JP2002056984A - Organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element with long emission life and excellent durability. SOLUTION: The organic electroluminescent element has at least one layer held between a pair of electrodes containing at least one kind of compound shown by the formula (1), where; Ar1-Ar3 represent biphenyl groups with or without substitution, and Ar4 represents a phenyl group with or without substitution or a naphtyl group with or without substitution, independently with each other.

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, 2,5-bis [4′-
(N, N-diarylamino) phenyl] -3,4-diphenylthiophene derivative [for example, 2,5-bis [4 ′-(N, N-diphenylamino) phenyl]-
3,4-diphenylthiophene, 2,5-bis [4′-
It has been proposed to use [[N-phenyl-N- (4 "-phenylphenyl) amino] phenyl] -3,4-diphenylthiophene] (JP-A-10-125468).
No.). 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 element comprising at least one layer containing at least one compound containing at least one compound represented by the following general formula (1) (formula 2) between a pair of electrodes. The organic electroluminescent device according to the above, wherein the layer containing the compound represented by 1) is a hole injection / transport layer, and the organic electroluminescent device, wherein the layer containing the compound represented by the general formula (1) is a light emitting layer. An electroluminescent element, between the pair of electrodes, further having a light emitting layer;
The organic electroluminescent device according to any one of the above-mentioned, further comprising an electron injection / transport layer between a pair of electrodes.

[0006]

Embedded image (Wherein, Ar _{1 to} Ar ₃ each independently represent a substituted or unsubstituted biphenyl group, and Ar ₄ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group)

[0007]

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

[0008]

Embedded image (Wherein, Ar _{1 to} Ar ₃ each independently represent a substituted or unsubstituted biphenyl group, and Ar ₄ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group)

In the general formula (1), Ar _{1 to} Ar ₃ each independently represent a substituted or unsubstituted biphenyl group. Ar _{1 to} Ar ₃ are preferably unsubstituted or, as a substituent, for example, a total of 12 to 26 carbon atoms which may be mono- or polysubstituted by a halogen atom, an alkyl group, an alkoxy group, or an aryl group. And more preferably an unsubstituted or halogen atom, an alkyl group having 1 to 14 carbon atoms,
A total of 12 carbon atoms which may be mono- or polysubstituted by an alkoxy group having 4 or an aryl group having 6 to 10 carbon atoms
To 26 biphenyl groups, more preferably an unsubstituted or halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 6 to 26 carbon atoms.
A biphenyl group having 12 to 22 carbon atoms, which may be mono- or polysubstituted with 10 aryl groups.

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 halogen atom, an alkyl group, a phenyl group having a total of 6 to 24 carbon atoms which may be mono- or polysubstituted with an alkoxy group or an aryl group, or an unsubstituted or substituted group such as a halogen atom, A naphthyl group having a total of 10 to 24 carbon atoms which may be mono- or polysubstituted with an alkyl group, an alkoxy group or an aryl group, more preferably an unsubstituted or halogen atom, or an alkyl group having 1 to 14 carbon atoms. Group, carbon number 1-14
A total of 6 to 24 carbon atoms which may be mono- or polysubstituted by an alkoxy group or an aryl group having 6 to 10 carbon atoms
Or unsubstituted or mono- or polysubstituted with a halogen atom, an alkyl group having 1 to 14 carbon atoms, an alkoxy group having 1 to 14 carbon atoms or an aryl group having 6 to 10 carbon atoms. Good total carbon number 10-24
And more preferably unsubstituted 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. A phenyl group having a total of 6 to 16 carbon atoms, or an unsubstituted or halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl having 6 to 10 carbon atoms It is a naphthyl group having a total of 10 to 20 carbon atoms which may be mono- or polysubstituted.

Specific examples of the substituted or unsubstituted biphenyl groups in Ar _{1 to} Ar ₃ include, for example, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4′-methyl Phenyl) 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'-n-dodecylphenyl) phenyl group, 3- (4′-methylphenyl) phenyl group, 2- (4′-methylphenyl) phenyl group, 2-
(4′-ethylphenyl) phenyl group, 4- (4′-methoxyphenyl) phenyl group, 4- (3′-methoxyphenyl) phenyl group, 4- (4′-ethoxyphenyl)
Phenyl group, 4- (4'-n-butoxyphenyl) phenyl group, 4- (4'-n-hexyloxyphenyl) phenyl group, 4- (4'-n-octyloxyphenyl)
Phenyl group, 4- (4'-n-decyloxyphenyl)
Phenyl group, 3- (4'-methoxyphenyl) phenyl group, 2- (4'-methoxyphenyl) phenyl group, 2-
(2′-methoxyphenyl) phenyl group, 4- (4′-
Fluorophenyl) phenyl group, 4- (4′-chlorophenyl) phenyl group, 4- (3′-fluorophenyl)
Phenyl group, 4- (2′-fluorophenyl) phenyl group, 2- (4′-fluorophenyl) phenyl group,

A 3-methyl-4-phenylphenyl group, 4
-Methyl-3-phenylphenyl group, 4-methyl-2-
Phenylphenyl group, 5-methyl-2-phenylphenyl group, 6-methyl-3-phenylphenyl group, 2-ethyl-4-phenylphenyl group, 4-ethyl-2-phenylphenyl group, 2-methoxy-4- Phenylphenyl group, 3-methoxy-4-phenylphenyl group, 4-methoxy-2-phenylphenyl group, 4-fluoro-2-phenylphenyl group, 3-fluoro-4-phenylphenyl group, 3-fluoro-2- Phenylphenyl group, 5-fluoro-2-phenylphenyl group, 2,4-diphenylphenyl group, 2-phenyl-4- (4′-methylphenyl) phenyl group, 3,4-diphenylphenyl group, 3,
Examples thereof include a 5-diphenylphenyl group, but are not limited thereto.

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, 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-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxy A phenyl group, a 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′-n-dodecylphenyl) phenyl group, 3-
(4′-methylphenyl) phenyl group, 2- (4′-methylphenyl) phenyl group, 2- (4′-ethylphenyl) phenyl group, 4- (4′-methoxyphenyl) phenyl group, 4- (3 '-Methoxyphenyl) phenyl group,
4- (4′-ethoxyphenyl) phenyl group, 4-
(4′-n-butoxyphenyl) phenyl group, 4-
(4′-n-hexyloxyphenyl) phenyl group, 4
A-(4'-n-octyloxyphenyl) phenyl group,
4- (4′-n-decyloxyphenyl) phenyl group,
3- (4'-methoxyphenyl) phenyl group, 2-
(4′-methoxyphenyl) phenyl group, 2- (2′-
Methoxyphenyl) phenyl group, 4- (4′-fluorophenyl) phenyl group, 4- (4′-chlorophenyl)
Phenyl group, 4- (3′-fluorophenyl) phenyl group, 4- (2′-fluorophenyl) phenyl group, 2-
A (4′-fluorophenyl) phenyl group,

A 3-methyl-4-phenylphenyl group, 4
-Methyl-3-phenylphenyl group, 4-methyl-2-
Phenylphenyl group, 5-methyl-2-phenylphenyl group, 6-methyl-3-phenylphenyl group, 2-ethyl-4-phenylphenyl group, 4-ethyl-2-phenylphenyl group, 2-methoxy-4- Phenylphenyl group, 3-methoxy-4-phenylphenyl group, 4-methoxy-2-phenylphenyl group, 4-fluoro-2-phenylphenyl group, 3-fluoro-4-phenylphenyl group, 3-fluoro-2- Phenylphenyl group, 5-fluoro-2-phenylphenyl group, 2,4-diphenylphenyl group, 2-phenyl-4- (4′-methylphenyl) phenyl group, 3,4-diphenylphenyl group, 3,
5-diphenylphenyl group, 4-fluorophenyl group,
3-fluorophenyl group, 2-fluorophenyl group, 4
-Chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group, 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- A fluoro-4-ethoxyphenyl group, a 3-chloro-4-methoxyphenyl group, a 2-methoxy-5-chlorophenyl group, a 3-methoxy-6-chlorophenyl group, a 5-chloro-2,4-dimethoxyphenyl group, and the like. However, the present invention is not limited to these.

In Ar ₄ , specific examples of a substituted or unsubstituted naphthyl group include, for example, a 1-naphthyl group,
-Naphthyl group, 2-methyl-1-naphthyl group, 4-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, 1-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 6-ethyl-2-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 group, 6-phenyl-2-naphthyl group, 4-fluoro-1-naphthyl group, 2-fluoro-1-naphthyl group, 4-chloro-1-naphthyl group, 4-
Chloro-2-naphthyl group, 6-chloro-2-naphthyl group, 6-bromo-2-naphthyl group, 2,4-dichloro-
Examples thereof include a 1-naphthyl group and a 1,6-dichloro-2-naphthyl group, but are not limited thereto. Specific examples of the compound represented by the general formula (1) according to the present invention include, for example, the following compounds (Chem.
5), but the present invention is not limited to these.

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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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) and a compound represented by the general formula (3)
The compound represented by the general formula (4) (Chemical formula 26), the compound represented by the general formula (5) (Chemical formula 26), and the compound represented by the general formula (6) (Chemical formula 26) It can be produced by reacting in the presence (Ullman reaction).

[0041]

Embedded image [In the above formula, X _{1 to} X ₄ represent a halogen atom, and Ar ₁ to
Ar ₄ has the same meaning as in Formula (1). For example, a compound represented by Formula (7), a compound represented by Formula (8) (Formula 27), It can also be produced by reacting a compound represented by the general formula (9) (Formula 27) in the presence of a copper compound (Ullman reaction).

[0042]

Embedded image [In the above formula, X ₅ and X ₆ represent a halogen atom, and Ar ₁ to
Ar ₄ has the same meaning as in formula (1)] In formulas (3) to (7), X _{1 to} X ₆ represent a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom; More preferably, it represents a bromine atom or an iodine atom.

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 may be provided as desired. An electron injection / transport layer containing an injection / transport component can also be provided. For example, when the hole injection function, hole transport function and / or electron injection function, and electron transport function of the compound used for the light emitting layer are good, 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 Of course, depending on the case, a structure of a device (single-layer device) without both the hole injection transport layer and the electron injection transport layer may be employed. Further, each of the hole injection transport layer, the electron injection transport layer and the light emitting layer may have a single-layer structure or a multilayer structure,
The hole injecting and transporting layer and the electron injecting and transporting layer can be formed by separately providing a layer having an injection function and a layer having a transport function in each layer.

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

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

The organic electroluminescent device of the present invention is not limited to these device configurations, and each type of device may be provided with a plurality of hole injection / transport layers, light emitting layers, and electron injection / transport layers. it can. In each type of device, a light emitting component is provided between the hole injecting and transporting layer and the light emitting layer, and / or a mixed layer of the hole injecting and transporting component and the light emitting component. And a mixed layer of an electron injection and transport component. More preferred configurations of the organic electroluminescent device are (A) type device, (B) type device, (E)
Type element, (F) type element or (G) type element, and more preferably (A) type element, (B) type element 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 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 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 the compound represented by the general formula (1) is used in combination with another compound having a hole injecting and transporting function, the proportion of the compound represented by the general formula (1) 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, more preferably 1 to 9% by weight.
It is adjusted to about 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 10
6, Coumarin 138, Coumarin 151, Coumarin 15
2, Coumarin 153, Coumarin 307, Coumarin 31
1. Coumarin 314, Coumarin 334, Coumarin 33
8, coumarin 343, coumarin 500], pyran derivatives [eg, DCM1, DCM2], oxazone derivatives [eg, Nile Red], benzothiazole derivatives,
Benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamate derivatives, poly-
N-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 Derivatives, polythienylenevinylene and its derivatives)
Can be formed by using at least one kind of

In the organic electroluminescent device of the present invention, the light emitting layer preferably contains the 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. For example, rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene,
Tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, 9,10-diphenylanthracene, 9,10-bis (phenylethynyl) anthracene, 1,4-bis (9′-ethynylanthracenyl) benzene, 4,4′-bis (9 "-ethynylanthracenyl) biphenyl, etc. Of course, the polycyclic aromatic compound may be used alone or in combination of two or more.

When the compound represented by the general formula (1) is used as a guest compound to form a light-emitting layer, the host compound is preferably a light-emitting organometallic complex. In this case, the compound represented by the general formula (1) is preferably used in an amount of about 0.001 to 40% by weight, more preferably about 0.01 to 30% by weight, based on the luminescent organic metal complex. Preferably, about 0.1 to 20% by weight is used.

The light-emitting organometallic complex used in combination with the compound represented by the general formula (1) is not particularly limited, but a light-emitting organic aluminum 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-phenylphenolato) 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-te
rt-butylphenolato) 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-phenylphenolato) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3-phenylphenolato) aluminum, bis (2,4-dimethyl-8-quinolinolate) (4-phenylphenolato) 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 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.

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 10 to 5 nm.
Set to about 00 nm. In order to efficiently extract light emitted from the organic electroluminescent device, it is preferable that at least one of the anode and the cathode is transparent or translucent, and the transmittance of emitted light is generally 70% or more. It is more preferable to set the material and thickness of the anode.

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

The method for forming the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer is not particularly limited. For example, a vacuum evaporation method, an ionization evaporation method, a solution coating method (for example, a spin coating method, a 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.
Boat temperature of about 0 to 600 ° C (evaporation source temperature), -50
At a substrate temperature of about 300 ° C. to about 0.005 to 50 nm /
It is preferable to perform the deposition at a rate of about sec. In this case, by forming the layers such as the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer continuously under vacuum, an organic electroluminescent device having more excellent various characteristics can be manufactured.
When each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer is formed using a plurality of compounds by a vacuum deposition method, each boat containing the compounds is individually temperature-controlled and co-deposited. Is preferred.

When each layer is formed by a solution coating method,
The components forming each layer or the components and a binder resin or the like are dissolved or dispersed in a solvent to form a coating liquid. Examples of the binder resin that can be used for each of the hole injection transport layer, the light emitting layer, and the electron injection transport layer include poly-N-vinylcarbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl acrylate, and the like.
Polymethyl methacrylate, polyether, polycarbonate, polyamide, polyimide, polyamide imide,
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.

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

The thicknesses of the hole injecting and transporting layer, the light emitting layer and the electron injecting and transporting layer are not particularly limited, but are generally preferably set to about 5 nm to 5 μm.
A protective layer (sealing layer) may be provided on the fabricated device for the purpose of preventing contact with oxygen, moisture, or the like, or the device may be formed of, for example, paraffin, liquid paraffin, silicon oil, fluorocarbon oil, zeolite, or the like. It can be protected by being enclosed in an inert substance such as a contained fluorocarbon oil.

As the 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 films, amorphous silica, electrically insulating glass, metal oxides, metal nitrides, metal carbides, metal sulfides), and furthermore, photocurable resins, and the like. 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 being treated 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.

[0075]

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, the compound of Exemplified Compound No. 1 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 2 nm / sec to a thickness of 50 nm to form a light emitting layer also serving as an electron injection transport layer. Further thereon, magnesium and silver were used as cathodes 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 460 cd / m ² was confirmed. The half life of the luminance was 740 hours.

Examples 2 to 23 In Example 1, instead of using the compound of Exemplified Compound No. 1 in forming the hole injection transport layer, the compound of Exemplified Compound No. 3 (Example 2) and Exemplified Compound No. 7 were used. (Example 3), compound of Exemplified Compound No. 12 (Example 4), compound of Exemplified Compound No. 13 (Example 5), compound of Exemplified Compound No. 20 (Example 6), compound of Exemplified Compound No. 24 (Example 7), a compound of Exemplified Compound No. 28 (Example 8), a compound of Exemplified Compound No. 31 (Example 9), a compound of Exemplified Compound No. 33 (Example 10),
Compound of Exemplified Compound No. 40 (Example 11), Compound of Exemplified Compound No. 44 (Example 12), Exemplified Compound No. 4
Compound No. 8 (Example 13), Compound No. 52 (Example 14), Compound No. 55 (Example 15), Compound No. 58 (Example 1)
6), compound of Exemplified Compound No. 64 (Example 17), compound of Exemplified Compound No. 67 (Example 18), compound of Exemplified Compound No. 72 (Example 19), Exemplified Compound No. 75
(Example 20), the compound of Exemplified Compound No. 80 (Example 21), the compound of Exemplified Compound No. 83 (Example 22), and the compound of Exemplified Compound No. 88 (Example 23). An organic electroluminescent device was produced by the method described in Example 1. Green light emission was confirmed from each element. The characteristics were further examined, and the results are shown in Table 1 (Table 1).

Comparative Examples 1 to 3 In Example 1, instead of using the compound of Exemplified Compound No. 1 in forming the hole injecting and transporting layer, 4,4′-bis [N-phenyl-N- ( 3 "-methylphenyl) amino] biphenyl (Comparative Example 1), 2,5
-Bis [4 '-(N, N-diphenylamino) phenyl] -3,4-diphenylthiophene (Comparative Example 2),
Except that 2,5-bis [4 ′-[N-phenyl-N- (4 ″ -phenylphenyl) amino] phenyl] -3,4-diphenylthiophene (Comparative Example 3) was used, the description is in Example 1. An organic electroluminescent device was produced by the method described in Example 1. Green light emission was confirmed from each device, and its characteristics were further examined.

[0078]

[Table 1]

Example 24 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr.
First, poly (thiophene-2,5) was placed on the ITO transparent electrode.
-Diyl) was deposited at a deposition rate of 0.1 nm / sec to a thickness of 20 nm to form a first hole injection / transport layer. Next, the compound of Exemplified Compound No. 4 was deposited at a deposition rate of 0.2 nm / sec.
Was evaporated to a thickness of 55 nm to form a second hole injection / transport layer. Then, tris (8-quinolinolanote) aluminum was deposited thereon at a deposition rate of 0.2 nm / sec.
It was deposited to a thickness of nm to form a light emitting layer which also served as 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. Applying a DC voltage to the produced organic electroluminescent device,
The device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere. Initially, 6.4 V, luminance 780 cd / m
Green light emission of ² was confirmed. Brightness half-life is 1300
It was time.

Example 25 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, 4,4 ′, 4 ″ -tris [N- (3 ″ ′-methylphenyl) -N-phenylamino] triphenylamine was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / sec.
Then, it was deposited to a thickness of 50 nm to form a first hole injection transport layer. Next, the compound of Exemplified Compound No. 11 and rubrene were separated from different evaporation sources at a deposition rate of 0.2 nm / sec.
Co-evaporation (weight ratio: 10: 1) was performed to a thickness of 0 nm to obtain a light emitting layer also serving as a second hole injection / transport layer. Then, on top of that,
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 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 direct current 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, luminance 600c
A yellow emission of d / m ² was confirmed. Brightness half-life is 1
400 hours.

Example 26 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr.
First, poly (thiophene-2,5) was placed on the ITO transparent electrode.
-Diyl) was deposited at a deposition rate of 0.1 nm / sec to a thickness of 20 nm to form a first hole injection / transport layer. After returning the vapor deposition tank to the atmospheric pressure, the pressure of the vapor deposition tank was again reduced to 3 × 10 ⁻⁶ Torr. Next, the compound of Exemplified Compound No. 21 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. While maintaining the reduced pressure state, tris (8-quinolinolate) aluminum was further deposited thereon at a deposition rate of 0.2 nm / sec for 50 n.
m to form an electron injecting and transporting layer. While maintaining the reduced pressure, magnesium and silver were further co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to form a cathode to produce an organic electroluminescent device. did. A direct current 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, luminance 620c
A yellow emission of d / m ² was confirmed. Brightness half-life is 1
650 hours.

Example 27 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, a compound of Exemplified Compound No. 5 was deposited on an 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. 41 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, tris (8-quinolinolate) aluminum is further deposited thereon at a deposition rate of 0.2 nm / sec for 50 n.
m 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 is applied to the manufactured organic electroluminescent device, and 10
The device was continuously driven at a constant current density of mA / cm ² . Initially, yellow light emission of 6.1 V and a luminance of 640 cd / m ² was confirmed. The half life of the luminance was 1600 hours.

Example 28 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. 2 was deposited on the ITO transparent electrode to a thickness of 55 nm at a deposition rate of 0.2 nm / sec to form a hole injecting and transporting layer. Next, tris (8-quinolinolato) aluminum and the compound of Exemplified Compound No. 53 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 direct current 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 6.2 V and luminance of 660 cd / m ² was confirmed. The half life of the luminance was 1800 hours.

Example 29 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. 27 in a weight ratio of 100: 50.
Was used as a hole injection transport layer having a thickness of 40 nm by a dip coating method using a 3% by weight dichloroethane solution. Next, after fixing the glass substrate having the hole injecting and transporting layer to the substrate holder of the vapor deposition apparatus, the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. Next, tris (8-quinolinolato) aluminum was deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form a light-emitting layer also serving as an electron injection / transport layer. Furthermore, on the light emitting layer,
Magnesium and silver are deposited at a deposition rate of 0.2 nm / sec.
Co-deposit (weight ratio 10: 1) to a thickness of nm to form a cathode,
An organic electroluminescent device was manufactured. 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 1180c
Green light emission of d / m ² was confirmed. Brightness half-life is 3
60 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, 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 the substrate holder of the vapor deposition apparatus, the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. Further, magnesium and silver were deposited on the light emitting layer 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. 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 680
Green light emission of cd / m ² was confirmed. The half life of the luminance was 440 hours.

[0086]

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 Continuing on the front page (72) Inventor Takehiko Shimamura 580-2, Takuji, Nagaura-shi, Sodegaura-shi, Chiba Inside Mitsui Chemicals, Inc. (72) Inventor Yoshiyuki Toya 580-Takuji, Nagaura, Sodegaura-shi, Chiba 32 Mitsui Chemicals, Inc. F-term (reference) 3K007 AB00 BB06 CA01 CA02 CA05 CA06 CB01 CB03 DA00 DB03 EB00 FA01

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 containing at least one compound containing a compound represented by the formula: Embedded image (Wherein, Ar _{1 to} Ar ₃ each independently represent a substituted or unsubstituted biphenyl group, and Ar ₄ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl 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.