JP2002265938A - Material for organic electroluminescence device and organic electroluminescence device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescence(EL) device which has good luminescence color, high luminosity, luminescence efficiency, positive hole injection, positive hole transport and a long life time; a material satisfactory for the organic EL device. SOLUTION: The material for the organic EL device is a spiro compound represented by formulae (1)-(3), wherein R<1> to R<42> and X<1> to X<4> are independently H, a halogen, a cyano group, a nitro group, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a siloxy group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an amino group or a styryl group. R<1> to R<42> and X<1> to X<4> may couple with an adjacent C or substituent group to form a ring. Y<1> is a direct bond, a bivalent alkylene group, an aliphatic ring residue, an arylene group, an aromatic heterocyclic residue, or a styryl residue, which may have O, S, N.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent (EL) device material used for a flat light source and a display, and an organic EL device using the same. More specifically, the present invention relates to an organic EL device material having high luminance, high efficiency, and long life, and an organic EL device using the same.

[0002]

2. Description of the Related Art An EL device using an organic substance is expected to be used as an inexpensive, large-area, full-color display device of a solid light emitting type, and many developments have been made. Generally, an EL element includes a light-emitting layer and a pair of opposed electrodes sandwiching the light-emitting layer. In light emission, when an electric field is applied between both electrodes, electrons are injected from the cathode side, holes are injected from the anode side, and the electrons recombine with holes in the light emitting layer, and the energy level is changed to the conduction band. This is a phenomenon in which energy is emitted as light when returning to the valence band from.

[0003] Conventional organic EL devices have a higher driving voltage and lower luminous brightness and luminous efficiency than inorganic EL devices.
In addition, the characteristic deterioration was remarkable, and it had not been put to practical use.
2. Description of the Related Art In recent years, an organic EL in which a thin film containing an organic compound having high fluorescence quantum efficiency that emits light at a low voltage of 10 V or less is laminated.
Devices have been reported and are of interest (see Applied Physics Letters, vol. 51, p. 913, 1987). This method uses a metal chelate complex for a light emitting layer and an amine compound for a hole injection layer to obtain high-brightness green light emission.
(Cd / m ² ) and a maximum luminous efficiency of 1.5 (lm / W), which is close to the practical range.

[0004] Spiro compounds have been studied in order to develop a light emitting material having a high light efficiency and a hole injecting material having a high hole injection efficiency. Until now, spiro compounds such as JP-A-7-278538 and JP-T-10-509996 have been synthesized and prototyped as organic EL devices.
The luminous efficiency and the life were not sufficient.

[0005]

The organic EL device described in the prior art, although the light emission intensity has been improved due to the improved structure, it cannot be said that it still has sufficient light emission luminance. In addition, there is a major problem that the stability upon repeated use is poor. This is because, for example, a metal chelate complex such as a tris (8-hydroxyquinolinato) aluminum complex becomes chemically unstable at the time of electroluminescence and has poor adhesion to a cathode, so that it is deteriorated by short-time light emission. by. For the above reasons, there has been a demand for an organic EL device exhibiting good luminescent color, high luminous brightness and luminous efficiency, and having a longer life, and an organic EL device material capable of satisfying the same. In order to achieve this, development of a light emitting material having high luminous efficiency and a hole injecting material having high hole injecting efficiency have been desired.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems in consideration of the above problems, and as a result, have reached the present invention.

That is, the present invention is an organic electroluminescent device material represented by the following general formula [1]. General formula [1]

[0008]

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[Wherein R ^{1 to} R ¹⁶ , X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group; Group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted siloxy group, substituted or unsubstituted cycloalkyl group,
It is a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted amino group, or a substituted or unsubstituted styryl group. R ^{1 to} R ¹⁶ , X ¹ ,
X ² may combine with an adjacent carbon atom or a substituent to form a ring. Further, the present invention is a light-emitting material for an organic electroluminescence device represented by the following general formula [1]. General formula [1]

[0010]

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[Wherein R ^{1 to} R ¹⁶ , X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group; Group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted siloxy group, substituted or unsubstituted cycloalkyl group,
It is a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted amino group, or a substituted or unsubstituted styryl group. R ^{1 to} R ¹⁶ , X ¹ ,
X ² may combine with an adjacent carbon atom or a substituent to form a ring. Further, the present invention is a hole injection material for an organic electroluminescence device represented by the following general formula [1]. General formula [1]

[0012]

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[Wherein R ^{1 to} R ¹⁶ , X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group; Group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted siloxy group, substituted or unsubstituted cycloalkyl group,
It is a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted amino group, or a substituted or unsubstituted styryl group. R ^{1 to} R ¹⁶ , X ¹ ,
X ² may combine with an adjacent carbon atom or a substituent to form a ring. Further, the present invention is an organic electroluminescence device material represented by the following general formula [2]. General formula [2]

[0014]

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[Wherein, R ^{1 to} R ²⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group; Aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted siloxy group,
A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted amino group, and a substituted or unsubstituted styryl group. R ^{1 to} R ²⁶ may combine with an adjacent carbon atom or a substituent to form a ring. Further, the present invention is a light-emitting material for an organic electroluminescence device represented by the following general formula [2]. General formula [2]

[0016]

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[Wherein, R ^{1 to} R ²⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group; Aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted siloxy group,
A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted amino group, and a substituted or unsubstituted styryl group. R ^{1 to} R ²⁶ may combine with an adjacent carbon atom or a substituent to form a ring. Further, the present invention is a hole injection material for an organic electroluminescence element represented by the following general formula [2]. General formula [2]

[0018]

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[Wherein, R ^{1 to} R ²⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group; Aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted siloxy group,
A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted amino group, and a substituted or unsubstituted styryl group. R ^{1 to} R ²⁶ may combine with an adjacent carbon atom or a substituent to form a ring. Further, the present invention is an organic electroluminescence device material represented by the following general formula [3]. General formula [3]

[0020]

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[Wherein R ^{1 to} R ¹⁶ , R ^{27 to} R ⁴² , X ³ , X ⁴ ,
Each independently represents a hydrogen atom, a halogen atom, a cyano group,
Nitro group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group,
Substituted or unsubstituted arylthio group, substituted or unsubstituted siloxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted amino Group, a substituted or unsubstituted styryl group. R ¹ 〜
R ¹⁶ , R ^{27 to} R ⁴² , X ³ , and X ⁴ may be bonded to adjacent carbon atoms or substituents to form a ring. Y ¹ is
Direct bond, or a divalent, substituted or unsubstituted alkylene group, a substituted or unsubstituted aliphatic ring residue, a substituted or unsubstituted arylene group, a substituted or unsubstituted aromatic heterocyclic residue, styryl residue And each group may have oxygen, sulfur, or nitrogen. Further, the present invention is a light-emitting material for an organic electroluminescence device represented by the following general formula [3]. General formula [3]

[0022]

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Wherein R ^{1 to} R ¹⁶ , R ^{27 to} R ⁴² , X ³ , X ⁴ ,
Each independently represents a hydrogen atom, a halogen atom, a cyano group,
Nitro group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group,
Substituted or unsubstituted arylthio group, substituted or unsubstituted siloxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted amino Group, a substituted or unsubstituted styryl group. R ¹ 〜
R ¹⁶ , R ^{27 to} R ⁴² , X ³ , and X ⁴ may be bonded to adjacent carbon atoms or substituents to form a ring. Y ¹ is
Direct bond, or a divalent, substituted or unsubstituted alkylene group, a substituted or unsubstituted aliphatic ring residue, a substituted or unsubstituted arylene group, a substituted or unsubstituted aromatic heterocyclic residue, styryl residue And each group may have oxygen, sulfur, or nitrogen. Further, the present invention is a hole injection material for an organic electroluminescence device represented by the following general formula [3]. General formula [3]

[0024]

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Wherein R ^{1 to} R ¹⁶ , R ^{27 to} R ⁴² , X ³ , X ⁴ ,
Each independently represents a hydrogen atom, a halogen atom, a cyano group,
Nitro group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group,
Substituted or unsubstituted arylthio group, substituted or unsubstituted siloxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted amino Group, a substituted or unsubstituted styryl group. R ¹ 〜
R ¹⁶ , R ^{27 to} R ⁴² , X ³ , and X ⁴ may be bonded to adjacent carbon atoms or substituents to form a ring. Y ¹ is
Direct bond, or a divalent, substituted or unsubstituted alkylene group, a substituted or unsubstituted aliphatic ring residue, a substituted or unsubstituted arylene group, a substituted or unsubstituted aromatic heterocyclic residue, styryl residue And each group may have oxygen, sulfur, or nitrogen. Further, according to the present invention, there is provided an organic electroluminescence device having at least one light emitting layer formed between a pair of electrodes including an anode and a cathode, wherein at least one layer is a layer containing the organic electroluminescence device material. It is an electroluminescent element.

According to the present invention, there is provided an organic electroluminescent device comprising at least one light emitting layer formed between a pair of electrodes comprising an anode and a cathode, wherein the light emitting layer contains the light emitting material for an organic electroluminescent device. The organic electroluminescent device is a layer.

The present invention also relates to an organic electroluminescence device comprising at least one light-emitting layer formed between a pair of electrodes comprising an anode and a cathode, wherein at least one layer comprises the hole injection material for an organic electroluminescence device. It is an organic electroluminescence element which is a layer containing.

Further, the present invention is the above-mentioned organic electroluminescence device, further comprising at least one electron injection layer formed between the light emitting layer and the cathode.

Further, the present invention is the above-described organic electroluminescence device, further comprising at least one hole injection layer formed between the light emitting layer and the anode.

[Detailed Description of the Invention]

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the material for an organic EL device of the present invention will be described. The novel spiro compound of the present invention can be used as a light emitting material or a hole injection material,
As the organic EL device using this, a light emitting device with high luminance, high efficiency and long life has been obtained.

Next, the reason why the material for an organic EL device of the present invention is useful will be described.

The novel spiro compound of the present invention is designed as a skeleton having a high electron-donating or hole-injecting or transporting property due to the stericity and resistance of the spiro skeleton and the nitrogen atom in the spiro skeleton. . As a result, it is considered that concentration quenching is less likely to occur, and the amorphous property of the light emitting layer can be maintained for a long time, so that a light emitting element with high luminance, high efficiency and long life can be obtained. These compounds may be used as a mixture of two or more. When used as a hole injection material, the hole injection layer may be formed of two or more layers. In that case, a hole injection layer from the anode side,
It may be called a hole transport layer. In many cases, these are collectively set as a hole transport band.

Here, the substituents of the general formulas [1] to [3] will be described. Substituents R ¹ to R ¹ to R ³ to R ³ to
R ⁴² and X ^{1 to} X ^{4 each} represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group,
Substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted siloxy group, substituted or unsubstituted cycloalkyl group, Examples include a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted amino group, and a substituted or unsubstituted styryl group.

Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituted or unsubstituted alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group,
sec-butyl group, tert-butyl group, pentyl group,
Hexyl group, heptyl group, octyl group, unsubstituted alkyl group having 1 to 30 carbon atoms such as stearyl group, 2-phenylisopropyl group, trichloromethyl group, trifluoromethyl group, benzyl group, α-phenoxybenzyl group, α , Α-dimethylbenzyl group, α, α-methylphenylbenzyl group, α, α-bis (trifluoromethyl)
Examples thereof include a substituted alkyl group having 1 to 30 carbon atoms such as a benzyl group, a triphenylmethyl group and an α-benzyloxybenzyl group.

The substituted or unsubstituted alkoxy group includes methoxy, ethoxy, propoxy, butoxy, tert-butoxy, octyloxy,
Examples thereof include an unsubstituted alkoxy group having 1 to 20 carbon atoms such as a tert-octyloxy group, and a substituted alkoxy group having 1 to 20 carbon atoms such as a 3,3,3-trifluoroethoxy group and a benzyloxy group.

Examples of the substituted or unsubstituted aryloxy groups include phenoxy, 4-tert-butylphenoxy, 1-naphthyloxy, 2-naphthyloxy and 9-anthryloxy groups. 20
And substituted aryloxy groups having 6 to 20 carbon atoms such as 4-nitrophenoxy group, 3-fluorophenoxy group, pentafluorophenoxy group, and 3-trifluoromethylphenoxy group.

The substituted or unsubstituted alkylthio group includes a methylthio group, an ethylthio group, a tert-
An unsubstituted alkylthio group having 1 to 20 carbon atoms such as a butylthio group, a hexylthio group, and an octylthio group;
C1-C20 such as 1,1-tetrafluoroethylthio group, benzylthio group and trifluoromethylthio group
Is a substituted alkylthio group.

Examples of the substituted or unsubstituted arylthio groups include unsubstituted arylthio groups having 6 to 20 carbon atoms such as phenylthio, 2-methylphenylthio, and 4-tert-butylphenylthio, and 3-fluoro. Phenylthio group, pentafluorophenylthio group, 3-
6-20 carbon atoms such as a trifluoromethylphenylthio group
Is a substituted arylthio group.

Examples of the substituted or unsubstituted siloxy group include substituted or unsubstituted siloxy groups having 3 to 30 carbon atoms such as trimethylsiloxy group, triethylsiloxy group, triphenylsiloxy group and tolylsiloxy group. .

The substituted or unsubstituted cycloalkyl group includes a cyclopentyl group, a cyclohexyl group,
Examples thereof include a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as a 4-methylcyclohexyl group, a 4-phenylcyclohexyl group, and a 3,5-dimethylcyclohexyl group.

The substituted or unsubstituted aryl group includes a phenyl group, an o-tolyl group, an m-tolyl group,
-Tolyl, 2,4-xylyl, p-cumenyl, mesityl, 1-naphthyl, 2-naphthyl, 1-anthryl, 9-phenanthryl, 1-acenaphthyl, 2-azulenyl, 1 An unsubstituted aryl group having 6 to 30 carbon atoms, such as -pyrenyl group, 2-triphenyler group,
Carbon number of p-cyanophenyl group, p-diphenylaminophenyl group, p-styrylphenyl group, 4-[(2-tolyl) ethenyl] phenyl group, 4-[(2,2-ditolyl) ethenyl] phenyl group and the like 6 to 30 substituted aryl groups.

Examples of the substituted or unsubstituted aromatic heterocyclic group include 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl, and 3-furyl. Pyrrolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazyl group, 2-oxazolyl group, 3-isoxazolyl group, 2-thiazolyl group, 3-isothiazolyl group, 2-imidazolyl group, 3-
Pyrazolyl group, 2-quinolyl group, 3-quinolyl group, 4-
Quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 2-
Quinoxalinyl group, 2-benzofuryl group, 2-benzothienyl group, N-indolyl group, N-carbazolyl group, N
-An unsubstituted aromatic heterocyclic group having 3 to 20 carbon atoms such as an acridinyl group, a 2- (5-phenyl) furyl group,
Examples thereof include a substituted aromatic heterocyclic group having 3 to 20 carbon atoms, such as a (5-phenyl) thienyl group and a 2- (3-cyano) pyridyl group.

The substituted or unsubstituted amino group includes N-methylamino group, N-ethylamino group, N,
N-diethylamino group, N, N-diisopropylamino group, N, N-dibutylamino group, N-benzylamino group, N, N-dibenzylamino group, N-phenylamino group, N-phenyl-N-methylamino Group, N, N-diphenylamino group, N, N-bis (m-tolyl) amino group, N, N-bis (p-tolyl) amino group, N, N-bis (p-biphenylyl) amino group, bis [4- (4-methyl) biphenylyl] amino group, Np-biphenylyl-N-phenylamino group, N-α-naphthyl-N-phenylamino group, N-β-naphthyl-N-phenylamino group, N An unsubstituted amino group having 1 to 30 carbon atoms such as -phenanthryl-N-phenylamino group or N, N-bis (m
-Fluorophenyl) amino group, N, N-bis (p-cyanophenyl) amino group, bis [4- (α, α'-dimethylbenzyl) phenyl] amino group, etc.
A substituted amino group.

The substituted or unsubstituted styryl group may be any substituent as long as it has a styryl bond in the substituent.

Among the above substituents, preferred are a hydrogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, A substituted or unsubstituted amino group, a substituted or unsubstituted styryl group,
More preferred are a hydrogen atom, a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, and a substituted or unsubstituted styryl group.

As Y ^{1 in the} general formula [3], a direct bond,
A substituted or unsubstituted alkylene group, or a divalent,
A substituted or unsubstituted aliphatic ring residue, a substituted or unsubstituted arylene group, a substituted or unsubstituted aromatic heterocyclic residue, and a styryl residue, each of which has oxygen, sulfur, and nitrogen. May be.

Examples of the substituted or unsubstituted alkylene group include a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms such as a methylene group, an ethylene group and a propylene group. Each group may have oxygen, sulfur, and nitrogen.

As the divalent substituted or unsubstituted aliphatic ring residue, a C 1 -C 1 formed from 5 to 8 carbon atoms is preferable.
Up to 30 substituted or unsubstituted aliphatic ring residues. Each group may have oxygen, sulfur, and nitrogen.

Examples of the divalent substituted or unsubstituted arylene group include a substituted or unsubstituted arylene group having 1 to 30 carbon atoms, such as a phenylene group, a naphthylene group, an anthranylene group, a phenanthrylene group, and a biphenylene group. Can be Each group may have oxygen, sulfur, and nitrogen.

The divalent substituted or unsubstituted aromatic heterocyclic residue includes a substituted or unsubstituted aromatic heterocyclic residue having 1 to 30 carbon atoms.

The divalent substituted or unsubstituted styryl residue may be any styryl residue as long as it has a styryl bond in the substituent.

Table 1 shows typical examples of the compounds which can be used as the material for an organic EL device of the present invention.
The present invention is not limited to these. Table 1

[0055]

[Table 1]

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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The organic EL device is a device in which a single or multilayer organic thin film is formed between an anode and a cathode.
Here, the single-layer type organic EL element has a light emitting layer made of a light emitting material between an anode and a cathode. On the other hand, multilayer organic EL
The devices were (anode / hole injection layer / light emitting layer / cathode), (anode / light emitting layer / electron injection layer / cathode), (anode / hole injection layer / cathode).
It is an organic EL device stacked in a multilayer structure such as a light emitting layer / an electron injection layer / a cathode. Each layer may have a plurality of layers for the purpose of improving functionality and durability. In particular, the hole injection layer includes a hole injection layer for efficiently injecting holes from the anode, and a hole transport layer for injecting holes from the hole injection layer and further injecting the holes into the light emitting layer. It is often provided. In some cases, a hole blocking layer is provided between the light emitting layer and the electron injection layer.

The material for an organic EL device of the present invention can be suitably used as a light emitting material or a hole injecting material for these single-layer or multilayer organic EL devices. When a single-layer organic EL device is manufactured using the present organic EL device material, a hole injection material or an electron injection material for efficiently transporting holes injected from an anode or electrons injected from a cathode to a light emitting material. Can be contained.

Here, the hole injection material has an excellent hole injection effect on the light emitting layer or the light emitting material and prevents excitons generated in the light emitting layer from moving to the electron injection layer or the electron injection material. And a compound having excellent thin film forming properties. Examples of such hole injection materials include phthalocyanine compounds, naphthalocyanine compounds, porphyrin compounds, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole , Hydrazone, acylhydrazone, polyarylalkane, stilbene, butadiene,
Benzidine-type triphenylamine, styrylamine-type triphenylamine, diamine-type triphenylamine and the like, and derivatives thereof, and polyvinyl carbazole,
Examples thereof include polysilane and conductive polymer, but the present invention is not limited to these.

Among the above hole injection materials, a particularly effective hole injection material is an aromatic tertiary amine derivative or a phthalocyanine derivative. Examples of aromatic tertiary amine derivatives include triphenylamine, tolylamine, tolyldiphenylamine, N, N'-diphenyl-
N, N '-(3-methylphenyl) -1,1'-biphenyl-4,4'-diamine, N, N, N', N '-(4
-Methylphenyl) -1,1'-phenyl-4,4'-
Diamine, N, N, N ′, N ′-(4-methylphenyl) -1,1′-biphenyl-4,4′-diamine,
N, N'-diphenyl-N, N'-dinaphthyl-1,
1'-biphenyl-4,4'-diamine, N, N'-
(Methylphenyl) -N, N ′-(4-n-butylphenyl) -phenanthrene-9,10-diamine, N, N
-Bis (4-di-4-tolylaminophenyl) -4-phenyl-cyclohexane, or an oligomer or polymer having an aromatic tertiary amine skeleton. As the phthalocyanine (Pc) derivative, H
₂ Pc, CuPc, CoPc, NiPc, ZnPc, P
dPc, FePc, MnPc, ClAlPc, ClGa
Pc, ClInPc, ClSnPc, Cl ₂ SiPc,
(HO) AlPc, (HO) GaPc, VOPc, Ti
Examples include phthalocyanine derivatives such as OPc, MoOPc, and GaPc-O-GaPc, and naphthalocyanine derivatives. The above-described hole injecting materials can be further sensitized by adding an electron accepting material. Organic EL of the present invention
The material also exhibits effective characteristics as a hole injection material.

On the other hand, the electron injecting material has an excellent electron injecting effect on the light emitting layer or the light emitting material and prevents the exciton generated in the light emitting layer from moving to the hole injecting layer or the hole injecting material. And a compound having excellent thin film forming properties.
Examples of such electron injecting materials include quinoline metal complexes, oxadiazoles, benzothiazole metal complexes, benzoxazole metal complexes, benzimidazole metal complexes, fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxadioxide Azole, thiadiazole, tetrazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane,
Examples include anthrone and the like and derivatives thereof, but the present invention is not limited to these.

Among the above electron injecting materials, particularly effective electron injecting materials include metal complex compounds and nitrogen-containing five-membered ring derivatives. Specific examples of the metal complex compound include bis (2-methyl-8-hydroxyquinolinate)
(1-Naphtholate) gallium complex, bis (2-methyl-8-hydroxyquinolinate) (2-naphtholate)
Gallium complex, bis (2-methyl-8-hydroxyquinolinate) (phenolate) gallium complex, bis (2-
Methyl-8-hydroxyquinolinate) (4-cyano-
1-naphtholate) gallium complex, bis (2,4-dimethyl-8-hydroxyquinolinate) (1-naphtholate) gallium complex, bis (2,5-dimethyl-8-hydroxyquinolinate) (2-naphtholate) Gallium complex, bis (2-methyl-5-phenyl-8-hydroxyquinolinate) (phenolate) gallium complex, bis (2-methyl-5-cyano-8-hydroxyquinolinate) (4-cyano-1- Naphtholate) gallium complex,
Bis (2-methyl-8-hydroxyquinolinato) chlorogallium complex, bis (2-methyl-8-hydroxyquinolinato) (o-cresolate) gallium complex and the like can be mentioned, but the present invention is not limited to these. Not something.

Among the electron injecting materials usable in the present invention, preferable metal complex compounds include lithium 8-hydroxyquinolinato, bis (8-hydroxyquinolinato) zinc, and bis (8-hydroxyquinolinate). Nart)
Copper, bis (8-hydroxyquinolinato) manganese, tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, Bis (10-hydroxybenzo [h] quinolinate) beryllium, bis (10-hydroxybenzo [h]
Quinolinato) zinc and the like.

Among the electron-injecting materials usable in the present invention, preferred nitrogen-containing five-membered derivatives include oxazole, thiazole, oxadiazole, thiadiazole and triazole derivatives.
5-bis (1-phenyl) -1,3,4-oxazole, dimethyl POPOP, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1-phenyl)- 1,3,4-oxadiazole, 2- (4 ′
-Tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazole, 2,5-bis (1
-Naphthyl) -1,3,4-oxadiazole, 1,4
-Bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene], 2- (4 ′
-Tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1
-Naphthyl) -1,3,4-thiadiazole, 1,4-
Bis [2- (5-phenylthiadiazolyl)] benzene,
2- (4'-tert-butylphenyl) -5- (4 "
-Biphenyl) -1,3,4-triazole, 2,5-
Bis (1-naphthyl) -1,3,4-triazole,
1,4-bis [2- (5-phenyltriazolyl)] benzene and the like. The above-described electron injecting materials can be further sensitized by adding an electron donating material.

The material for an organic EL device of the present invention may be used alone in the light emitting layer or may be used after doping. In this case, the organic E
The L element material is preferably contained in the range of 0.001 to 50% by weight, more preferably 0.01 to 10% by weight, based on the host material described below. preferable.

When the material for an organic EL device of the present invention is used as a doping material, the host material that can be used together includes a quinoline metal complex, a benzoquinoline metal complex, a benzoxazole metal complex, a benzothiazole metal complex, a benzimidazole metal complex. And electron transport materials such as benzotriazole metal complexes, imidazole derivatives, oxadiazole derivatives, thiadiazole derivatives, and triazole derivatives. Or a hole-transporting material such as a stilbene derivative, a butadiene derivative, a benzidine-type triphenylamine derivative, a styrylamine-type triphenylamine derivative, a diaminoanthracene-type triphenylamine derivative, a diaminophenanthrene-type triphenylamine derivative, and polyvinyl carbazole; Polymer materials such as a conductive polymer such as polysilane may be used.

Further, in the light emitting layer of the present organic EL device, in addition to the material for the organic EL device of the present invention, two or more kinds of other light emitting materials and doping materials can be used in combination. Other light emitting materials and doping materials that can be used together with the material for an organic EL device of the present invention include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene,
Phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene,
Tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, Merocyanine, imidazole chelated oxinoid compound, quinacridone,
And rubrene and the derivatives thereof.

In the light emitting layer of the present organic EL device, in addition to the material for the organic EL device of the present invention, if necessary, not only other light emitting materials and doping materials but also the above-described hole injection material. Also, two or more kinds of electron injection materials can be used in combination. Further, each of the hole injection layer, the light emitting layer, and the electron injection layer may be formed in a layer structure of two or more layers.

Further, as the conductive material used for the anode of the organic EL device of the present invention, those having a work function larger than 4 eV are suitable.
Aluminum, vanadium, iron, cobalt, nickel,
Tungsten, silver, gold, platinum, palladium and the like and alloys thereof, an ITO substrate, a metal oxide such as a tin oxide and an indium oxide called a NESA substrate, and an organic conductive polymer such as polythiophene and polypyrrole can be given.

Further, as the conductive material used for the cathode of the organic EL device of the present invention, those having a work function of less than 4 eV are suitable, such as magnesium, calcium, tin, lead, and the like. Examples include titanium, yttrium, lithium, lithium fluoride, ruthenium, manganese, and the like, and alloys thereof. Here, alloys include magnesium / silver, magnesium / indium,
Representative examples include lithium / aluminum, but are not limited thereto. The alloy ratio is
Since the temperature can be controlled by the heating temperature, atmosphere, and degree of vacuum during preparation, an alloy having an appropriate ratio can be prepared. These anodes and cathodes may be formed of two or more layers if necessary.

In order for the organic EL device of the present invention to emit light efficiently, it is desirable that the material constituting the device is sufficiently transparent in the emission wavelength region of the device, and that the substrate is also transparent. The transparent electrode can be formed by a method such as vapor deposition or sputtering using the above conductive material. In particular, the electrode on the light emitting surface has a light transmittance of 1
Desirably, it is 0% or more. The substrate is not particularly limited as long as it has mechanical and thermal strength and is transparent. For example, a glass substrate and a transparent polymer such as polyethylene, polyethersulfone, and polypropylene are recommended.

The method of forming each layer of the organic EL device of the present invention includes vacuum deposition, sputtering, plasma,
Either a dry film forming method such as ion plating or a wet film forming method such as spin coating, dipping, or flow coating can be applied.
The thickness of each layer is not particularly limited, but needs to be set to an appropriate thickness. If the film thickness is too large, a large applied voltage is required to obtain a constant light output, and the efficiency is reduced. Conversely, if the film thickness is too small, pinholes and the like occur, making it difficult to obtain sufficient light emission luminance even when an electric field is applied.
Therefore, the normal film thickness is suitably in the range of 1 nm to 1 μm, but is more preferably in the range of 10 nm to 0.2 μm.

In the case of the wet film forming method, each layer forms a thin film by dissolving or dispersing the material constituting the layer in an appropriate solvent such as toluene, chloroform, tetrahydrofuran, dioxane or the like. The solvent used here may be either a single solvent or a mixed solvent. In any of the wet film forming methods, a suitable polymer or additive may be used for improving film forming properties, preventing pinholes in the film, and the like. Examples of such polymers include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose; and photoconductive materials such as poly-N-vinyl carbazole and polysilane. And conductive polymers such as polythiophene and polypyrrole. In addition, examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer. When the material of the present invention is formed by a wet method, since the affinity between the molecules of each compound is good, even if the compound alone has a high cohesiveness and the film tends to be non-uniform, it may be mixed with a derivative having a low cohesiveness. A good film can be obtained by using the material.

In order to improve the stability of the organic EL device obtained according to the present invention against temperature, humidity, atmosphere, etc.,
Further, a protective layer may be provided on the surface of the device, or the entire device may be covered with silicone oil, polymer, or the like.

As described above, the organic EL device prepared using the light emitting material for an organic EL device according to the present invention can improve characteristics such as luminous efficiency and maximum luminous brightness. In addition, the present organic EL device is extremely stable against heat and current, and furthermore, can obtain a practically usable emission luminance at a low driving voltage, so that the deterioration which has been a major problem until now is greatly reduced. It is possible to lower. Therefore, this organic E
The L element can be applied to a flat panel display such as a wall-mounted television or a flat illuminator, and further to a light source such as a copying machine or a printer, a light source such as a liquid crystal display or an instrument, a display board, or a sign lamp.

[0101]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. Prior to the examples, a synthesis example of the material for an organic electroluminescence device of the present invention will be described. Synthesis Example 1 Synthesis of o-bromotriphenylamine In 50 ml of o-dichlorobenzene, 8.4 g of diphenylamine, 14.1 g of o-bromoiodobenzene, 13.8 g of potassium carbonate, and 3.2 g of copper powder were added, and the mixture was added under a nitrogen atmosphere. The mixture was heated at 180 ° C. for 3 days with stirring. After cooling, the reaction mixture was filtered, the filtrate was evaporated to dryness, and the obtained residue was purified by column chromatography (silica gel, hexane) to obtain 9.0 g of o-bromotriphenylamine. The structure was confirmed by mass spectrum and NMR spectrum analysis. Synthesis Example 2 Synthesis of Compound (9) In 8 mL of diethyl ether, 1.33 g of o-bromotriphenylamine was added and dissolved. This was cooled to −5 ° C. in a nitrogen atmosphere, and tert-butyllithium in pentane solution (concentration: 1.6 mol / L) with stirring.
5.2 mL was added over 0.5 hours. Temperature down to -5 ° C
After stirring for 2.5 hours while keeping the temperature at 25 ° C., 25 mL of a toluene solution containing 1.0 g of N-phenylacridone was added.
Was added dropwise. After completion of the dropwise addition, the reaction solution was stirred at 25 ° C. for 10 hours. 6 mL of 1 mol / L-hydrochloric acid was added to the reaction mixture, and extracted with 30 mL of benzene. The extract was evaporated to dryness, 20 mL of acetic acid and 25 μL of methylsulfuric acid were added, and the mixture was heated under reflux for 2 hours. Then, 100 m of water was added to the reaction solution.
L was added and extracted with 300 mL of toluene. The extract was evaporated to dryness and recrystallized from 120 mL of toluene to obtain 0.98 g of (compound 9). The structure was confirmed by mass spectrum and NMR spectrum analysis. Synthesis Example 3 4,4′-bis (9H-acridin-10-yl) bif
Synthesis of phenyl In 50 mL of dioxane, 4.00 g of 9,10-dihydroacridine, 3.12 g of 4,4′-biphenyl, 2.40 g of sodium-tert-butoxide, 0.001 g of palladium acetate and 0% of tri-tert-butylphosphine 0.003 g, and the mixture was heated and refluxed for 17 hours under a nitrogen atmosphere. After cooling, the mixture was diluted with 300 ml of water and extracted with chloroform. After the extract was concentrated, reprecipitation was performed from tetrahydrofuran / methanol, and 4,4′-bis (9H-acridin-10-yl) biphenyl 4.41 was obtained.
g was obtained. The structure was confirmed by mass spectrum and NMR spectrum analysis. Synthesis Example 4 4,4′-bis (9-oxoacridin-10-yl)
Synthesis of biphenyl 4,4′-bis (9H-
Acridine-10-yl) biphenyl 4.00 g, te
7.57 g of rt-butyl hydroperoxide and 0.17 g of chromium (IV) oxide were added, and the mixture was stirred under a nitrogen atmosphere at room temperature for 2 days. Then it was diluted with 300 ml of water and extracted with chloroform. After concentrating the extract,
Recrystallized from N, N-dimethylformamide,
4,4'-bis (9-oxoacridin-10-yl)
2.81 g of biphenyl were obtained. Mass spectrum, NMR
The structure was confirmed by spectral analysis. Synthesis Example 5 Synthesis of (Compound 100) In 8 mL of tetrahydrofuran, 1.49 g of o-bromotriphenylamine was added and dissolved. This was cooled to −5 ° C. in a nitrogen atmosphere, and a pentane solution of tert-butyllithium (concentration: 1.6 mol /
L) 5.8 mL was added over 0.5 hours. Temperature
After further stirring for 2.5 hours while maintaining the temperature at 5 ° C., 175 mL of a toluene solution containing 1.0 g of 4,4′-bis (9-oxoacridin-10-yl) biphenyl synthesized in Synthesis Example 4 was added dropwise. . After completion of the dropwise addition, the reaction solution was heated to 56 ° C.
For 23 hours. 6 mL of 1 mol / L-hydrochloric acid was added to the reaction mixture, and extracted with 100 mL of chloroform.
The extract was evaporated to dryness, 20 mL of acetic acid and 30 μL of methylsulfuric acid were added thereto, and the mixture was heated under reflux for 2 hours. Next, 100 mL of water was added to the reaction solution, and 300 mL of chloroform was added.
Extracted in mL. The extract was evaporated to dryness and recrystallized from chloroform (60 mL) to obtain 0.82 g of the desired product. The structure of (Compound 100) was confirmed by mass spectrometry and NMR spectroscopy.

Hereinafter, Examples using the compound of the present invention will be described. In this example, all mixing ratios are weight ratios. In addition, characteristics of an organic EL element having an electrode area of 2 mm × 2 mm were measured.

Example 1 A compound (10) shown in Table 1 and 2,5-bis (1-naphthyl) -1,3,4 were placed on a washed glass plate with an ITO electrode.
-Oxadiazole and a polycarbonate resin (Teijin Kasei: Panlite K-1300) were dissolved in tetrahydrofuran at a weight ratio of 1: 2: 10, and an organic layer having a thickness of 100 nm was obtained by spin coating. An electrode having a thickness of 150 nm was formed thereon using an alloy in which magnesium and silver were mixed at a weight ratio of 10: 1 to obtain an organic EL device.
The light emission characteristics of this element are such that the light emission luminance at a DC voltage of 5 V is 60.
(Cd / m ² ), maximum emission luminance 1020 (cd / m ² ),
Blue light emission with a light emission efficiency of 0.35 (lm / W) was obtained.

Example 2 On a cleaned glass plate with ITO electrodes, N, N ′-(3
-Methylphenyl) -N, N'-diphenyl-1,1 '
-Biphenyl-4,4'-diamine (TPD) was vacuum-deposited to obtain a hole injection layer having a thickness of 40 nm. Then, Table 1
Compound (16) was vapor-deposited to form a light-emitting layer having a thickness of 40 nm, and then tris (8-hydroxyquinolinato) aluminum complex (Alq3) was vapor-deposited to obtain a 30-nm-thick electron injection layer. Add magnesium and silver 10:
An electrode having a thickness of 100 nm was formed from the alloy mixed at 1 (weight ratio) to obtain an organic EL device. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. This device has an emission luminance of 140 at a DC voltage of 5 V.
(Cd / m ² ), maximum emission luminance 12,500 (cd / m ² )
m ² ) and blue luminescence with a luminous efficiency of 1.3 (lm / W) was obtained.

Example 3 A compound (9) shown in Table 1 was dissolved in methylene chloride on a washed glass plate with an ITO electrode, and a hole injection type light emitting layer having a thickness of 50 nm was obtained by a spin coating method. Then, bis (2-methyl-8-hydroxyquinolinate)
(1-Naphtholate) gallium complex was vacuum-deposited to form an electron injection layer having a thickness of 40 nm, on which an alloy obtained by mixing magnesium and silver at a weight ratio of 10: 1 was used.
An 0 nm electrode was formed to obtain an organic EL device. The light emitting layer and the electron injection layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. This device has a light emission luminance of 240 (cd / m ² ) at a DC voltage of 5 V and a maximum light emission luminance of 140.
Blue light emission having a luminance of 00 (cd / m ² ) and a luminous efficiency of 1.8 (lm / W) was obtained.

Example 4 The compound (56) shown in Table 1 was vacuum-deposited on a washed glass plate with an ITO electrode to obtain a hole injection type luminescent layer having a thickness of 50 nm. Next, bis (2-methyl-8-hydroxyquinolinato) (p-cyanophenolate) gallium complex was vacuum-deposited to form a 30-nm-thick electron injection layer.
An electrode having a thickness of 100 nm is formed thereon by using an alloy in which magnesium and silver are mixed at a weight ratio of 10: 1 to form an organic EL.
An element was obtained. The light emitting layer and the electron injection layer are 10 ^-6 Torr
Vacuum was deposited in a vacuum at a substrate temperature of room temperature. This device has a light emission luminance of 820 (cd /
m ² ), blue-green light emission with a maximum light emission luminance of 20900 (cd / m ² ) and a light emission efficiency of 2.3 (lm / W) was obtained.

Example 5 Copper phthalocyanine was vacuum-deposited on a washed glass plate with an ITO electrode to obtain a hole injection layer having a thickness of 50 nm. Then, N, N '-(3-methylphenyl) -N, N'-
Diphenyl-1,1′-biphenyl-4,4′-diamine (TPD) was vacuum-deposited to obtain a hole transporting (second hole injecting) layer having a thickness of 20 nm. Further, the compound (2
8) was vacuum-deposited to obtain a 50 nm-thick light emitting layer. Then, bis (2-methyl-8-hydroxyquinolinate)
(P-cyanophenolate) gallium complex was vacuum-deposited to form an electron injection layer having a thickness of 30 nm, and Li
An electrode having a film thickness of 0.5 nm for F and then a film thickness of 100 nm for Al was formed to obtain an organic EL device. The light emitting layer and the electron injection layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. This device has an emission luminance of 1200 (cd / m ² ) at a DC voltage of 5 V and a maximum emission luminance of 21000 (c
d / m ² ), and blue-green light emission with a luminous efficiency of 2.2 (lm / W) was obtained.

Example 6 4,4 ′, 4 ″ was placed on a washed glass plate with ITO electrodes.
-Tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine was vacuum deposited to a film thickness of 40
As a result, a hole injection layer having a thickness of nm was obtained. Next, α-NPD was vacuum-deposited to obtain a hole transport layer having a thickness of 20 nm. Further, a compound (100) shown in Table 1 was vacuum-deposited to form a light-emitting layer having a thickness of 30 nm, and a bis (2-methyl-8-hydroxyquinolinate) (phenolate) gallium complex was further vacuum-deposited to form a film. An electron injection layer having a thickness of 30 nm is formed, and an electrode having a thickness of 150 nm is formed on the electron injection layer using an alloy in which aluminum and lithium are mixed at a weight ratio of 25: 1.
An L element was obtained. The hole injection layer and the light emitting layer are 10 ^-6 Torr
The film was deposited under the condition of room temperature and substrate temperature in a vacuum of r. This device has a light emission luminance of 980 (cd /
m ² ), blue light emission having a maximum light emission luminance of 18000 (cd / m ² ) and a light emission efficiency of 2.0 (lm / W) was obtained.

Examples 7 to 37 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) was vacuum-deposited on a washed glass plate with an ITO electrode to form a film. A hole injection layer having a thickness of 30 nm was formed. Next, the material shown in Table 1 was vacuum-deposited as a light emitting material to obtain a light emitting layer having a thickness of 30 nm. Then
Bis (2-methyl-8-hydroxyquinolinato) (phenolate) gallium complex was vacuum-deposited to a thickness of 30 nm.
An electron injection layer was formed, and an electrode having a thickness of 100 nm was formed thereon using an alloy in which magnesium and silver were mixed at a weight ratio of 10: 1 to obtain an organic EL device. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. Table 2 shows the light emission characteristics of this device. The emission luminance here is the luminance at a DC voltage of 5V. The organic EL device of this example was able to obtain high luminance characteristics. Table 2

[0110]

[Table 2]

Example 38 An organic EL device was obtained in the same manner as in Example 7, except that a compound (21) and quinacridone were co-deposited at a weight ratio of 30: 1 to form a light-emitting layer having a thickness of 40 nm. . This element
Emission luminance of 1200 (cd / m ² ) at a DC voltage of 5 V, maximum emission luminance of 33000 (cd / m ² ), and luminous efficiency of 4.2
Green light emission of (lm / W) was obtained.

Example 39: Compound (53) and red light-emitting material DCJTB were added in a weight ratio of 2
An organic EL device was obtained in the same manner as in Example 7, except that a light-emitting layer having a thickness of 40 nm was formed by co-evaporation at a ratio of 5: 1. This device has an emission luminance of 500 (cd / m) at a DC voltage of 5 V.
² ) Red light emission having a maximum light emission luminance of 14000 (cd / m ² ) and a light emission efficiency of 1.2 (lm / W) was obtained.

Example 40 Example 7 was repeated except that Alq3 and the compound (34) were co-deposited at a weight ratio of 25: 1 to form a light-emitting layer having a thickness of 40 nm.
An organic EL device was obtained in the same manner as described above. This device has an emission luminance of 650 (cd / m ² ) at a DC voltage of 5 V, a maximum emission luminance of 17000 (cd / m ² ), and an emission efficiency of 1.9 (lm).
/ W) was obtained.

Example 41 A light-emitting layer having a thickness of 40 nm was formed by co-evaporating a bis (2-methyl-8-hydroxyquinolinato) (phenolate) aluminum complex and a compound (9) at a weight ratio of 25: 1. Except for the above, an organic EL device was obtained in the same manner as in Example 7. This device has an emission luminance of 1200 at a DC voltage of 5 V.
(Cd / m ² ), maximum emission luminance 22000 (cd / m ² )
m ² ) and blue luminescence with a luminous efficiency of 2.2 (lm / W) was obtained.

Example 42 Bis (2-methyl-8-hydroxyquinolinato) (phenolate) gallium complex and compound (100) were co-deposited at a weight ratio of 25: 1 to form a 40 nm-thick light emitting layer. Except for the above, an organic EL device was obtained in the same manner as in Example 7. This device has an emission luminance of 950 (c) at a DC voltage of 5 V.
d / m ² ), blue-green light emission with a maximum light emission luminance of 18000 (cd / m ² ) and a light emission efficiency of 2.0 (lm / W) was obtained.

Examples 43 to 73 The compounds shown in Table 3 were vacuum-deposited on a washed glass plate with an ITO electrode to form a hole injection layer having a thickness of 30 nm. Obtained. Further, a bis (2-methyl-8-hydroxyquinolinato) (phenolate) gallium complex is vacuum-deposited to form an electron injection layer having a thickness of 30 nm, and magnesium and silver are further deposited on the electron injection layer.
An electrode having a thickness of 100 nm was formed from an alloy mixed at a ratio of 0: 1 (weight ratio) to obtain an organic EL device. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. Table 3 shows the light emission characteristics of this device. The emission luminance here is the luminance at a DC voltage of 5V. The organic EL device of this example was able to obtain high luminance characteristics.
Table 3

[0117]

[Table 3]

The device fabricated in this example was 2 (mA / cm
^When continuous light emission was performed in ² ), stable light emission was observed for 3000 hours or more.

Comparative Example 1 Copper phthalocyanine was vacuum-deposited on a washed glass plate with an ITO electrode to obtain a hole injection layer having a thickness of 50 nm. Then, N, N '-(3-methylphenyl) -N, N'-
Diphenyl-1,1′-biphenyl-4,4′-diamine (TPD) was vacuum-deposited to obtain a hole transporting (second hole injecting) layer having a thickness of 20 nm. Further, Alq3 and quinacridone are vacuum-deposited at a weight ratio of 100: 1 to a thickness of 50 nm.
Was obtained. Next, a bis (2-methyl-8-hydroxyquinolinato) (p-cyanophenolate) gallium complex was vacuum-deposited to form an electron injection layer having a thickness of 30 nm, and LiF was deposited thereon to a thickness of 0.1 nm. 5 nm, then Al
To form an electrode having a thickness of 100 nm, thereby obtaining an organic EL device. The light emitting layer and the electron injection layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. This device has a light emission luminance of 230 (cd / m ² ) at a DC voltage of 5 V, a maximum light emission luminance of 11000 (cd / m ² ), and a light emission efficiency of 1.2 (l).
m / W), but almost no light was emitted after about 100 hours.

Comparative Example 2 Alq3 and quinacridone were used as a light emitting layer in a weight ratio of 10
An organic EL device was manufactured in the same manner as in Example 43, except that a light-emitting layer having a thickness of 50 nm was provided by vacuum evaporation at 0: 1. This device has an emission luminance of 130 (c) at a DC voltage of 5 V.
d / m ² ), maximum emission luminance 12000 (cd / m ² ),
Green luminescence with a luminous efficiency of 1.1 (lm / W) was obtained,
The unevenness on the light emitting surface was large. This element was converted to 2 (mA / c
m ² ), when it was continuously illuminated, the deterioration was fast and about 100
After time, the unevenness became more remarkable.

The organic EL device shown in this example has a maximum light emission luminance of 10,000 in a device structure of two layers or more.
Light emission of (cd / m ² ) or more was obtained, and high luminous efficiency was obtained in all cases. When the organic EL device shown in this example was continuously emitted at 2 (mA / cm ² ), a life of 3000 hours or more was observed.

The organic EL device of the present invention achieves improvement of luminous efficiency, luminous luminance and long life, and is used together with a luminescent material, a doping material, a hole injection material, an electron injection material, and a sensitizer. It does not limit the agent, resin, electrode material and the like, and the element manufacturing method.

[0123]

The organic EL device prepared using the material for an organic EL device of the present invention has higher luminous efficiency, higher luminance, and a longer luminous life as compared with the prior art, and is therefore used in flat panel displays such as wall-mounted televisions. Therefore, it can be suitably used as a light source for copiers and printers, a light source for liquid crystal displays and instruments, a display board, a sign lamp, and the like.

Claims (14)

[Claims] 1. An organic electroluminescent device material represented by the following general formula [1]. General formula [1] [Wherein, R ^{1 to} R ¹⁶ , X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted siloxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted Alternatively, it is an unsubstituted aromatic heterocyclic group, a substituted or unsubstituted amino group, or a substituted or unsubstituted styryl group. R ^{1 to} R ¹⁶ , X ¹ and X ² may be bonded to an adjacent carbon atom or a substituent to form a ring. ] 2. A light-emitting material for an organic electroluminescence device represented by the following general formula [1]. General formula [1] [Wherein, R ^{1 to} R ¹⁶ , X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted siloxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted Alternatively, it is an unsubstituted aromatic heterocyclic group, a substituted or unsubstituted amino group, or a substituted or unsubstituted styryl group. R ^{1 to} R ¹⁶ , X ¹ and X ² may be bonded to an adjacent carbon atom or a substituent to form a ring. ] 3. A hole injection material for an organic electroluminescence device represented by the following general formula [1]. General formula [1] [Wherein, R ^{1 to} R ¹⁶ , X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted siloxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted Alternatively, it is an unsubstituted aromatic heterocyclic group, a substituted or unsubstituted amino group, or a substituted or unsubstituted styryl group. R ^{1 to} R ¹⁶ , X ¹ and X ² may be bonded to an adjacent carbon atom or a substituent to form a ring. ] 4. An organic electroluminescent device material represented by the following general formula [2]. General formula [2] [Wherein, R ^{1 to} R ²⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy Group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted siloxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aromatic A heterocyclic group, a substituted or unsubstituted amino group, and a substituted or unsubstituted styryl group. R ^{1 to} R ²⁶ may combine with an adjacent carbon atom or a substituent to form a ring. ] 5. A light-emitting material for an organic electroluminescence device represented by the following general formula [2]. General formula [2] [Wherein, R ^{1 to} R ²⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy Group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted siloxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aromatic A heterocyclic group, a substituted or unsubstituted amino group, and a substituted or unsubstituted styryl group. R ^{1 to} R ²⁶ may combine with an adjacent carbon atom or a substituent to form a ring. ] 6. A hole injection material for an organic electroluminescence device represented by the following general formula [2]. General formula [2] [Wherein, R ^{1 to} R ²⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy Group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted siloxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aromatic A heterocyclic group, a substituted or unsubstituted amino group, and a substituted or unsubstituted styryl group. R ^{1 to} R ²⁶ may combine with an adjacent carbon atom or a substituent to form a ring. ] 7. An organic electroluminescent device material represented by the following general formula [3]. General formula [3] [Wherein, R ^{1 to} R ¹⁶ , R ^{27 to} R ⁴² , X ³ and X ⁴ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted An alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted siloxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted An aryl group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted amino group, and a substituted or unsubstituted styryl group. R ^{1 to} R ¹⁶ , R ²⁷ to
R ⁴² , X ³ and X ⁴ may form a ring by bonding to adjacent carbon atoms or substituents. Y ¹ is a direct bond,
Or a divalent, substituted or unsubstituted alkylene group,
A substituted or unsubstituted aliphatic ring residue, a substituted or unsubstituted arylene group, a substituted or unsubstituted aromatic heterocyclic residue, and a styryl residue, each of which has oxygen, sulfur, and nitrogen. May be. ] 8. A light emitting material for an organic electroluminescence device represented by the following general formula [3]. General formula [3] [Wherein, R ^{1 to} R ¹⁶ , R ^{27 to} R ⁴² , X ³ and X ⁴ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted An alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted siloxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted An aryl group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted amino group, and a substituted or unsubstituted styryl group. R ^{1 to} R ¹⁶ , R ²⁷ to
R ⁴² , X ³ and X ⁴ may form a ring by bonding to adjacent carbon atoms or substituents. Y ¹ is a direct bond,
Or a divalent, substituted or unsubstituted alkylene group,
A substituted or unsubstituted aliphatic ring residue, a substituted or unsubstituted arylene group, a substituted or unsubstituted aromatic heterocyclic residue, and a styryl residue, each of which has oxygen, sulfur, and nitrogen. May be. ] 9. A hole injection material for an organic electroluminescence device represented by the following general formula [3]. General formula [3] [Wherein, R ^{1 to} R ¹⁶ , R ^{27 to} R ⁴² , X ³ and X ⁴ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted An alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted siloxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted An aryl group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted amino group, and a substituted or unsubstituted styryl group. R ^{1 to} R ¹⁶ , R ²⁷ to
R ⁴² , X ³ and X ⁴ may form a ring by bonding to adjacent carbon atoms or substituents. Y ¹ is a direct bond,
Or a divalent, substituted or unsubstituted alkylene group,
A substituted or unsubstituted aliphatic ring residue, a substituted or unsubstituted arylene group, a substituted or unsubstituted aromatic heterocyclic residue, and a styryl residue, each of which has oxygen, sulfur, and nitrogen. May be. ] 10. An organic electroluminescence device comprising at least one light-emitting layer formed between a pair of electrodes comprising an anode and a cathode, wherein at least one layer has at least one layer. An organic electroluminescence device which is a layer containing a device material. 11. An organic electroluminescence device comprising at least one light emitting layer formed between a pair of electrodes comprising an anode and a cathode, wherein the light emitting layer is formed.
20. An organic electroluminescent element, which is a layer containing the light emitting material for an organic electroluminescent element according to any one of the above. 12. An organic electroluminescence device comprising at least one light-emitting layer formed between a pair of electrodes comprising an anode and a cathode, wherein at least one layer has at least one layer. An organic electroluminescence device which is a layer containing a hole injection material for a device. 13. The organic electroluminescent device according to claim 10, further comprising at least one electron injection layer formed between the light emitting layer and the cathode. 14. The organic electroluminescence device according to claim 10, further comprising at least one hole injection layer formed between the light emitting layer and the anode.