituted naphthyl group, Ar ₄ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, R ₁ and R ₂ Are each independently a hydrogen atom, a straight-chain,
Represents a branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and Z ₁ and Z ₂ each independently represent a hydrogen atom, a halogen atom, a straight-chain, branched or cyclic alkyl Represents a linear, branched, or cyclic alkoxy group, or a substituted or unsubstituted aryl group)

The organic electroluminescent device described above, wherein the layer containing the compound represented by the general formula (1) is a hole injection / transport layer, and the layer containing the compound represented by the general formula (1) emits light. The organic electroluminescent device according to any one of the above, wherein the organic electroluminescent device is a layer, between a pair of electrodes, the organic electroluminescent device further includes a light emitting layer, or between the pair of electrodes, further includes an electron injection transport layer. And an organic electroluminescent device according to (1).

[0008]

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 is formed by sandwiching at least one layer containing at least one compound represented by the general formula (1).

[0009]

Embedded image (Wherein, Ar _{1 to} Ar ₃ each independently represent a substituted or unsubstituted naphthyl group, Ar ₄ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, R ₁ and R ₂ Are each independently a hydrogen atom, a straight-chain,
Represents a branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and Z ₁ and Z ₂ each independently represent a hydrogen atom, a halogen atom, a straight-chain, branched or cyclic alkyl Represents a linear, branched, or cyclic alkoxy group, or a substituted or unsubstituted aryl group)

In the general formula (1), Ar _{1 to} Ar ₃ represent a substituted or unsubstituted naphthyl group. Ar _{1 to} Ar ₃ are
Preferably, the unsubstituted or substituted group is, for example, a naphthyl group having a total carbon number of 10 to 24 which may be mono- or polysubstituted by a halogen atom, an alkyl group, an alkoxy group, or an aryl group. Preferably, it is unsubstituted or has a halogen atom and carbon number of 1 to 14.
Is a naphthyl group having a total of 10 to 24 carbon atoms which may be mono- or polysubstituted by an alkyl group having 1 to 14 carbon atoms or an aryl group having 6 to 10 carbon atoms, and more preferably The total number of carbon atoms which may be substituted or mono- or polysubstituted by 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 20 is a naphthyl group.

Ar ₄ is a substituted or unsubstituted phenyl group,
Alternatively, it represents a substituted or unsubstituted naphthyl group. Ar ₄
Is preferably unsubstituted or, as a substituent, for example, a phenyl group having a total carbon number of 6 to 24 which may be mono- or polysubstituted by a halogen atom, an alkyl group, an alkoxy group, or an aryl group; or An unsubstituted or naphthyl group having a total of 10 to 24 carbon atoms which may be mono- or polysubstituted by a halogen atom, an alkyl group, an alkoxy group, or an aryl group, more preferably an unsubstituted or halogenated group; Atom, carbon number 1-14
A phenyl group having 6 to 24 carbon atoms, which may be mono- or polysubstituted by an alkyl group having 1 to 14 carbon atoms or an aryl group having 6 to 10 carbon atoms, or unsubstituted or halogen An atom, an alkyl group having 1 to 14 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, or a naphthyl group having a total carbon number of 10 to 24 which may be mono- or polysubstituted by an aryl group having 6 to 10 carbon atoms. Yes,
More preferably, unsubstituted or halogen atom,
An alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group having 6 to 16 carbon atoms which may be mono- or polysubstituted by an aryl group having 6 to 10 carbon atoms, or A substituted or halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
Alternatively, it is a naphthyl group having a total of 10 to 20 carbon atoms which may be mono- or polysubstituted by an aryl group having 6 to 10 carbon atoms.

Specific examples of substituted or unsubstituted naphthyl groups in Ar _{1 to} Ar ₄ include, for example, 1-naphthyl group, 2-naphthyl group, 2-methyl-1-naphthyl group,
-Methyl-1-naphthyl group, 4-ethyl-1-naphthyl group, 4-n-butyl-1-naphthyl group, 4-n-hexyl-1-naphthyl group, 4-n-decyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-n-butyl-2
-Naphthyl group, 6-n-octyl-2-naphthyl 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,

4-phenyl-1-naphthyl, 6-phenyl-2-naphthyl, 4-fluoro-1-naphthyl, 2-fluoro-1-naphthyl, 4-chloro-1-
Examples thereof include a naphthyl group, a 4-chloro-2-naphthyl group, a 6-bromo-2-naphthyl group, a 2,4-dichloro-1-naphthyl group, and a 1,6-dichloro-2-naphthyl group. It is not limited to these.

Specific examples of the substituted or unsubstituted phenyl group in Ar ₄ include, for example, phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, -Ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec-butyl Phenyl 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′-methylcyclohexyl) phenyl group, 4- (4′-tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl 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-te
rt-butyl-2,6-dimethylphenyl group,

4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 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,

A 2-methyl-4-methoxyphenyl group, 2
-Methyl-5-methoxyphenyl group, 3-methyl-4-
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'-ethylphenyl) phenyl group, 4- (4'-isopropylphenyl) phenyl group, 4- (4'-tert-
Butylphenyl) phenyl group, 4- (4′-n-hexylphenyl) phenyl group, 4- (4′-n-octylphenyl) phenyl group, 4- (4′-methoxyphenyl)
Phenyl group, 4- (4'-n-butoxyphenyl) phenyl group, 4- (4'-n-hexyloxyphenyl) 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, 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-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-chloro-4-methylphenyl 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-ethoxyphenyl group, 3-chloro-4 -Methoxyphenyl group, 2-methoxy-5-chlorophenyl group, 3-methoxy-6-chlorophenyl group, 5-chloro-2,4-dimethoxyphenyl group, and the like, but are not limited thereto. .

In the compound represented by the general formula (1),
R ₁ and R ₂ 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 linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group having 4 to 16 carbon atoms, or a substituted or unsubstituted aralkyl group having 5 to 16 carbon atoms, more preferably a hydrogen atom, a carbon atom 1
-8 linear, branched or cyclic alkyl groups, 6-6 carbon atoms
A substituted or unsubstituted aryl group having 12 or a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms, and more preferably, R ₁ and R ₂ are a linear chain having 1 to 8 carbon atoms;
It is a branched or cyclic alkyl group, a carbocyclic aromatic group having 6 to 10 carbon atoms, or a carbocyclic aralkyl group having 7 to 10 carbon atoms.

Specific examples of the substituted or unsubstituted aryl group of R ₁ and R ₂ include, for example, the substituted or unsubstituted phenyl group and the substituted or unsubstituted phenyl group mentioned as specific examples of Ar _{1 to} Ar _4. Can be exemplified. Specific examples of the linear, branched or cyclic alkyl group of R ₁ and R ₂ include, for example, methyl group, ethyl group, n
-Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, n-hexyl, 2 -Ethylbutyl group, 3,3-dimethylbutyl group, cyclohexyl group, n-heptyl group, cyclohexylmethyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group,
Examples thereof include, but are not limited to, an n-nonyl group, an n-decyl group, an n-dodecyl group, an n-tetradecyl group, and an n-hexadecyl group.

Specific examples of the substituted or unsubstituted aralkyl group for R ₁ and R ₂ include, for example, a 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-nonylbenzyl group, 3,4-dimethylbenzyl group, 3-methoxybenzyl group, 4- Methoxybenzyl group, 4-ethoxybenzyl group, 4-n-butoxybenzyl group, 4-n
Aralkyl groups such as -hexyloxybenzyl group, 4-nonyloxybenzyl group, 4-fluorobenzyl group, 3-fluorobenzyl group, 2-chlorobenzyl group, and 4-chlorobenzyl group; It is not limited.

Z ₁ and Z ₂ are 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, preferably a hydrogen atom, a halogen atom,
A linear, branched or cyclic alkyl group having 1 to 16 carbon atoms,
A straight-chain, branched or cyclic alkoxy group having 1 to 16 carbon atoms or a substituted or unsubstituted aryl group having 3 to 25 carbon atoms, more preferably a hydrogen atom, a halogen atom, a straight-chain having 1 to 8 carbon atoms; A chain, branched or cyclic alkyl group, 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, more preferably a hydrogen atom .

Specific examples of the linear, branched or cyclic alkyl groups of Z ₁ and Z ₂ include, for example, R ₁ and R ₂
The linear, branched or cyclic alkyl groups mentioned as specific examples can be exemplified. Further, specific examples of the substituted or unsubstituted aryl group of Z ₁ and Z ₂ include, for example,
The substituted or unsubstituted phenyl group or the substituted or unsubstituted naphthyl group exemplified as specific examples of Ar _{1 to} Ar ₄ can be exemplified. A halogen atom for Z ₁ and Z ₂ ,
Specific examples of the linear, branched or cyclic alkoxy group include, for example, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butoxy group. Group, isobutoxy group, sec-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-dodecyloxy group, n-tetradecyloxy group, An alkoxy group such as an n-hexadecyloxy group can be exemplified.

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. In the formula, Ph represents a phenyl group, Tol represents a 4-methylphenyl group, and Bz represents a benzyl group.

[0024]

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[0028]

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[0029]

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[0032]

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[0034]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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The compound represented by the general formula (1) according to the present invention can be produced by a method known per se.
That is, for example, a compound represented by the general formula (2):
It can be produced by reacting a compound represented by the general formula (3) and a compound represented by the general formula (4) in the presence of a copper compound (Ullman reaction). Also,
For example, it can also be produced by reacting a compound represented by the general formula (5) with a compound represented by the general formula (4) in the presence of a copper compound (Ullman reaction). Further, for example, a compound represented by the general formula (6):
It can also be produced by reacting the compound represented by the general formula (3) in the presence of a copper compound (Ullman reaction).

[0046]

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

In the above formula, X _{1 to} X ₄ represent a halogen atom,
It preferably represents a chlorine atom, a bromine atom or an iodine atom, and more preferably a bromine atom or an iodine atom.

The organic electroluminescent device 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.
(B) anode / hole injection / transport layer / light emitting layer / cathode device (FIG. 2), (C) anode / light emission Layer / electron injection / transport layer / cathode device (FIG. 3), (D) anode / light-emitting layer / cathode device (FIG. 4), and the like. Further, the device is a device of a type in which a light emitting layer is sandwiched between electron injection transport layers (E).
Anode / hole injection / transport layer / electron injection / transport layer / emission layer / electron injection / transport layer / cathode 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. An element of the type sandwiched between a pair of electrodes in the form of a single layer in which an electron injecting and transporting component is mixed (FIG. 6). 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 / light emitting 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, for example, a vapor deposition method, a sputtering method, or the like. 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 used, but is generally about 5 to 1000 nm, more preferably,
It is set to about 10 to 500 nm.

The hole injection / transport 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-carbazolyyl) triphenylamine, 4,4', 4 "-
Tris [N- (3 "'-methylphenyl) -N-phenylamino] triphenylamine, 4,4', 4" -tris [N, N-bis (4 ""-tert-butylbiphenyl-
4 ""-yl) amino] triphenylamine, 1,3
5-tris [N- (4'-diphenylaminophenyl)
-N-phenylamino] benzene), polythiophene and derivatives thereof, and poly-N-vinylcarbazole derivatives are more preferred. When a compound represented by the general formula (1) is used in combination with another compound having a hole injection / transport function,
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 about 0.1 to 99.9% by weight, and still more preferably. , About 1 to 99% by weight, particularly preferably about 5 to 95% by weight.

The light emitting layer 4 has a hole and electron injection function,
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 diketopyrrolopyrrole 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], triarylamine derivatives [for example, the compounds described above as compounds having a hole injection / transport function] can be mentioned. , An organometallic complex [for example, Tris 8-quinolinolate) aluminum, bis (10-benzo [h] quinolinolate) beryllium, zinc salt of 2- (2′-hydroxyphenyl) benzoxazole, zinc salt of 2- (2′-hydroxyphenyl) benzothiazole, 4- Hydroxyacridine zinc salt, 3-hydroxyflavone zinc salt, 5-hydroxyflavone beryllium salt, 5-hydroxyflavone aluminum salt], stilbene derivatives [for example,
1,4,4-tetraphenyl-1,3-butadiene,
4,4′-bis (2,2-diphenylvinyl) biphenyl, 4,4′-bis [(1,1,2-triphenyl) ethenyl] biphenyl], coumarin derivatives [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 3
38, 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-vinylcarbazole and its derivatives, polythiophene and its derivatives, polyphenylene and its derivatives, polyfluorene and its derivatives, polyphenylenevinylene and its derivatives, polybiphenylenevinylene and its derivatives, polyterphenylenevinylene and its derivatives, polynaphthylenevinylene 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 the other compound having a light emitting function used in the present invention, a polycyclic aromatic compound and a light emitting organic metal 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 preferably added to the compound represented by the general formula (1).
About 001 to 40% by weight, more preferably 0.01 to 40% by weight.
About 30% by weight, more preferably about 0.1 to 20% by weight is used.

The polycyclic aromatic compound used in combination with the compound represented by the general formula (1) is not particularly limited. Examples thereof include 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 0.01 to 30% by weight, based on the luminescent organic metal complex. Preferably, about 0.1 to 20% by weight is used.

The luminous organometallic complex used in combination with the compound represented by the general formula (1) is not particularly limited, but a luminous organoaluminum complex is preferable, and a substituted or unsubstituted 8-quinolinolate coordination is preferred. A luminescent organic aluminum complex having an atom is 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-μ-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, 5-hydroxyflavone Beryllium salt, aluminum salt of 5-hydroxyflavone], oxadiazole derivative [for example, 1,3-bis
[5 ′-(p-tert-butylphenyl) -1,3,4-
Oxadiazol-2'-yl] benzene], triazole derivatives [for example, 3- (4'-tert-butylphenyl) -4-phenyl-5- (4 "-biphenyl) -1,
2,4-triazole], a triazine derivative, a perylene derivative, a quinoline derivative, a quinoxaline derivative, a diphenylquinone derivative, a nitro-substituted fluorenone derivative, and a thiopyrandioxide derivative. 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 materials, 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. Note that 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 to be 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.

In the organic electroluminescent device of the present invention, at least one layer 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 preferable. 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 0.01 to 50% by weight, preferably 0.0
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 deposition method, an ionization deposition 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, an inkjet method, or the like. By vacuum evaporation method,
In the case of forming each layer, the conditions of vacuum deposition are not particularly limited, but the vacuum deposition is performed under a vacuum of about 10 ⁻⁵ Torr or less.
~ 600 ° C boat temperature (deposition source temperature), -50 ~
At a substrate temperature of about 300 ° C., 0.005 to 50 nm / se
It is preferable to carry out at a deposition rate of about c. 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. As a binder resin that can be used for each of the hole injection transport layer, the light emitting layer, and the electron injection transport layer, for example, poly-N-vinylcarbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl acrylate,
Polymethyl methacrylate, polyether, polycarbonate, polyamide, polyimide, polyamide imide,
Polyparaxylene, polyethylene, polyethylene ether, polypropylene ether, polyphenylene oxide, polyether sulfone, polyaniline and its derivatives, polythiophene and its derivatives, polyphenylene vinylene and its derivatives, polyfluorene and its derivatives, polythienylene vinylene and its derivatives, etc. High molecular compounds are exemplified. The binder resin may be used alone or in combination of two or more.

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, ethyl acetate, butyl acetate, ester solvents such as amyl acetate, for example, methanol, ethanol, propanol, butanol, pentanol, hexanol, Alcohol-based solvents such as cyclohexanol, methyl cellosolve, ethyl cellosolve, and ethylene glycol, for example, dibutyl ether, tetrahydrofuran, dioxane Down, ether solvents anisole, for example, N, N-dimethylformamide, N, N-
Dimethylacetamide, 1-methyl-2-pyrrolidone,
A polar solvent such as 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide) and / or dissolved or dispersed in water to form a coating solution, and a thin film can be formed by various coating methods. .

The method of dispersion is not particularly limited. For example, the particles can be dispersed in 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
Degree, 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.

As a material used for the protective layer, for example,
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 oxides, metal nitrides, metal carbides, metal sulfides), and furthermore, photocurable resins. They may be used, or a plurality of them may be used in combination. 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 may 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) made of an organic phosphorus compound, polysilane, an aromatic amine derivative, a phthalocyanine derivative (for example, copper phthalocyanine), or carbon can be provided. In addition, an electrode, for example, an anode,
For example, it can be used after treatment with an 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.

[0076]

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 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. 7 was deposited on the ITO transparent electrode to a thickness of 75 nm at a deposition rate of 0.2 nm / sec to form a hole injection / transport layer. Then tris (8-quinolinolato) aluminum was deposited thereon with a deposition rate of 0,1.
Vapor deposition was performed at a thickness of 50 nm at a rate of 2 nm / sec to form a light emitting layer also serving as an electron injection transport layer. Further, as a cathode, magnesium and silver were 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 00 nm to produce 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 at 50 ° C. in a dry atmosphere,
The device was continuously driven at a constant current density of 0 mA / cm ² . Initially, green light emission of 6.5 V and a luminance of 550 cd / m ² was confirmed. The half life of the luminance was 740 hours.

Examples 2 to 24 In Example 1, instead of using the compound of Exemplified Compound No. 7 in forming the hole injecting and transporting layer, the compound of Exemplified Compound No. 8 (Example 2) and Exemplified Compound No. 10 were used. (Example 3), the compound of Exemplified Compound No. 12 (Example 4), the compound of Exemplified Compound No. 14 (Example 5),
Compound of Exemplified Compound No. 18 (Example 6), Compound of Exemplified Compound No. 19 (Example 7), Compound of Exemplified Compound No. 23 (Example 8), Compound of Exemplified Compound No. 25 (Example 9), Exemplified Compound Compound No. 30 (Example 1
0), compound of Exemplified Compound No. 33 (Example 11), compound of Exemplified Compound No. 36 (Example 12), compound of Exemplified Compound No. 39 (Example 13), Exemplified Compound No. 40
(Example 14), the compound of Exemplified Compound No. 41 (Example 15), the compound of Exemplified Compound No. 45 (Example 16), the compound of Exemplified Compound No. 48 (Example 17),
Compound of Exemplified Compound No. 50 (Example 18), Compound of Exemplified Compound No. 52 (Example 19), Exemplified Compound No. 5
Compound No. 7 (Example 20), Compound No. 66 (Example 21), Compound No. 73 (Example 22), Compound No. 75 (Example 2)
3) An organic electroluminescent device was produced by the method described in Example 1 except that the compound of Exemplified Compound No. 83 (Example 24) was used. Green light emission was confirmed from each element. The characteristics were further examined, and the results are shown in Table 1.

Comparative Examples 1-2 In Example 1, when forming the hole injecting and transporting layer, instead of using the compound of Exemplified Compound No. 7, 4,4 'was used.
-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.

[0080]

[Table 1]

[0081]

[Table 2]

Example 25 Glass having a 200-nm-thick ITO transparent electrode (anode)
Substrate with neutral detergent, acetone and ethanol
Sonic cleaning was performed. The substrate is dried using nitrogen gas,
After UV / ozone cleaning, the substrate holder of the evaporation system
After fixing to 3 × 10^-6The pressure was reduced to Torr. Ma
First, poly (thiophene-2,5-
Diyl) at a deposition rate of 0.1 nm / sec and a thickness of 20 nm.
Then, a first hole injection / transport layer was formed. Then, for example
Compound No. 7 was deposited at a deposition rate of 0.2 nm / sec.
It was deposited to a thickness of 55 nm to form a second hole injection / transport layer.
Then, a tris (8-quinolinola notebook)
Luminium was deposited at 50 nm at a deposition rate of 0.2 nm / sec.
The light-emitting layer was also deposited to a thickness to serve 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. Production
DC voltage is applied to the organic electroluminescent device
Below, 10mA / cm ^TwoWas continuously driven at a constant current density of
Initially, 6.4 V, luminance 580 cd / m^TwoGreen leaves
Light was confirmed. The half-life of luminance is 1300 hours.
Was.

Example 26 Glass having a 200 nm thick ITO transparent electrode (anode)
Substrate with neutral detergent, acetone and ethanol
Sonic cleaning was performed. The substrate is dried using nitrogen gas,
After UV / ozone cleaning, the substrate holder of the evaporation system
After fixing to 3 × 10^-6The pressure was reduced to Torr. Ma
4,4 ', 4 "-tris [N
-(3 "'-methylphenyl) -N-phenylamino]
Liphenylamine is deposited 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. 45 and rubrene are different
20 nm thickness from evaporation source at a deposition rate of 0.2 nm / sec
Co-evaporation (weight ratio: 10: 1) to form a second hole injection / transport layer
The light emitting layer also served as Then, on top of it, Tris (8
-Quinolinolate) aluminum at a deposition rate of 0.2 nm
/ Sec to a thickness of 50 nm as an electron injection transport layer
Was. Further, magnesium and silver are further deposited on the
Co-deposition to a thickness of 200 nm at 0.2 nm / sec (weight ratio
10: 1) to form an organic electroluminescent device as a cathode.
Was. The deposition was performed while maintaining the reduced pressure of the deposition tank.
Was. Apply a DC voltage to the fabricated organic electroluminescent device and dry it.
10mA / cm under dry atmosphere ^TwoContinuous drive at constant current density
I let it. Initially, 6.2 V, luminance 600 cd / m^Twoof
Yellow emission was observed. Brightness half-life is 1400 hours
Met.

Example 27 Glass having a 200 nm-thick ITO transparent electrode (anode)
Substrate with neutral detergent, acetone and ethanol
Sonic cleaning was performed. The substrate is dried using nitrogen gas,
After UV / ozone cleaning, the substrate holder of the evaporation system
After fixing to 3 × 10^-6The pressure was reduced to Torr. Ma
First, poly (thiophene-2,5-
Diyl) at a deposition rate of 0.1 nm / sec and a thickness of 20 nm.
Then, a first hole injection / transport layer was formed. Vapor deposition tank
After the pressure was reduced, the deposition tank was again set to 3 × 10^-6Decompress to Torr
Was. Next, the compound of Exemplified Compound No. 31 and rubrene
From different evaporation sources at a deposition rate of 0.2 nm / sec.
Co-deposition (weight ratio 10: 1) to a thickness of 5 nm, and second holes
The light emitting layer also served as the injection transport layer. Keep the pressure reduced
Then, on top of that, tris (8-quinolinolate)
Aluminum was deposited at 50 nm at a deposition rate of 0.2 nm / sec.
This was vapor-deposited to a thickness to form an electron injection transport layer. Keep decompression
With magnesium and silver deposited on top
Co-deposition to a thickness of 200 nm at a rate of 0.2 nm / sec (weight
Ratio of 10: 1) to form a cathode to produce an organic electroluminescent device.
Was. Apply a DC voltage to the fabricated organic electroluminescent device and dry it.
10mA / cm under dry atmosphere ^TwoContinuous drive at constant current density
I let it. Initially, 6.2 V, luminance 620 cd / m^Twoof
Yellow emission was observed. Brightness half-life is 1650 hours
Met.

Example 28 Glass having a 200 nm thick ITO transparent electrode (anode)
Substrate with neutral detergent, acetone and ethanol
Sonic cleaning was performed. The substrate is dried using nitrogen gas,
After UV / ozone cleaning, the substrate holder of the evaporation system
After fixing to 3 × 10^-6The pressure was reduced to Torr. Ma
And the compound of Exemplified Compound No. 12 on the ITO transparent electrode
At a deposition rate of 0.1 nm / sec to a thickness of 20 nm
Thus, a first hole injection transport layer was obtained. Next, the exemplified compound number
No. 53 compound and rubrene were deposited from different evaporation sources
Co-deposition to a thickness of 55 nm at a rate of 0.2 nm / sec (weight
10: 1), and a light emitting layer also serving as a second hole injection / transport layer.
did. Further, Tris (8-quinolinoler)
G) 50 n of aluminum at a deposition rate of 0.2 nm / sec
m to form an electron injecting and transporting layer. Moreover
On top, magnesium and silver were deposited at a deposition rate of 0.2 nm / sec.
And co-deposit to a thickness of 200 nm (weight ratio 10: 1)
As an electrode, an organic electroluminescent device was manufactured. In addition, vapor deposition is
The test was carried out while the pressure in the bath was maintained. Organic electricity produced
Apply a DC voltage to the field light emitting element, and in a dry atmosphere, 10 m
A / cm ^TwoWas continuously driven at a constant current density of Initially,
6.1 V, luminance 620 cd / m^TwoThe yellow emission is confirmed
Was. The half life of the luminance was 1700 hours.

Example 29 Glass having a 200-nm-thick ITO transparent electrode (anode)
Substrate with neutral detergent, acetone and ethanol
Sonic cleaning was performed. The substrate is dried using nitrogen gas,
After UV / ozone cleaning, the substrate holder of the evaporation system
After fixing to 3 × 10^-6The pressure was reduced to Torr. Ma
The compound of Exemplified Compound No. 9 was placed on the ITO transparent electrode.
At a deposition rate of 0.2 nm / sec to a thickness of 55 nm
Thus, a hole injection transport layer was obtained. Then, on top of it, Tris
(8-quinolinolate) aluminum and exemplified compound numbers
Compound 27 was deposited at a deposition rate of 0.2 nm / sec at 40 nm.
Was co-evaporated (weight ratio 10: 1) to obtain a light emitting layer.
Furthermore, tris (8-quinolinolate) aluminum
Is deposited at a deposition rate of 0.2 nm / sec to a thickness of 30 nm.
Thus, an electron injection transport layer was obtained. On top of that, Magneshi
Of silver and 200 nm at a deposition rate of 0.2 nm / sec.
Co-deposit (weight ratio 10: 1) to the thickness to form a cathode,
A field emission device was manufactured. The evaporation was performed under reduced pressure in the evaporation tank.
Was carried out while maintaining. Directly to the manufactured organic electroluminescent device
10 mA / cm under a dry atmosphere by applying a flowing voltage ^TwoConstant
It was continuously driven at a current density. Initially, 6.2V, brightness
660 cd / m^TwoGreen light emission was confirmed. Half the brightness
The life was 1600 hours.

Example 30 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. 43 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 a substrate holder of a vapor deposition apparatus, the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. Then tris (8-quinolinolato) aluminum was deposited thereon with a deposition rate of 0,1.
Vapor deposition was performed at a thickness of 50 nm at a rate of 2 nm / sec to form a light emitting layer also serving as an electron injection transport layer. Further, on the light emitting layer, magnesium and silver were deposited 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 1080c
Green light emission of d / m ² was confirmed. Brightness half-life is 3
50 hours.

Example 31 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, polymethyl methacrylate (weight average molecular weight 250
00), the compound of Exemplified Compound No. 54, and tris (8-quinolinolate) aluminum were each added at a weight ratio of 10
Using a 3% by weight dichloroethane solution containing 0: 50: 0.5 at a ratio of 100 n 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) at a deposition rate of 0.2 nm / sec to a thickness of 200 nm to form an organic electroluminescent device. When a DC voltage of 15 V was applied to the produced organic electroluminescent device in a dry atmosphere, a current of 80 mA / cm ² flowed. Brightness 65
Green light emission of 0 cd / m ² was confirmed. The half life of the luminance was 420 hours.

[0089]

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]

 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

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3K007 AB00 AB04 BB00 BB06 CA01 CA02 CA06 CB01 DA00 DB03 EB00 FA01

Claims (5)

[Claims] 1. An organic electroluminescent device comprising at least one layer containing at least one compound represented by the general formula (1) between a pair of electrodes. Embedded image (Wherein, Ar _{1 to} Ar ₃ each independently represent a substituted or unsubstituted naphthyl group, Ar ₄ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, R ₁ and R ₂ Are each independently a hydrogen atom, a straight chain,
Represents a branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and Z ₁ and Z ₂ each independently represent a hydrogen atom, a halogen atom, a straight-chain, branched or cyclic alkyl Represents 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.