JP2002151264A - Organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element with excellent light-emitting characteristics. SOLUTION: At least one layer of organic thin film layers contains a specific compound represented by the formula A, either by itself or as a mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescence device having excellent light emission characteristics.

[0002]

2. Description of the Related Art An organic electroluminescence element (hereinafter sometimes abbreviated as an "organic EL element") is a device that combines the recombination energy of holes injected from an anode with electrons injected from a cathode when an electric field is applied. Is a self-luminous element utilizing the principle that a fluorescent substance emits light.

[0003] Eastman Kodak C.I. W. Ta
ng et al. report on a low voltage driven organic EL device using a stacked device (CWTang, SAVanSlyke, Applied Physics)
Since the publication of Letters, 51, 913, 1987), research on organic EL devices using organic materials as constituent materials has been actively conducted.

Tang et al. Use tris (8-hydroxyquinolinol aluminum) for a light emitting layer and a triphenyldiamine derivative for a hole transport layer. The advantages of the stacked structure include the following: the efficiency of hole injection into the light emitting layer can be increased; the efficiency of exciton generation by blocking electrons injected from the cathode and recombination can be increased; And the like, which can confine the exciton generated therein. As in this example, the organic EL
As the element structure of the element, a two-layer type of a hole transporting (injection) layer and an electron transporting light emitting layer, or a three-layer type of a hole transporting (injection) layer, a light emitting layer, and an electron transporting (injection) layer are often used. Are known. In such an organic EL device having a laminated structure, a device structure and a method of forming each layer are devised in order to increase the recombination efficiency of injected holes and electrons. Various compounds have been developed as materials for organic EL devices.

[0005] As the hole transporting material, starburst molecules such as 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine and N, N'-diphenyl-N, N'-bis ( 3-methylphenyl)-
Triphenylamine derivatives such as [1,1′-biphenyl] -4,4′-diamine and aromatic diamine derivatives are well known (for example, Japanese Patent Application Laid-Open No. Hei 8-20771,
JP-A-8-40995, JP-A-8-40997, JP-A-8-53397, JP-A-8-871
No. 22, etc.). Also, oxadiazole derivatives, triazole derivatives and the like are well known as electron transporting materials.

[0006] Further, as the light emitting material, chelate complexes such as tris (8-quinolinolate) aluminum complex and the like, luminescent materials such as coumarin derivatives, tetraphenylbutadiene derivatives, bisstyrylarylene derivatives, oxadiazole derivatives and the like are known. It has been reported that the emission color can also emit light in the visible region from blue to red.
The realization of a color display element is expected (for example, JP-A-8-239655, JP-A-7-138561, JP-A-3-200289, etc.).

[0007]

A number of other materials for organic electroluminescent devices have been reported in addition to the above. However, certain compounds have too strong interaction between molecules and can be used for film formation. There was a problem that the process was limited. Further, when such a material having a strong intermolecular interaction is used as a light emitting material, the light emission luminance is reduced due to concentration quenching, and there is a problem that sufficient light emission luminance and light emission efficiency cannot be obtained.

Accordingly, the present invention has been made in view of such circumstances, and there is no limitation on a film forming process, and an organic electroluminescence device having sufficient light emission luminance and light emission efficiency and excellent light emission characteristics. The purpose is to provide.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that 2,2-bis (4-
(Cyclohexylidenemethine) phenyl) vinyl group is 2
Compounds having a molecular structure linked by a linking group,
Since the intermolecular interaction is weakened by the effect of steric hindrance caused by the cyclohexylidenemethine group, the limitation on the process at the time of film formation is solved. It has been found that high-luminance light emission can be obtained by improving the charge transporting characteristics provided by the structure. It has also been found that the introduction of the cyclohexylidenemethine group increases the maximum occupied orbital and facilitates charge injection depending on the device configuration, so that the luminous efficiency is greatly improved.

That is, an organic electroluminescent device according to the present invention comprises an organic electroluminescent device having one or more organic thin film layers including a light emitting layer between an anode and a cathode, wherein at least one of the organic thin film layers is as follows: It is characterized by containing the compound represented by the formula [A] alone or as a mixture.

Embedded image (However, in the formula [A], R ^{1 to} R ⁴⁰ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group,
Substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic group A heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxycarbonyl group, R ^{1 to} R ¹⁰ , R ¹¹
~R ^20, R ²¹ ~R ³⁰ and R ³¹ to R ⁴⁰ is 2 of them
Together to form a ring. R ^{41 to} R ⁵⁶ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted styryl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted It represents a substituted aralkyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxycarbonyl group, or a carboxyl group, and R ^{41 to} R ⁵⁶ may form a ring with two of them. X represents a divalent linking group. )

Further, the light emitting layer contains the compound represented by the general formula [A] alone or as a mixture.

Further, the compound represented by the above general formula [A] of the present invention has excellent charge transporting properties, and has excellent light emitting properties when used as an electron transporting material. I found it. Therefore, when an electron transport layer is provided as the organic thin film layer, the electron transport layer may be configured to contain the compound represented by the general formula [A] alone or as a mixture.

Further, the compound represented by the above general formula [A] of the present invention has excellent charge transporting properties, and a device using the compound as a hole transporting material has excellent light emitting properties. I found it. Therefore, when a hole transport layer is provided as the organic thin film layer, the hole transport layer may be configured to contain the compound represented by the general formula [A] alone or as a mixture.

Further, it is desirable that the organic thin film layer adjacent to the cathode contains a metal at the interface with the cathode, and by adopting such a structure, more excellent light emission characteristics can be obtained. Was found.

Further, the present invention has been found to be effective particularly when the light emitting layer is adjacent to the anode, and to obtain more excellent light emitting characteristics. Further, in a device having a structure in which the light-emitting layer is adjacent to the anode using the compound of the present invention, the anode is subjected to ultraviolet irradiation treatment having a wavelength of less than 200 nm or oxygen plasma treatment before the formation of the organic thin film layer. It has been found that excellent emission characteristics can be obtained. Therefore, in an element having a structure in which the light-emitting layer is adjacent to the anode, it is preferable that the anode be constituted by an anode subjected to an ultraviolet irradiation treatment with a wavelength of less than 200 nm or an anode subjected to an oxygen plasma treatment.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The compound of the present invention is a compound having a structure represented by the following general formula [A].

Embedded image

In the general formula [A], R ^{1 to} R ⁴⁰ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group,
Substituted or unsubstituted alkenyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted Represents a substituted aralkyl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted alkoxycarbonyl group, and represents R ^{1 to} R ¹⁰ , R ^{11 to} R ²⁰ , R ^{21 to} R ³⁰ and R ^{31 to} R
⁴⁰ may form a ring with two of them.

R ^{41 to} R ⁵⁶ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted Alkenyl group,
Substituted or unsubstituted styryl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted A substituted aralkyl group, a substituted or unsubstituted aryloxy group,
It represents a substituted or unsubstituted alkoxycarbonyl group or a carboxyl group, and R ^{41 to} R ⁵⁶ may form a ring with two of them.

Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, and n
-Pentyl group, n-hexyl group, n-heptyl group, n-
Octyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group, 1,2-dihydroxyethyl group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-
Butyl, 1,2,3-trihydroxypropyl, chloromethyl, 1-chloroethyl, 2-chloroethyl, 2-chloroisobutyl, 1,2-dichloroethyl, 1,3-dichloroisopropyl, 2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 3-dibromoisopropyl group, 2,3-
Dibromo t-butyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-diiodoisopropyl Group, 2, 3
T-butyl iodide, 1,2,3-triiodopropyl, aminomethyl, 1-aminoethyl, 2-aminoethyl, 2-aminoisobutyl, 1,2-diaminoethyl, 1, 3-diaminoisopropyl group, 2,
3-diamino t-butyl group, 1,2,3-triaminopropyl group, cyanomethyl group, 1-cyanoethyl group, 2-
Cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropyl group,
2,3-dicyano t-butyl group, 1,2,3-tricyanopropyl group, nitromethyl group, 1-nitroethyl group,
2-nitroethyl group, 2-nitroisobutyl group, 1,2
-Dinitroethyl group, 1,3-dinitroisopropyl group, 2,3-dinitro t-butyl group, 1,2,3-trinitropropyl group and the like.

Examples of the substituted or unsubstituted alkenyl group include vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butanedienyl, and
-Methylvinyl group, styryl group, 2,2-diphenylvinyl group, 1,2-diphenylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2-methylallyl group, 1-phenylallyl group, 2- Phenylallyl group, 3
-Phenylallyl group, 3,3-diphenylallyl group,
Examples thereof include a 1,2-dimethylallyl group, a 1-phenyl-1-butenyl group, and a 3-phenyl-1-butenyl group.

Examples of the substituted or unsubstituted cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a 4-methylcyclohexyl group. The substituted or unsubstituted alkoxy group is a group represented by -OY, wherein Y is a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t- Butyl group, n
-Pentyl group, n-hexyl group, n-heptyl group, n-
Octyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group, 1,2-dihydroxyethyl group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-
Butyl, 1,2,3-trihydroxypropyl, chloromethyl, 1-chloroethyl, 2-chloroethyl, 2-chloroisobutyl, 1,2-dichloroethyl, 1,3-dichloroisopropyl, 2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 3-dibromoisopropyl group, 2,3-
Dibromo t-butyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-diiodoisopropyl Group, 2, 3
T-butyl iodide, 1,2,3-triiodopropyl, aminomethyl, 1-aminoethyl, 2-aminoethyl, 2-aminoisobutyl, 1,2-diaminoethyl, 1, 3-diaminoisopropyl group, 2,
3-diamino t-butyl group, 1,2,3-triaminopropyl group, cyanomethyl group, 1-cyanoethyl group, 2-
Cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropyl group,
2,3-dicyano t-butyl group, 1,2,3-tricyanopropyl group, nitromethyl group, 1-nitroethyl group,
2-nitroethyl group, 2-nitroisobutyl group, 1,2
-Dinitroethyl group, 1,3-dinitroisopropyl group, 2,3-dinitro t-butyl group, 1,2,3-trinitropropyl group and the like.

Examples of the substituted or unsubstituted aromatic hydrocarbon group include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, and 1-phenanthryl. , 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9
-Phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-
Pyrenyl group, 4-pyrenyl group, 2-biphenylyl group,
3-biphenylyl group, 4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl Group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl group, p-
(2-phenylpropyl) phenyl group, 3-methyl-2-
Naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4′-methylbiphenylyl group,
4 ''-t-butyl-p-terphenyl-4-yl group and the like.

The substituted or unsubstituted aromatic heterocyclic group includes 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, pyrazinyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5
-Indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3
-Isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5 -Benzofuranyl group, 6-benzofuranyl group, 7
-Benzofuranyl group, 1-isobenzofuranyl group, 3-
Isobenzofuranyl group, 4-isobenzofuranyl group, 5
-Isobenzofuranyl group, 6-isobenzofuranyl group,
7-isobenzofuranyl 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, 3- Isoquinolyl group, 4-isoquinolyl group, 5
-Isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group,
5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, 1-phenanthridinyl group, 2-phenanthridinyl group , 3-
Phenanthridinyl group, 4-phenanthridinyl group, 6
-Phenanthridinyl group, 7-phenanthridinyl group,
8-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1 , 7-phenanthroline-2-yl group, 1,7-phenanthroline-3
-Yl group, 1,7-phenanthrolin-4-yl group,
1,7-phenanthrolin-5-yl group, 1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group, 1,7-phenanthrolin-9-yl group Group, 1,7-phenanthrolin-10-yl group, 1,8
-Phenanthroline-2-yl group, 1,8-phenanthrolin-3-yl group, 1,8-phenanthroline-4-
Yl group, 1,8-phenanthrolin-5-yl group, 1,
8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group, 1,8-phenanthroline-9
-Yl group, 1,8-phenanthrolin-10-yl group,
1,9-phenanthrolin-2-yl group, 1,9-phenanthrolin-3-yl group, 1,9-phenanthrolin-4-yl group, 1,9-phenanthrolin-5-yl Group, 1,9-phenanthrolin-6-yl group, 1,9-
Phenanthroline-7-yl group, 1,9-phenanthroline-8-yl group, 1,9-phenanthroline-10-
An yl group, a 1,10-phenanthrolin-2-yl group,
1,10-phenanthrolin-3-yl group, 1,10-
Phenanthroline-4-yl group, 1,10-phenanthrolin-5-yl group, 2,9-phenanthroline-1-
Yl group, 2,9-phenanthrolin-3-yl group, 2,
9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group, 2,9-phenanthroline-6
-Yl group, 2,9-phenanthrolin-7-yl group,
2,9-phenanthrolin-8-yl group, 2,9-phenanthrolin-10-yl group, 2,8-phenanthrolin-1-yl group, 2,8-phenanthrolin-3-yl Group, 2,8-phenanthrolin-4-yl group, 2,8-
Phenanthrolin-5-yl group, 2,8-phenanthrolin-6-yl group, 2,8-phenanthrolin-7-yl group, 2,8-phenanthrolin-9-yl group, 2, 8
-Phenanthroline-10-yl group, 2,7-phenanthrolin-1-yl group, 2,7-phenanthroline-3
-Yl group, 2,7-phenanthrolin-4-yl group,
2,7-phenanthrolin-5-yl group, 2,7-phenanthrolin-6-yl group, 2,7-phenanthrolin-8-yl group, 2,7-phenanthrolin-9-yl group Group, 2,7-phenanthrolin-10-yl group, 1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group, -Phenothiazinyl group, 1-phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group, 10-phenoxazinyl group, 2-oxazolyl group,
4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group, 2-methylpyrrole- 3-yl group, 2-methylpyrrole-4-yl group, 2-methylpyrrol-5-yl group, 3-methylpyrrol-1-yl group,
3-methylpyrrol-2-yl group, 3-methylpyrrol-4-yl group, 3-methylpyrrol-5-yl group, 2-
t-butylpyrrole-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl Group, 4-methyl-3-indolyl group, 2-t-butyl 1-indolyl group, 4-t-butyl 1-indolyl group, 2-t-butyl 3-indolyl group,
4-t-butyl 3-indolyl group, and the like.

The substituted or unsubstituted aralkyl group includes benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl-t-butyl, α-naphthyl Methyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-
α-naphthylisopropyl group, β-naphthylmethyl group,
1-β-naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, 2-β-naphthylisopropyl group, 1-pyrrolylmethyl group, 2- (1-
Pyrrolyl) ethyl group, p-methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromo Benzyl group, o
-Bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl group, m-amino Benzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p
-Cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, 1-chloro-2-phenylisopropyl group and the like.

The substituted or unsubstituted aryloxy group is represented by the general formula -OZ, wherein Z is a phenyl group, 1
-Naphthyl group, 2-naphthyl group, 1-anthryl group, 2
-Anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group,
4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl Group, 4
-Biphenylyl group, p-terphenyl-4-yl group,
p-terphenyl-3-yl group, p-terphenyl-2
-Yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group,
o-tolyl group, m-tolyl group, p-tolyl group, pt-
Butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-
Naphthyl group, 4-methyl-1-anthryl group, 4'-methylbiphenylyl group, 4 ''-t-butyl-p-terphenyl-4-yl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group , 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl , 3-isoindolyl group, 4-isoindolyl group, 5
-Isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7 -Benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl 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, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-
Isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 1-phenanthridinyl group , 2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl group, 6-phenanthridinyl group, 7-phenanthridinyl group, 8-phenanthridinyl group, 9 -Phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group,
9-acridinyl group, 1,7-phenanthroline-2-
Yl group, 1,7-phenanthrolin-3-yl group, 1,
7-phenanthrolin-4-yl group, 1,7-phenanthrolin-5-yl group, 1,7-phenanthroline-6
-Yl group, 1,7-phenanthrolin-8-yl group,
1,7-phenanthrolin-9-yl group, 1,7-phenanthrolin-10-yl group, 1,8-phenanthrolin-2-yl group, 1,8-phenanthrolin-3-yl Group, 1,8-phenanthrolin-4-yl group, 1,8-
Phenanthrolin-5-yl group, 1,8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group, 1,8-phenanthroline-9-yl group, 1, 8
-Phenanthroline-10-yl group, 1,9-phenanthrolin-2-yl group, 1,9-phenanthroline-3
-Yl group, 1,9-phenanthrolin-4-yl group,
1,9-phenanthrolin-5-yl group, 1,9-phenanthrolin-6-yl group, 1,9-phenanthrolin-7-yl group, 1,9-phenanthrolin-8-yl group Group, 1,9-phenanthrolin-10-yl group, 1,1
A 0-phenanthrolin-2-yl group, a 1,10-phenanthrolin-3-yl group, a 1,10-phenanthrolin-4-yl group, a 1,10-phenanthrolin-5-yl group, 2,9-phenanthrolin-1-yl group, 2,9-
Phenanthrolin-3-yl group, 2,9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group, 2,9-phenanthrolin-6-yl group, 2, 9
Phenanthroline-7-yl group, 2,9-phenanthroline-8-yl group, 2,9-phenanthroline-10
-Yl group, 2,8-phenanthrolin-1-yl group,
2,8-phenanthrolin-3-yl group, 2,8-phenanthrolin-4-yl group, 2,8-phenanthrolin-5-yl group, 2,8-phenanthrolin-6-yl group Group, 2,8-phenanthroline-7-yl group, 2,8-
Phenanthroline-9-yl group, 2,8-phenanthroline-10-yl group, 2,7-phenanthroline-1-
Yl group, 2,7-phenanthrolin-3-yl group, 2,
7-phenanthrolin-4-yl group, 2,7-phenanthrolin-5-yl group, 2,7-phenanthroline-6
-Yl group, 2,7-phenanthrolin-8-yl group,
2,7-phenanthrolin-9-yl group, 2,7-phenanthrolin-10-yl group, 1-phenazinyl group, 2
-Phenazinyl group, 1-phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group, 1-phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group, 2- An oxazolyl group, a 4-oxazolyl group,
5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group, 2-methylpyrrol-3-yl group, 2-methylpyrrole-4-yl group, 2-methylpyrrole-5-yl group,
3-methylpyrrol-1-yl group, 3-methylpyrrol-2-yl group, 3-methylpyrrol-4-yl group, 3-
Methylpyrrol-5-yl group, 2-t-butylpyrrol-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1- Indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl 1
-Indolyl group, 4-t-butyl 1-indolyl group, 2
-T-butyl 3-indolyl group, 4-t-butyl 3-indolyl group and the like.

The substituted or unsubstituted alkoxycarbonyl group is represented by the general formula -COOY, and Y represents a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group. -Butyl group, n
-Pentyl group, n-hexyl group, n-heptyl group, n-
Octyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group, 1,2-dihydroxyethyl group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-
Butyl, 1,2,3-trihydroxypropyl, chloromethyl, 1-chloroethyl, 2-chloroethyl, 2-chloroisobutyl, 1,2-dichloroethyl, 1,3-dichloroisopropyl, 2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 3-dibromoisopropyl group, 2,3-
Dibromo t-butyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-diiodoisopropyl Group, 2, 3
T-butyl iodide, 1,2,3-triiodopropyl, aminomethyl, 1-aminoethyl, 2-aminoethyl, 2-aminoisobutyl, 1,2-diaminoethyl, 1, 3-diaminoisopropyl group, 2,
3-diamino t-butyl group, 1,2,3-triaminopropyl group, cyanomethyl group, 1-cyanoethyl group, 2-
Cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropyl group,
2,3-dicyano t-butyl group, 1,2,3-tricyanopropyl group, nitromethyl group, 1-nitroethyl group,
2-nitroethyl group, 2-nitroisobutyl group, 1,2
-Dinitroethyl group, 1,3-dinitroisopropyl group, 2,3-dinitro t-butyl group, 1,2,3-trinitropropyl group and the like.

Examples of the divalent group forming a ring include:
Tetramethylene group, pentamethylene group, hexamethylene group, diphenylmethane-2,2'-diyl group, diphenylethane-3,3'-diyl group, diphenylpropane-
4,4'-diyl group and the like.

The substituted or unsubstituted amino group is represented by the general formula -NX ³ X ⁴ , wherein X ³ and X ⁴ are each independently a hydrogen atom, the above-mentioned substituted or unsubstituted alkyl group, Alternatively, examples thereof include an unsubstituted alkenyl group, the aforementioned substituted or unsubstituted aralkyl group, the aforementioned substituted or unsubstituted aromatic hydrocarbon group, and the aforementioned substituted or unsubstituted aromatic heterocyclic group.

Examples of the substituted or unsubstituted styryl group include an unsubstituted styryl group, 2,2-diphenylvinyl group, 1,2,2-triphenylvinyl group, a terminal phenyl group and a substituent of vinyl carbon. As a halogen atom, a hydroxyl group, the above-mentioned substituted or unsubstituted amino group, nitro group, cyano group, the above-mentioned substituted or unsubstituted alkyl group, the above-mentioned substituted or unsubstituted alkenyl group, the above-mentioned substituted or unsubstituted A substituted or unsubstituted alkoxy group, the substituted or unsubstituted aromatic hydrocarbon group, the substituted or unsubstituted aromatic heterocyclic group, the substituted or unsubstituted aralkyl group The substituted or unsubstituted aryloxy group, the substituted or unsubstituted alkoxycarbonyl group, Substituted styryl group having such a substituted 2,2-diphenyl vinyl group and substituted 1,2,2-phenylvinyl group and the like.

In the general formula [A], X represents a divalent linking group. Examples of the linking group include a single bond, a divalent group in which one hydrogen atom has been further removed from the above-mentioned substituted or unsubstituted alkenyl group, a divalent group in which two hydrogen atoms have been removed from a substituted or unsubstituted ether, And a divalent group in which one hydrogen atom is further removed from an unsubstituted aromatic hydrocarbon group, and a divalent group in which one hydrogen atom is further removed from the above-mentioned substituted or unsubstituted aromatic heterocyclic group.

Examples thereof include a vinylene group, a divalent group obtained by removing two hydrogen atoms from diphenyl ether, a naphthylene group,
Anthranilylene group, perylenylene group, 1: 2 benzoperylenylene group, 1: 2: 7: 8 dibenzoperylenenylene group,
1: 2: 11: 12 dibenzoperyleneylene group, terylenelenylene group, pentasenylene group, bisanthryleneylene group,
4,4′-biphenylene group, 10,10 ′-(9,9 ′
-Bianthryl) ylene group, 4,4 '-(1,1'-binaphthyl) ylene group, 4,10'-(1,9'-naphthylanthryl) ylene group, general formula -Ar ¹ -Ar ² -Ar ^A divalent group represented by ^3- (wherein, Ar ^{1 to} Ar ³ each represent either a naphthyl group or an anthranyl group); an aromatic hydrocarbon such as phenanthrene, pyrene, biphenyl, or terphenyl; or a condensed polycyclic ring Formula hydrocarbon, carbazole, pyrrole, thiophene, furan, imidazole, pyrazole, isothiazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, furazane, tianthrene, isobenzofuran, phenoxazine, indolizine, indole, isoindole, 1H- Indazole, purine, quinoline, isoquinoline, phthalazine, naphthyridine, quino Sarin, quinazoline, cinnoline, pteridine, carbazole, β- Karubazorin,
Heterocyclic compounds such as phenanthridine, acridine, perimidine, phenanthroline, phenazine, phenothiazine, phenoxazine or condensed heterocyclic compounds, and divalent groups obtained by removing two hydrogen atoms and derivatives thereof, but are not limited thereto. It is not something to be done.

The compounds (1) to (31) are shown below as examples of the compound of the present invention, but the present invention is not limited thereto unless it exceeds the gist.

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Next, the structure of the organic electroluminescence device (organic EL device) of the present invention will be described. The organic EL device of the present invention has a structure in which one or more organic thin film layers including a light emitting layer are sandwiched between an anode and a cathode.

Hereinafter, a configuration example of the organic EL device of the present invention will be described with reference to FIGS. 1 to 4
FIG. 2 is a schematic cross-sectional view of the organic EL element of the present invention, and the same components are denoted by the same reference numerals. 1 to 4, reference numeral 1 denotes a substrate, reference numeral 2 denotes an anode, reference numeral 3 denotes a hole transport layer, reference numeral 4 denotes a light emitting layer, reference numeral 5 denotes an electron transport layer, and reference numeral 6 denotes a cathode. The transport layer, the light emitting layer, and the electron transport layer are composed of organic thin film layers.

As shown in FIGS. 1 to 4, the organic EL device of the present invention comprises an anode 2, a light emitting layer 4 and a cathode 6 on a surface of a substrate 1.
Are sequentially formed as a basic structure. As an organic EL element of the present invention, as shown in FIG. 1, an element structure having only a light emitting layer 4 between an anode 2 and a cathode 6;
As shown in FIG. 3, an element structure including a hole transport layer 3 and an electron transport layer 5 between the anode 2 and the light emitting layer 4 and between the cathode 6 and the light emitting layer 4, respectively, as shown in FIG. An element structure having a hole transport layer 3 between the anode 2 and the light-emitting layer 4 and no electron transport layer between the cathode 6 and the light-emitting layer 4 or, as shown in FIG. An element structure or the like in which the electron transport layer 5 is provided between the light emitting layer 4 and the hole transport layer is not provided between the anode 2 and the light emitting layer 4 can be adopted.

In the organic EL device of the present invention, the compound of the present invention represented by the above general formula [A] is used for the anode 2 and the cathode 6
Are contained alone or as a mixture in at least one of the organic thin film layers (the hole transport layer 3, the light emitting layer 4, and the electron transport layer 5) sandwiched therebetween. The organic thin film layer containing the compound of the present invention may contain the compound of the present invention, and may be composed of only the compound of the present invention. Alternatively, an electron transport material doped with the compound of the present invention may be used.

The hole transporting material used for the hole transporting layer 3 is not particularly limited, and any compound which is generally used as a hole transporting material may be used. For example, the following bis (di (p-tolyl) aminophenyl) -1,1-cyclohexane [41], N, N′-diphenyl-N, N ′
-Bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine [42], N, N'-diphenyl-NN-bis (1-naphthyl) -1,1'-biphenyl ) -4,4'-Diamine [43] and other triphenyldiamines, and starburst-type molecules ([44] to [4]
6] etc.).

[0038]

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The electron transporting material used for the electron transporting layer 5 is not particularly limited, and any compound may be used as long as it is a compound usually used as an electron transporting material. For example, 2
-(4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole [47], bis {2- (4-t-butylphenyl) -1,3,4- Oxadiazole derivatives such as oxadiazole {-m-phenylene [48], triazole derivatives ([49],
[50]), quinolinol-based metal complexes ([51]-
[54] etc.).

[0040]

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The anode 2 of the organic EL device of the present invention has a role of injecting holes into the emission band, and has a role of 4.5 eV.
It is desirable to have the above work function. As the anode material used in the present invention, indium tin oxide alloy (hereinafter referred to as “ITO”), tin oxide (NES)
A), gold, silver, platinum, copper and the like.

As the cathode 6, it is preferable to use a material having a small work function for the purpose of injecting electrons into the electron transport zone or the emission zone. The cathode material is not particularly limited, but specifically, indium, aluminum, magnesium, magnesium-indium alloy, magnesium-
Aluminum alloy, aluminum-lithium alloy, aluminum-scandium-lithium alloy, magnesium-silver alloy and the like can be used.

The method of forming each organic thin film layer of the organic EL device of the present invention is not particularly limited, but a known thin film forming method such as a known vacuum evaporation method and spin coating method can be used. In the organic EL device of the present invention, the organic thin film layer containing the compound represented by the general formula [A] may be formed by a dipping method, a spin coating method, a casting method, a bar coating method, or a roll in which a compound solution dissolved in a solvent is applied. In addition to coating methods such as a coating method, a vacuum deposition method, a molecular beam deposition method (MBE), which cannot be applied because a compound having a strong intermolecular interaction cannot obtain a sufficient film formation rate or cannot form a film at all. Method) or the like. The thickness of each organic thin film layer of the organic EL device of the present invention is not particularly limited. However, in general, if the thickness is too small, defects such as pinholes are likely to occur. Conversely, if the thickness is too large, a high applied voltage is required, resulting in poor efficiency. Therefore, the range of several nm to 1 μm is usually preferable.

It is preferable that the organic thin film layer adjacent to the cathode 6 contains a metal at the interface with the cathode 6.
Examples of the metal to be contained in the organic thin film layer adjacent to the above include, but are not particularly limited to, cesium, lithium, beryllium, magnesium, calcium, and the like, in addition to the metal or alloy used for the cathode 6.

By adopting the above configuration, there is no limitation on the film forming process, sufficient luminous luminance and luminous efficiency can be obtained, and an organic EL device having excellent luminous characteristics can be provided. Further, the present invention relates to the organic E shown in FIGS.
Among the L elements, those having a structure in which the light emitting layer 4 is adjacent to the anode 2 are particularly effective, and more excellent light emitting characteristics can be obtained.

In a device using the compound of the present invention and having a structure in which the light emitting layer 4 is adjacent to the anode 2, the anode 2 before forming the organic thin film layer is subjected to an ultraviolet irradiation treatment having a wavelength of less than 200 nm. It is desirable to keep. As described above, by performing the ultraviolet irradiation treatment on the anode 2 in advance, more excellent light emission characteristics can be obtained. An ultraviolet irradiation lamp for treating the anode 2 has a wavelength of 20 nm.
It emits light having a wavelength of less than 0 nm and has an irradiation intensity of 1 mW / cm.
Any kind of ^two or more may be used. Specific examples include an excimer UV lamp, an excimer laser, and a deuterium lamp, but are not limited thereto.
Further, the UV irradiation treatment of the anode 2 with a wavelength of less than 200 nm can obtain a further effect by performing a wet cleaning method, ozone cleaning, plasma irradiation treatment with oxygen or the like in advance.

[0047]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

(Synthesis Example 1) Synthesis of Compound (3) 4- (2,2-bis (4-bromomethylphenyl) vinyl) phenyl bromide and 2 equivalents of triethyl phosphite were placed in a reaction vessel and stirred. Heated to 140 ° C. for 6 hours. The remaining triethyl phosphite was removed from the obtained mixture by distillation under reduced pressure to obtain a reaction intermediate. This was reacted with 2 equivalents of cyclohexanone and 2.4 equivalents of sodium hydride in a mixed solvent of toluene and dimethyl sulfoxide while gently heating. The obtained reaction mixture was purified according to a conventional method to obtain 4- (2,2-bis (4-cyclohexylidenemethinephenyl) vinyl) phenylbromide.

This was added little by little to dry tetrahydrofuran and 1 equivalent of magnesium ribbon while gently heating, and after the heat generation was stopped, the mixture was refluxed for 5 hours. A small amount of bis (diphenylphosphinopropane) nickel dichloride and one equivalent of 4- (2,2-bis (4-cyclohexylidenemethinephenyl) vinyl) phenyl bromide were added, and the mixture was refluxed for 9 hours while stirring. After completion of the reaction, the resultant was separated and purified according to a conventional method to obtain the desired compound (3).

(Synthesis Example 2) Synthesis of Compound (1) 1,1,4,4, -tetrakis (4-methylphenyl)
Butadiene and 4 equivalents of N-bromosuccinimide were refluxed for 30 hours in cyclohexane with stirring. The resulting reaction solution was diluted with toluene, washed with water and dried. This was purified according to a conventional method to obtain 1,1,4,4, -tetrakis (4-bromomethylphenyl) butadiene. Put this into a reaction vessel with 5 equivalents of triethyl phosphite,
Heat to 140 ° C. with stirring for 9 hours.

The residual triethyl phosphite was removed from the obtained mixture by distillation under reduced pressure to obtain a reaction intermediate. This was reacted with 4 equivalents of cyclohexanone and 5 equivalents of sodium hydride in dimethyl sulfoxide with gentle heating. The obtained reaction mixture was purified according to a conventional method to obtain the desired compound (1).

(Synthesis Example 3) Synthesis of Compound (12) 4- (2,2-bis (4-cyclohexylidenemethinephenyl) vinyl) phenylbromide was gently heated to dry tetrahydrofuran and one equivalent of magnesium ribbon. The mixture was added little by little and the heat generation was stopped, and the mixture was refluxed for 5 hours. A small amount of bis (diphenylphosphinopropane)
Nickel dichloride and 0.5 equivalent of 9,10-dibromoanthracene were added, and the mixture was refluxed for 30 hours with stirring. After completion of the reaction, the desired compound (1) is separated and purified according to a conventional method.
2) was obtained.

In Examples 1 to 29, the compounds (3), (1) and (12) synthesized above were used, and these compounds or a mixed thin film of these compounds and a hole transport material was used. Alternatively, an example in which a light emitting layer of an organic EL element is formed by a mixed thin film of these compounds and an electron transport material will be described.

Example 1 An ITO was formed on a glass substrate by sputtering so that the sheet resistance was 20 Ω / □, and used as an anode. A compound (3) having a thickness of 40 nm was formed thereon as a light emitting layer by a vacuum evaporation method. Next, as a cathode, a magnesium-silver alloy was deposited by vacuum evaporation for 20 minutes.
An organic EL element was formed by forming the layer to a thickness of 0 nm. When a DC voltage of 5 V was applied to this device, light emission of 90 cd / m ² was obtained.

Example 2 An organic EL device was manufactured in the same manner as in Example 1 except that the compound (1) was used as a light emitting material. When a DC voltage of 5 V was applied to this device, light emission of 80 cd / m ² was obtained.

Example 3 As a light emitting material, compound (1)
An organic EL device was manufactured in the same manner as in Example 1, except that 2) was used. When a DC voltage of 5 V was applied to this device, light emission of 100 cd / m ² was obtained.

Example 4 An ITO was formed on a glass substrate by a sputtering method so that the sheet resistance became 20 Ω / □, and used as an anode. On top of this, 40 n was formed by a spin coating method using a chloroform solution of compound (12).
m light emitting layers were formed. Next, as a cathode, a magnesium-silver alloy was formed to a thickness of 200 nm by a vacuum evaporation method to produce an organic EL device. When a DC voltage of 5 V was applied to this device, light emission of 60 cd / m ² was obtained.

Example 5 An ITO was formed on a glass substrate by a sputtering method so that the sheet resistance was 20 Ω / □. N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'- is formed thereon as a hole transport layer.
Diamine [42] was formed to a thickness of 50 nm by a vacuum evaporation method.
Next, as a light emitting layer, the compound (3) was coated with 4
0 nm was formed. Next, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,
3,4-oxadiazole [47]
0 nm was formed. Next, as a cathode, a magnesium-silver alloy is formed to a thickness of 200 nm by a vacuum evaporation method,
An L element was produced. When a DC voltage of 10 V was applied to this device, light emission of 3060 cd / m ² was obtained.

Example 6 An organic EL device was manufactured in the same manner as in Example 5, except that the compound (1) was used as the light emitting material. When a DC voltage of 10 V was applied to this device, light emission of 2570 cd / m ² was obtained.

Example 7 As a light emitting material, compound (1)
An organic EL device was manufactured in the same manner as in Example 5, except that 2) was used. When a DC voltage of 10 V was applied to this device, light emission of 3960 cd / m ² was obtained.

(Example 8) N, N'-
Diphenyl-NN-bis (1-naphthyl) -1,1 '
-Biphenyl) -4,4'-diamine [43] as bis {2- (4-t-butylphenyl)-
1,3,4-oxadiazole {-m-phenylene [4
8], except that [8] was used, to produce an organic EL device. When a DC voltage of 10 V was applied to this device, light emission of 3330 cd / m ² was obtained.

(Example 9) [44] as a hole transport layer
Was performed in the same manner as in Example 5, except that Compound (3) was used as the light emitting layer and [51] was used as the electron transporting layer.
An organic EL device was manufactured. Apply a DC voltage of 10 V to this element.
Upon application, light emission of 3730 cd / m ² was obtained.

(Example 10) [45] as a hole transport layer
Was performed in the same manner as in Example 5, except that Compound (12) was used as the light-emitting layer and [52] was used as the electron transport layer.
An organic EL device was manufactured. Apply a DC voltage of 10 V to this element.
Upon application, light emission of 4260 cd / m ² was obtained.

Example 11 An ITO was formed on a glass substrate by sputtering so that the sheet resistance was 20 Ω / □, and used as an anode. [43] As a hole transport layer, [43] was formed thereon by a vacuum evaporation method to a thickness of 50 nm. A thin film having a thickness of 50 nm was formed thereon as a light emitting layer by co-evaporating [43] and the compound (3) at a weight ratio of 1:10.
Next, 2- (4-biphenylyl) -5 was used as an electron transport layer.
-(4-t-butylphenyl) -1,3,4-oxadiazole [47] was formed to a thickness of 20 nm by a vacuum evaporation method.
Next, as a cathode, a magnesium-silver alloy was formed to a thickness of 200 nm by a vacuum evaporation method to produce an organic EL device. When a DC voltage of 10 V was applied to this element, 32
Emission of 80 cd / m ² was obtained.

Example 12 An organic EL device was prepared in the same manner as in Example 11, except that the compound (12) was used instead of the compound (3). When a DC voltage of 10 V was applied to this device, light emission of 3920 cd / m ² was obtained.

Example 13 An ITO was formed on a glass substrate by sputtering so that the sheet resistance was 20 Ω / □, and used as an anode. N, N'-diphenyl-NN-bis (1-naphthyl) is formed thereon as a light emitting layer.
-1,1'-biphenyl) -4,4'-diamine [4
3] and compound (3) were co-evaporated at a weight ratio of 1:10 to form a thin film having a thickness of 50 nm. Next, [49] was formed as an electron transporting layer to a thickness of 50 nm by a vacuum evaporation method. next,
A 200 nm thick magnesium-silver alloy was formed as a cathode to produce an organic EL device. DC voltage is applied to this element by 1
When 0 V was applied, light emission of 3550 cd / m ² was obtained.

Example 14 An organic EL device was manufactured in the same manner as in Example 13, except that the compound (12) was used instead of the compound (3). When a DC voltage of 10 V was applied to this device, light emission of 3600 cd / m ² was obtained.

Example 15 An ITO was formed on a glass substrate by sputtering so that the sheet resistance was 20 Ω / □, and used as an anode. Compound (12) on top
Solution containing N, N'-diphenyl-NN-bis (1-naphthyl) -1,1'-biphenyl) -4,4'-diamine [43] in a molar ratio of 1:10 A 40 nm light emitting layer was formed by spin coating using Next, [50] is made 50 n by a vacuum evaporation method.
m of an electron transport layer, and a magnesium-silver alloy was formed thereon as a cathode by vacuum evaporation to a thickness of 200 nm.
An organic EL device was manufactured. Apply a DC voltage of 10 V to this element.
Upon application, light emission of 1470 cd / m ² was obtained.

Example 16 An ITO was formed on a glass substrate by sputtering so that the sheet resistance was 20 Ω / □, and used as an anode. N, N′-diphenyl-NN-bis (1-naphthyl) -1,1′-biphenyl) -4,4′-diamine [43] is formed thereon as a hole transport layer by a vacuum evaporation method to a thickness of 50 nm. Formed. Next, as a light emitting layer, a film was formed by vacuum co-evaporation of [51] and the compound (1) at a weight ratio of 20: 1 to a thickness of 50 nm. Next, a 200 nm thick magnesium-silver alloy was formed as a cathode to produce an organic EL device. When a DC voltage of 10 V was applied to this device, light emission of 2030 cd / m ² was obtained.

Example 17 As a light emitting layer, [51] and compound (3) were co-deposited in a vacuum at a weight ratio of 20: 1.
An organic EL device was manufactured in the same manner as in Example 16 except that a 0 nm film was used. DC voltage is applied to this element by 1
When a voltage of 0 V was applied, light emission of 2120 cd / m ² was obtained.

Example 18 An organic EL device was produced in the same manner as in Example 17, except that the compound (12) was used instead of the compound (3). When a DC voltage of 10 V was applied to this device, light emission of 2150 cd / m ² was obtained.

Example 19 An organic EL device was manufactured in the same manner as in Example 5, except that Compound (3) was used as the hole transport layer and [53] was used as the light emitting layer. When a DC voltage of 10 V was applied to this element, 1120 cd
/ M ² .

Example 20 An organic EL device was manufactured in the same manner as in Example 5, except that the compound (12) was used as the hole transporting material. DC voltage is applied to this element by 1
When 0 V was applied, light emission of 970 cd / m ² was obtained.

Example 21 N, N 'was used as the hole transport layer.
-Diphenyl-NN-bis (1-naphthyl) -1,
1′-biphenyl) -4,4′-diamine [43]
[53] was used as the light emitting layer, and the compound (1) was used as the electron transporting layer.
An organic EL device was manufactured in the same manner as in Example 5, except that 2) was used. When a DC voltage of 10 V was applied to this device, light emission of 800 cd / m ² was obtained.

Example 22 The same operation as in Example 21 was performed except that Compound (3) was used as the electron transporting layer.
An organic EL device was manufactured. Apply a DC voltage of 10 V to this element.
Upon application, light emission of 920 cd / m ² was obtained.

Example 23 The same operation as in Example 21 was carried out except that Compound (1) was used as the electron transporting layer.
An organic EL device was manufactured. Apply a DC voltage of 10 V to this element.
Upon application, light emission of 870 cd / m ² was obtained.

Example 24 An ITO was formed on a glass substrate by sputtering so that the sheet resistance became 20 Ω / □, and used as an anode. The ITO substrate was cleaned using an alkaline cleaning solution and then using isopropyl alcohol. The washed ITO substrate was set in a Xe ₂ ultraviolet irradiation device, and the substrate was irradiated with 172 nm ultraviolet light for 3 minutes.
On this substrate, as a hole transport layer, N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1 '
-Biphenyl] -4,4'-diamine [42] was formed to a thickness of 50 nm by a vacuum evaporation method.

Next, the compound (3) was formed to a thickness of 40 nm by a vacuum evaporation method as a light emitting layer. Next, 20-nm 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole [47] was formed as an electron transporting layer by a vacuum evaporation method. Next, a magnesium-silver alloy was formed as a cathode to a thickness of 200 nm by a vacuum evaporation method to produce an organic EL device. DC voltage is applied to this element by 1
When 0 V was applied, light emission of 3620 cd / m ² was obtained.

Example 25 An ITO was formed on a glass substrate by a sputtering method so that the sheet resistance was 20 Ω / □, and used as an anode. The ITO substrate was cleaned using an alkaline cleaning solution and then using isopropyl alcohol. The washed ITO substrate was set in a Xe ₂ ultraviolet irradiation device, and the substrate was irradiated with 172 nm ultraviolet light for 3 minutes.

Further, N, N′-diphenyl-NN-bis (1-naphthyl) -1,1′-biphenyl) -4,4′-diamine [43] and compound (3) were formed thereon as a light emitting layer. A thin film produced by co-evaporation at a weight ratio of 1:10 is 50 nm
Formed. Next, [49] was formed as an electron transporting layer to a thickness of 50 nm by a vacuum evaporation method. Next, a 200 nm thick magnesium-silver alloy was formed as a cathode to produce an organic EL device. When a DC voltage of 10 V was applied to this element,
Light emission of 3870 cd / m ² was obtained.

Example 26 An ITO was formed on a glass substrate by sputtering so that the sheet resistance became 20 Ω / □, and used as an anode. The ITO substrate was cleaned using an alkaline cleaning solution and then using isopropyl alcohol. The washed ITO substrate was set in a Xe ₂ ultraviolet irradiation device, and the substrate was irradiated with 172 nm ultraviolet light for 3 minutes.

A compound (3) was formed thereon as a light emitting layer to a thickness of 50 nm by a vacuum evaporation method. Next, [49] was formed as an electron transporting layer to a thickness of 50 nm by a vacuum evaporation method. Next, a 200 nm-thick magnesium-silver alloy was formed as a cathode to produce an organic EL device. DC voltage is applied to this element by 1
When 0 V was applied, light emission of 3730 cd / m ² was obtained.

Example 27 An ITO was formed on a glass substrate by sputtering so that the sheet resistance became 20 Ω / □, and used as an anode. [43] As a hole transport layer, [43] was formed thereon by a vacuum evaporation method to a thickness of 50 nm. A thin film having a thickness of 50 nm was formed thereon as a light emitting layer by co-evaporating [43] and the compound (3) at a weight ratio of 1:10.
Next, 2- (4-biphenylyl) -5 was used as an electron transport layer.
-(4-t-butylphenyl) -1,3,4-oxadiazole [47] is formed to a thickness of 20 nm by a vacuum evaporation method, and then [47] and cesium are co-evaporated at a weight ratio of 10: 1 to form a film of 5 nm.
nm. Next, a magnesium-silver alloy was formed to a thickness of 200 nm by a vacuum evaporation method as a cathode to form an organic EL.
An element was manufactured. When a DC voltage of 10 V was applied to this device, light emission of 3890 cd / m ² was obtained.

Example 28 An ITO was formed on a glass substrate by sputtering so that the sheet resistance was 20 Ω / □. N, N′-diphenyl-NN-bis (1-naphthyl) -1,1′-biphenyl) -4,4′-diamine [43] is formed thereon as a hole transport layer by a vacuum evaporation method to a thickness of 50 nm. Formed. Next, as the light emitting layer, a film in which the compound (3) was vacuum-deposited was formed to a thickness of 50 nm. Thereafter, (3) and cesium were formed to a thickness of 5 nm by co-evaporation at a weight ratio of 10: 1. Next, a magnesium-silver alloy was formed as a cathode to a thickness of 200 nm by a vacuum evaporation method, to produce an organic EL device. When a DC voltage of 10 V was applied to this device, light emission of 3530 cd / m ² was obtained.

(Example 29) An ITO was formed on a glass substrate by a sputtering method so that the sheet resistance became 20 Ω / □, thereby forming an anode. The ITO substrate was cleaned using an alkaline cleaning solution and then using isopropyl alcohol. The washed ITO substrate was set in a Xe ₂ ultraviolet irradiation device, and the substrate was irradiated with 172 nm ultraviolet light for 3 minutes.

On top of that, compound (3) was applied as a light emitting layer under vacuum.
50 nm was formed by a vapor deposition method. Then (3) and cesium
Was formed to a thickness of 5 nm by co-evaporation at a weight ratio of 10: 1. Next, the cathode
Magnesium-silver alloy by vacuum evaporation
An organic EL device was fabricated by forming the film to a thickness of 0 nm. This element
When a DC voltage of 10 V was applied, 2230 cd / m ^Two
Was obtained.

As described above, as shown in Examples 1 to 29, it was found that the present invention can provide a high-luminance organic EL device.

[0088]

As described above, by using the compound of the present invention in at least one of the organic thin film layers constituting the organic electroluminescence device, the organic electroluminescence having excellent emission characteristics can be obtained without any limitation on the film formation process. An element can be provided.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an organic electroluminescence device according to the present invention.

FIG. 2 is a cross-sectional view of the organic electroluminescence device of the present invention.

FIG. 3 is a cross-sectional view of the organic electroluminescence device of the present invention.

FIG. 4 is a cross-sectional view of the organic electroluminescence device of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole transport layer 4 Light emitting layer 5 Electron transport layer 6 Cathode

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) H05B 33/26 H05B 33/26 Z (72) Inventor Hiroshi Tada 5-7-1 Shiba, Minato-ku, Tokyo NEC Corporation (72) Inventor Atsushi Oda 5-7-1 Shiba, Minato-ku, Tokyo NEC Corporation F-term (reference) 3K007 AB02 AB03 AB18 CA01 CB01 DA01 DB03 EB00

Claims (8)

[Claims] 1. An organic electroluminescent device having one or more organic thin film layers including a light emitting layer between an anode and a cathode, wherein at least one of the organic thin film layers is a compound represented by the following general formula [A]. Or a mixture thereof. Embedded image (However, in the formula [A], R ^{1 to} R ⁴⁰ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group,
Substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic group A heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxycarbonyl group, R ^{1 to} R ¹⁰ , R ¹¹
~R ^20, R ²¹ ~R ³⁰ and R ³¹ to R ⁴⁰ is 2 of them
Together to form a ring. R ^{41 to} R ⁵⁶ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted styryl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted It represents a substituted aralkyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxycarbonyl group, or a carboxyl group, and R ^{41 to} R ⁵⁶ may form a ring with two of them. X represents a divalent linking group. ) 2. The organic electroluminescent device according to claim 1, wherein the light emitting layer contains the compound represented by the general formula [A] alone or as a mixture. 3. The method according to claim 1, wherein the organic thin film layer has an electron transporting layer, and the electron transporting layer contains the compound represented by the general formula [A] alone or as a mixture. 3. The organic electroluminescent device according to 1.). 4. The method according to claim 1, wherein the organic thin film layer has a hole transport layer, and the hole transport layer contains the compound represented by the general formula [A] alone or as a mixture. Item 2. An organic electroluminescent device according to item 1. 5. The method according to claim 1, wherein the light emitting layer is adjacent to the anode.
13. The organic electroluminescent device according to item 6. 6. The organic electroluminescence device according to claim 5, wherein the anode is an anode that has been subjected to an ultraviolet irradiation treatment with a wavelength of less than 200 nm. 7. The organic electroluminescence device according to claim 5, wherein the anode is an anode subjected to an oxygen plasma treatment. 8. The organic thin film layer adjacent to the cathode,
The organic electroluminescence device according to any one of claims 1 to 7, wherein a metal is contained in an interface with the cathode.