JP2002124385A - Organic electroluminescence device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescence device having a long life and high luminous efficiency and a novel compound realizing the same. SOLUTION: An organic electroluminescence element having at least a single layer or a plurality of organic thin film layers having a light emitting layer between a pair of electrodes, wherein at least one of the organic thin film layers is a polycyclic alicyclic carbonized material. An organic electroluminescence device comprising a compound having a light-emitting molecular skeleton substituted with at least one hydrogen group, and a novel compound for realizing the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound and an organic electroluminescence device, and more particularly to an organic electroluminescence device having a long life and high luminous efficiency and a novel compound for realizing the same.

[0002]

2. Description of the Related Art Organic electroluminescent devices (organic EL devices) using organic substances are used as light sources such as flat light-emitting bodies for wall-mounted televisions and backlights for displays, and are being actively developed. Organic EL elements
This is a self-luminous element utilizing the principle that a fluorescent substance emits light by the recombination energy of holes injected from an anode and electrons injected from a cathode by applying an electric field. Eastman Kodak's CWTang et al. Report on low-voltage driven organic EL devices using stacked devices (CWTang, SAVans
1yke, Applied Physics Letters (App1ied Physi
cs Letters), vol. 51, p. 913, 1987), research on organic EL devices using organic materials as constituent materials has been actively conducted. Tang et al., Tris (8
-Hydroxyquinolinol aluminum) in the light-emitting layer,
A triphenyldiamine derivative is used for the hole transport layer. The advantages of the stacked structure include: increasing the efficiency of injecting holes into the light emitting layer; increasing the efficiency of generating excitons generated by recombination by blocking electrons injected from the cathode; And confinement of excitons. Examples of the laminated structure of the organic EL element include a two-layer type of a hole transport (injection) layer and an electron transport / emission layer, and a three-layer type of a hole transport (injection) layer, a light-emitting layer, and an electron transport (injection) layer. well known. In order to increase the recombination efficiency of injected holes and electrons in these stacked structure devices, device structures and formation methods have been studied. For example, JP-A-8-239
655, JP-A-7-138561 and JP-A-3-200289 disclose chelating complexes such as tris (8-quinolinolato) aluminum complex, coumarin derivatives, and tetraphenylbutadiene as light emitting materials for organic EL devices. It has been reported that light emission in the visible region from blue to red can be obtained by using a light-emitting material such as a derivative, a bisstyrylarylene derivative, or an oxadiazole derivative, and the realization of a color display element is expected. Japanese Patent No. 3008897 and Japanese Patent Application Laid-Open No. 8-12600 disclose devices using a bisanthracene derivative as a hole transporting material or a light emitting material. A bisanthracene derivative is used as a blue light-emitting material, but its luminous efficiency and life have not reached the levels that can be used for practical use.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide an organic electroluminescent device having a long lifetime and high luminous efficiency and a novel compound for realizing the same. It is the purpose.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to develop an organic EL device having the above-mentioned preferable properties, and as a result, it has been found that at least one is substituted with a polycyclic alicyclic hydrocarbon group. The inventors have found that high-luminance light emission is achieved by including a compound having a light-emitting molecular skeleton in an organic thin film layer of an organic EL device, and completed the present invention. In addition, the compound has a high carrier-transport property, and when used as a hole-transport material or an electron-transport material of a device, the device has high luminous efficiency and a long lifetime. Particularly, the compound has an arylamine compound or an aromatic compound having a styryl group. It has been found that, when the compounds are mixed, a device having higher luminous efficiency and longer life is obtained.

That is, the present invention relates to an organic EL device having an organic thin-film layer comprising at least a single layer or a plurality of layers having at least a light-emitting layer between a pair of electrodes, wherein at least one of the organic thin-film layers is a polycyclic thin film. It is an object of the present invention to provide an organic EL device comprising a compound having a light-emitting molecular skeleton substituted with at least one alicyclic hydrocarbon group.
The present invention also provides a novel compound represented by the following general formula (1) and a novel quinacridone-based dye compound represented by the following general formula (2).

[0006]

Embedded image (Wherein, R _{1 to} R ₁₈ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, or a substituted or unsubstituted carbon atom having 1 to 30 carbon atoms. Alkyl group, substituted or unsubstituted alkenyl group having 3 to 40 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 40 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substitution Or an unsubstituted aromatic hydrocarbon group having 5 to 40 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 2 to 40 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, Substituted or unsubstituted 6 to 3 carbon atoms
0 represents an aryloxy group, a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms or a carboxyl group. However, at least one of R _{1 to} R ₁₈ is a polycyclic alicyclic hydrocarbon group. )

[0007]

Embedded image (Wherein R ₁ ′ to R ₈ ′ each independently represent a hydrogen atom, a halogen atom, a straight-chain, branched or cyclic substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a straight-chain, branched or A cyclic substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, X _{1 to} X ₂ each independently represent a hydrogen atom, A branched or cyclic substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms. Where R
₁ at least one of 'to R _8' and X ₁ to X ₂ is a polycyclic alicyclic hydrocarbon group. )

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The organic EL device of the present invention is an organic electroluminescence device having at least a single layer or a plurality of organic thin film layers having a light emitting layer between a pair of electrodes, wherein at least one of the organic thin film layers is a polycyclic thin film. It contains a compound having a light-emitting molecular skeleton substituted with at least one alicyclic hydrocarbon group. Here, the polycyclic alicyclic hydrocarbon group is a group having a plurality of aliphatic hydrocarbon rings in the alicyclic hydrocarbon group, and examples thereof include bicyclo and tricyclo rings. (1) adamantane and its derivatives, (2) norbornane and its derivatives, (3) perhydroanthracene and its derivatives, (4) perhydronaphthalene and its derivatives,
(5) Tricyclo [5.2.1.0 ^2,6 ] decane and its derivatives, (6) Spiro [4,4] nonane and its derivatives, (7) Spiro [4,5] decane and its derivatives, etc. No. Among them, (2) norbornane and its derivatives, (3) perhydroanthracene and its derivatives, (4) perhydronaphthalene and its derivatives are preferable, and a group represented by the following general formula (A) is particularly preferable.

[0009]

Embedded image (In the formula (A), R ₁ ″ to R ₁₅ ″ each independently represent a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, an ester group, a cyano group, an amide group, an imide group, a silyl group or The hydrocarbon groups substituted by these, a and b are an integer of 0 to 2, and c represents 1 or 2.)

Further, more preferred examples of the polycyclic alicyclic hydrocarbon group are shown below, and these groups may be further substituted.

Embedded image

The luminescent molecular skeleton is preferably a polycyclic aromatic ring or a derivative thereof, for example, biphenyl, fluorene, anthracene, bisanthracene, naphthacene, pentacene, perylene, pyrene, chrysene, or the like.
Examples include picene, rubicene, rubrene, fluoranthene, acenaphthofluoranthene, and derivatives thereof. Preferred derivatives include anthracene, bisanthracene, naphthacene, pentacene, perylene, pyrene, chrysene, picene, rubicene, rubrene, and fluoranthene. And amino-substituted, alkyl-substituted, aryl-substituted and alkenyl-substituted acenaphthofluoranthene, with amino-substituted being particularly preferred. These substitutions are 2
It may be a to 4-substituted product.

Further, the luminescent molecular skeleton includes a fluorescent dye,
For example, stilbene, polyphenyl, perylene, coumarin, cyanine, merocyanine, thioxanthene, xanthene, pyran, quinacridone, oxazine, phenoxazone, cyanine, merocyanine or acridone-based dyes can be mentioned.

In the present invention, a novel compound represented by the following general formula (1) can be used as the compound having a luminescent molecular skeleton substituted by at least one of the polycyclic alicyclic hydrocarbon groups.

Embedded image In the formula, R _{1 to} R ₁₈ 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 having 1 to 30 carbon atoms. A substituted or unsubstituted alkenyl group having 3 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 40 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, Unsubstituted aromatic hydrocarbon group having 5 to 40 carbon atoms, substituted or unsubstituted aromatic heterocyclic group having 2 to 40 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substitution Or 6 to 3 unsubstituted carbon atoms
0 represents an aryloxy group, a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms or a carboxyl group. However, at least one of R _{1 to} R ₁₈ is a polycyclic alicyclic hydrocarbon group.

Hereinafter, specific examples of R _{1 to} R ₁₈ in the general formula (1) will be described. Halogen atoms include fluorine, chlorine, bromine and iodine. As the substituted or unsubstituted amino group, when the amino group is -NY ₁ Y ₂ , Y ₁ and Y ₂ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group. Group, s-butyl group, isobutyl group, 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 group, 1,2,3-trihydroxypropyl group,
Chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl group, 1,2-dichloroethyl group, 1,3-dichloroisopropyl group, 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, 1,3-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, two, three
-Diiodo-t-butyl group, 1,2,3-trichodopropyl group, aminomethyl group, 1-aminoethyl group, 2-
Aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group, 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, 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, 4
-Styrylphenyl 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 ″ -tert-butyl-p-terphenyl-4-yl group, 2-pyrrolyl group, 3 -Pyrrolyl, pyrazinyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl Group, 1
-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-isobenzozofuranyl 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-inknolyl 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-phenanthrolin-2-yl group, 1,7-phenanthrolin-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, 1,7-phenanthrolin-10-yl group, 1,
8-phenanthrolin-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-phenanthroline-7-yl group, 1,8-phenanthrolin-9-yl group, 1,8-phenanthrolin-10-yl group 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
-Yl group, 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, 1 -Phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl group, 4-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-methylpyrrol-4-yl group, 2-methylpyrrol-5-yl group, 3-methylpyrrol-1-yl group, 3-
Methylpyrrole-2-yl group, 3-methylpyrrole-4
-Yl group, 3-methylpyrrole-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-
And a butyl 3-indolyl group.

As the substituted or unsubstituted alkyl group, methyl, ethyl, propyl, isopropyl, n-
Butyl, s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl Group, 2-hydroxydiisobutyl group, 1,2-dihydroxyethyl group, 1,
3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl group, 2-dichloroethyl group, 1,3-dichloroisopropyl group, 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, 1,3-dibromoisopropyl group,
2,3-dipromo-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-diiodo-t-butyl group, 1,2,3
-Triiodopropyl group, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group, 2,3-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-troisobutyl group, 1,2-dinitroethyl group, 1,3-dinitroisopropyl group, 2,3-dinitro-t-butyl group, 1,2,3-tri And a nitropropyl group.

The substituted or unsubstituted alkenyl group includes
Vinyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 1-
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, 1,2
-Dimethylallyl group, 1-phenyl-1-butenyl group,
A 3-phenyl-1-butenyl group and the like. 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.

As the substituted or unsubstituted alkoxy group, when the alkoxy group is —NY, Y is a methyl group,
Ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, 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, 3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl group, 2-dichloroethyl group, 1,3-dichloroisopropyl group, 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, 1,3-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-diiodo Isopropyl group, 2,
3-diiodo-t-butyl group, 1,2,3-triiodopropyl group, aminomethyl group, 1-aminoethyl group, 2
-Aminoethyl group, 2-aminoisobutyl group, 1,2-
Diaminoethyl group, 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,
A 2,3-trinitropropyl group and the like.

The substituted or unsubstituted aromatic hydrocarbon group includes a phenyl group, a 1-naphthyl group, a 2-naphthyl group,
-Anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-fetentryl 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, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, 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, 6-benzofuranyl, 7-benzofuranyl, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzo Furanyl 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
An -yl group, a 1,7-phentensulolin-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, 9
-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, 2,9-phenanthrolin-10-yl group, 1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group, 10 -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-methylpyrrole-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 A 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 group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, α-naphthylmethyl 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-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxy Benzyl group, p-aminobenzyl group, m-aminobenzyl 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. No.

As the substituted or unsubstituted aryloxy group, when the aryloxy group is -OZ, Z is phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, -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, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m
-Terphenyl-3-yl group, m-terphenyl-2-
Yl, o-tolyl, m-tolyl, p-tolyl,
pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4′-methyl Hyphenylyl group, 4 ″ -t-butyl-p-terphenyl-4-yl group, 2-pyrrolyl group, 3
-Pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 3-
Pyridinyl group, 4-pyridinyl group, 2-indolyl group,
3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-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, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzo Furanyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzozofuranyl 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-inknolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2 A -quinoxalinyl group, a 5-quinoxalinyl group, a 6-quinoxalinyl group, a 1-carbazolyl group, a 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, 1
0-phenanthridinyl group, 1-acridinyl group, 2-
Acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1,7-phenanthrolin-2-yl group, 1,7-phenanthrolin-3-yl group, 1,7-phenanth Lorin-4-yl group, 1,7-
Phenanthrolin-5-yl group, 1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group, 1,7-phenanthroline-9-yl group, 1, 7
-Phenanthroline-10-yl group, 1,8-phenanthrolin-2-yl group, 1,8-phenanthroline-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-phenanthrolin-9-yl group Group, 1,8-phenanthrolin-10-yl group, 1,9
-Phenanthroline-2-yl group, 1,9-phenanthroline-3-yl group, 1,9-phenanthroline-4-
An yl group, a 1,9-phenanthrolin-5-yl group,
9-phenanthrolin-6-yl group, 1,9-phenanthrolin-7-yl group, 1,9-phenanthroline-8
-Yl group, 1,9-phenanthrolin-10-yl group,
1,10-phenanthrolin-2-yl group, 1,10-
Phenanthrolin-3-yl group, 1,10-phenanthrolin-4-yl group, 1,10-phenanthroline-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 Group, 2,9-phenanthrolin-7-yl group, 2,9-
Phenanthroline-8-yl group, 2,9-phenanthroline-10-yl group, 2,8-phenanthroline-1-
Yl group, 2,8-phenanthrolin-3-yl group, 2,
8-phenanthrolin-4-yl group, 2,8-phenanthrolin-5-yl group, 2,8-phenanthroline-6
An -yl group, a 2,8-phenanthroline-7-yl group,
2,8-phenanthrolin-9-yl group, 2,8-phenanthrolin-10-yl group, 2,7-phenanthrolin-1-yl group, 2,7-phenanthrolin-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, 2, 7
-Phenanthroline-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-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxazolyl group,
5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group, 2-methylpyrrol-3-yl group, 2-methylpyrrol-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-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-
And an indolyl group.

As the substituted or unsubstituted alkoxycarbonyl group, when the alkoxycarbonyl group is -COOA, A is a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group. ,
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 group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group ,
2-chloroethyl group, 2-chloroisobutyl group, 1,2
-Dichloroethyl group, 1,3-dichloroisopropyl group, 2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromo Isobutyl group,
1,2-dibromoethyl group, 1,3-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-diiodo-t-butyl Group, 1,
2,3-triiodopropyl group, aminomethyl group, 1-
Aminoethyl group, 2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group, 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-tricia Propyl, nitromethyl, 1-nitroethyl, 2-nitroethyl, 2-nitroisobutyl, 1,2-dinitroethyl, 1,3
-Dinitroisopropyl group, 2,3-dinitro-t-butyl group, 1,2,3-trinitropropyl group and the like.

In the present invention, a novel quinacridone compound represented by the following general formula (2) can be used as the compound having a luminescent molecular skeleton substituted with at least one of the polycyclic alicyclic hydrocarbon groups. .

Embedded image In the formula, R ₁ ′ to R ₈ ′ each independently represent a hydrogen atom, a halogen atom, a straight-chain, branched or cyclic substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a straight-chain, branched or cyclic Represents a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and X _{1 to} X ₂ each independently represent a hydrogen atom, a straight chain, Represents a branched or cyclic substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and a substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms. . Where R ₁ '
At least one of to R ₈ 'and X ₁ to X ₂ is a polycyclic alicyclic hydrocarbon group.

Hereinafter, specific examples of R ₁ ′ to R ₈ ′ in the general formula (2) will be described. Halogen atoms include fluorine, chlorine, bromine and iodine. The linear, branched or cyclic substituted or unsubstituted alkyl group is the same as the example of the alkyl group in the general formula (1). Linear,
The branched or cyclic substituted or unsubstituted alkoxy group is the same as the example of the alkoxy group in the general formula (1).

Examples of the substituted or unsubstituted aryl group include a phenyl group, a naphthyl group, an anthryl group,
Examples include a phenanthryl group, a naphthacenyl group and a pyrenyl group. Examples of the substituent of the aryl group include a halogen source, a hydroxyl group, the above-mentioned substituted or unsubstituted amino group, a nitro group, a cyano group, the above-mentioned substituted or unsubstituted alkyl group, the above-mentioned substituted or An unsubstituted alkenyl group, the substituted or unsubstituted cycloalkyl group, the substituted or unsubstituted alkoxy group, the substituted or unsubstituted aromatic hydrocarbon group, the substituted or unsubstituted aromatic heterocyclic group A ring group, the above-mentioned substituted or unsubstituted aralkyl group, the above-mentioned substituted or unsubstituted aryloxy group, the above-mentioned substituted or unsubstituted alkoxydicarbonyl group, and a carboxyl group.

Hereinafter, specific examples of X _{1 to} X ₂ in the general formula (2) will be described. Examples of the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group include the aforementioned R ₁ ′
The same as the examples of the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group of R ₈ ′. The substituted or unsubstituted aralkyl group is the same as the example of the aralkyl group in the general formula (1).

In the organic EL device of the present invention, it is preferable that the organic thin film layer has an electron transporting layer and / or a hole transporting layer containing a compound of the general formula (1) or (2). In the organic EL device of the present invention, it is preferable that the light emitting layer contains a compound having a light emitting molecular skeleton substituted with at least one of the polycyclic alicyclic hydrocarbon group and an arylamine compound. As the arylamine compound, a compound represented by the following general formula (3) or (4) is preferable.

Embedded image (Wherein, Ar ₅ is an aromatic group having 6 to 40 carbon atoms, A
r ₆ and Ar ₇ are each independently a hydrogen atom or an aromatic group having 6 to 40 carbon atoms, and Ar ₅ , Ar ₆ and Ar ₇ may be substituted. m is an integer of 1 to 6. )

Embedded image(Wherein, Ar₈And Ar₁₄Is a group having 6 to 40 carbon atoms.
Aromatic group, Ar₉~ Ar ₁₃Is independently a hydrogen atom
Or an aromatic group having 6 to 40 carbon atoms, and Ar₈~ A
r₁₄May be substituted. p, q, r and s are
It is 0 or 1, respectively. )

In the general formulas (3) and (4), examples of the aromatic group having 6 to 40 carbon atoms include a phenyl group, a naphthyl group, an anthranyl group, a phenanthryl group, a pyrenyl group, a coronyl group, and a biphenyl group. , Terphenyl group, pyrrolyl group, furanyl group, thiophenyl group,
Benzothiophenyl group, oxadiasolyl group, diphenylanthranyl group, indolyl group, carpazolyl group, pyridyl group, benzoquinolyl group, fluoranthenyl group, aryl group such as acenaphthofluoranthenyl group, phenylene group, naphthylene group, andranylene group, Phenanthrylene group, pyrenylene group, colonylene group, biphenylene group, terphenylene group, pyrrolylene group, furanylene group, thiophenylene group, benzotheophenylene group, oxadiazolylene group, diphenylanthranylene group, indolylene group, galvazolylene group, viridylene group, And an arylene group such as a benzoquinolylene group, a fluoranthenylene group, and an acenaphthofluoranthenylene group. This aromatic group may be substituted by a substituent. As the substituent, an alkyl group having 1 to 6 carbon atoms (ethyl group, methyl group, i-propyl group, n-propyl group, s-
Butyl group, t-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group, etc.), having 1 carbon atom
To 6 alkoxy groups (ethoxy, methoxy, i-propoxy, n-propoxy, s-butoxy, t-
Butoxy group, pentoxy group, hexyloxy group, cyclopentoxy group, cyclohexyloxy group, etc.), aryl group having 6 to 40 carbon atoms, amino group substituted with aryl group having 6 to 40 carbon atoms, carbon atom number Examples thereof include an ester group having an aryl group of 6 to 40, an ester group having an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, and a halogen atom.

In the organic EL device according to the present invention, the light emitting layer may be
It is preferable to contain a compound having a luminescent molecular skeleton substituted with at least one of the polycyclic alicyclic hydrocarbon groups and an aromatic compound having a styryl group. As the aromatic compound having a styryl group, a compound represented by the following general formula (5), (6) or (7) is preferable.

Embedded image(Wherein, Ar₁'Is an aromatic group having 6 to 40 carbon atoms, A
r_Two'~ Ar_Four'Independently represent a hydrogen atom or a carbon atom
An aromatic group having 6 to 40 children, and Ar₁'~ Ar _Four'Out of
At least one is an aromatic group. n 'is an integer of 1 to 6
It is. )

Embedded image (Wherein, Ar ₅ ′ is an aromatic group having 6 to 40 carbon atoms, A
r ₆ ′ and Ar ₇ ′ are each independently a hydrogen atom or an aromatic group having 6 to 40 carbon atoms, and at least one of Ar ₅ ′ to Ar ₇ ′ is substituted with a styryl group. m '
Is an integer of 1 to 6. )

Embedded image (Wherein, Ar ₈ ′ and Ar ₁₄ ′ are an aromatic group having 6 to 40 carbon atoms, and Ar ₉ ′ to Ar ₁₃ ′ are each independently a hydrogen atom or an aromatic group having 6 to 40 carbon atoms. And Ar ₈ ′
At least one of Ar ₁₄ ′ to Ar ₁₄ ′ may be substituted with a styryl group. p ′, q ′, r ′ and s ′ are each 0 or 1. )

In the general formulas (5) to (7), the aromatic group having 6 to 40 carbon atoms includes the general formula (3)
And (4) the same as the aromatic group having 6 to 40 carbon atoms. More preferred aromatic compounds having a styryl group include the following compounds.

Embedded image

Hereinafter, typical examples (A1) to (A15) of the novel compounds represented by the general formula (1) and typical examples (B1) to (B1) to (B1) of the novel compounds represented by the general formula (2) will be described. B1
0), but the present invention is not limited to these representative examples.

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

The structure of the organic EL device of the present invention is a structure in which one or more organic layers are laminated between electrodes, for example, (anode / light-emitting layer / negative electrode), (anode / hole transport layer / light-emitting layer). Layer / electron transport layer / cathode), (anode / hole transport layer / emission layer /
And a structure such as (cathode) or (anode / light-emitting layer / electron transport layer / cathode). The compound in the present invention may be used in any of the above organic layers, and may be doped into other hole transporting materials, light emitting materials, and electron transporting materials. The electron transporting material used in the electron transporting layer is not particularly limited, and may be any compound that is generally used as an electron transporting agent. For example, 2- (4-biphenylyl) -5- (4
-T-butylphenyl) -1,3,4-oxadiazole, bis {2- (4-t-butylphenyl) -1,3,3
Examples thereof include oxadiazole derivatives such as 4-oxadiazole-m-phenylene, triazole derivatives, and quinolinol-based metal complexes. Further, it is preferable to use an insulator or a semiconductor as the inorganic compound constituting the electron transport layer. If the electron transport layer is made of an insulator or a semiconductor, current leakage can be effectively prevented, and electron injection properties can be improved. As such an insulator, it is preferable to use at least one metal compound selected from an alkali metal chalcogenide, an alkaline earth metal chalcogenide, an alkali metal halide and an alkaline earth metal halide. Injectability can be further improved.

Examples of alkali metal chalcogenides include:
For example, Li_TwoO, LiO, Na_TwoS, Na_TwoSe or Na
O is preferred, and as an alkaline earth metal chalcogenide
Is, for example, CaO, BaO, SrO, BeO, BaS or
Is preferably CaSe, and is a halide of an alkali metal.
For example, LiF, NaF, KF, LiCl or K
Cl or the like is preferable, and a halide of an alkaline earth metal
For example, CaF _Two, BaF_Two, SrF_Two, MgF
_TwoOr BeF_TwoHalides other than fluorides are preferred
No. Further, as a semiconductor constituting the electron transport layer, B
a, Ca, Sr, Yb, Al, Ga, In, Li, N
a, Cd, Mg, Si, Ta, Sb and Zn
Oxides containing at least one element
Or a combination of two or more
Inorganic compounds. Also forms an electron transport layer
Is a microcrystalline or amorphous insulating thin film.
Preferably. The electron transport layer is made of these insulating thin films
If configured, a more uniform thin film will be formed
In addition, pixel defects such as dark spots can be reduced.
Wear. In addition, as such an inorganic compound,
Potassium metal chalcogenide, alkaline earth metal chalcogena
Id, alkali metal halides and alkaline earths
And metal halides.

The work function of the electron injection layer is 2.9 e.
V or less may be contained. Here, the reducing dopant is a substance capable of reducing the electron transporting compound. Therefore, various substances having a certain reducing property are used, for example, alkali metals, alkaline earth metals, rare earth metals, oxides and halides of alkali metals, and oxides of alkaline earth metals. And at least one selected from halides, oxides and halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals can be suitably used. Among these, a preferable reducing dopant is Na (work function:
2.36 eV), K (work function: 2.28 eV), Rb
(Work function: 2.16 eV) and Cs (work function: 1.
95 eV), at least one alkali metal selected from the group consisting of Ca (work function: 2.9 eV), Sr (work function: 2.0 to 2.5 eV) and Ba (work function: 2. eV).
52 eV), at least one kind of alkaline earth metal selected from the group consisting of K, Rb and Cs, and more preferably at least one kind of alkali metal selected from the group consisting of K, Rb and Cs.
Rb or Cs, most preferably Cs. These metals have particularly high reducing ability, and the addition of a relatively small amount to the electron injection region can improve the emission luminance and extend the life of the organic EL element. Further, as the reducing dopant, it is preferable to combine these alkali metals,
In particular, Cs and Na, Cs and K, Cs and Rb or Cs and Na
And K are preferred. By including Cs, the reduction ability can be efficiently exhibited, and the addition to the electron injection region can improve the emission luminance and extend the life of the organic EL element.

The anode of the organic EL element plays a role of injecting holes into the hole transport layer or the light emitting layer.
It is effective to have a work function of 4.5 eV or more. Examples of such an anode material include indium tin oxide alloy (ITO), tin oxide (NESA), gold, silver, platinum and steel. As the cathode, a material having a small work function is preferable for the purpose of injecting electrons into the electron transport layer or the light emitting layer. The cathode material is not particularly limited, but specifically, indium, aluminum, magnesium, magnesium-indium alloy, magnesium-aluminum alloy, aluminum-lithium alloy, aluminum-
A scandium-lithium alloy, a magnesium-silver alloy or the like can be used.

The method of forming each layer of the organic EL device of the present invention is not particularly limited. Examples of the method of forming the organic thin film layer include an organic thin film method, a vacuum evaporation method, a molecular beam evaporation method (MBE method), and a method of dissolving in a solvent. It can be formed by a known method such as a solution dipping method, a spin coating method, a casting method, a bar coating method, and a roll coating method.
The thickness of each organic 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, and if the thickness is too large, a high applied voltage is required, resulting in poor efficiency. Therefore, it is usually preferable to be several nm to 1 μm.

The organic EL device of the present invention can be used, for example, as a flat light-emitting body such as a flat panel display of a wall-mounted television, a copier, a printer, a light source such as a backlight or an instrument of a liquid crystal display, a display board, a sign lamp and the like. .

[0043]

The present invention will be described below in more detail with reference to Synthesis Examples and Examples. Synthesis Example 1 ((A1): Ad = 1-adamantane) A reaction route of the intermediate a and the intermediate b is shown below.

Embedded image Synthesis of Intermediate a To a solution of 100 g (0.515 mol) of anthrone, 1 liter of acetic acid and 400 ml of hydrochloric acid, 200 g of tin was added little by little at 80 ° C. After the addition was completed, the mixture was stirred overnight at the same temperature. After the reaction, isopropyl ether was added,
Tin was removed by decantation. The obtained crude crystals are
HF, filtered and concentrated under reduced pressure to give a white solid a89
g (98% yield).

Synthesis of Intermediate b A slurry of 56 g (0.158 mol) of intermediate a and 3 liters of carbon tetrachloride was added with 56 g (0.35 mol) of bromine /
A solution of 60 ml of carbon tetrachloride was added dropwise at 0 ° C. After the addition, the mixture was stirred at room temperature overnight. After the reaction,
The reaction solution was poured into 1 liter of ice water, the organic layer was separated, and concentrated under reduced pressure. The obtained crude crystals were recrystallized from THF / methanol to obtain 51 g of the desired intermediate b (63% yield).

Synthesis of Compound ((A1): Ad = 1-adamantane) A compound ((A1): Ad = 1-adamantane) was synthesized as follows.

Embedded image 1.6 g (66 mmol) of magnesium were placed in a 500 ml three-necked flask equipped with a condenser under a stream of argon.
A small piece of iodine, 50 ml of THF was added. After stirring at room temperature for 30 minutes, 6.5 g of 1-bromoadamantane
(30 mmol) / 100 ml of THF solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour to prepare a Grignard reagent. Under a stream of argon, with cooling tube 50
In a 0 ml three-necked flask, 3.1 g of intermediate b
(10 mmol), 0.4 g (5 mol%) of dichlorobis (triphenylphosphine) palladium, 1 ml of diisobutylaluminum hydride / toluene solution (1 M, 1 mmol) and 100 ml of THF were added. After the above Grignard reagent was added dropwise at room temperature, the mixture was heated and stirred overnight. After the completion of the reaction, the reaction solution was cooled with ice water, and the precipitated crystals were collected by filtration and washed with 50 ml of methanol and 50 ml of acetone in this order to obtain 1.2 g of a yellow powder. It has NMR, IR and FD
The compound ((A1): Ad = 1-adamantane) was identified by measurement of -MS (field desorption mass spectrum) (yield: 20%).

Synthesis Example 2 ((A1): Ad = 2-adamantane) Synthesis of Compound ((A1): Ad = 2-adamantane) Compound ((A1): Ad = 2-adamantane) was synthesized as follows. did.

Embedded image 0.8 g (33 mmol) of magnesium was placed in a 500 ml three-necked flask equipped with a condenser under a stream of argon.
A small piece of iodine, 50 ml of THF was added. After stirring at room temperature for 30 minutes, 6.5 g of 2-bromoadamantane
(30 mmol) / 100 ml of THF solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour to prepare a Grignard reagent. Under a stream of argon, with cooling tube 50
In a 0 ml three-necked flask, 3.1 g of intermediate b
(10 mmol), 0.4 g (5 mol%) of dichlorobis (triphenylphosphine) palladium, 1 ml of diisobutylaluminum hydride / toluene solution (1 M, 1 mmol) and 100 ml of THF were added. After the above Grignard reagent was added dropwise at room temperature, the mixture was heated and stirred overnight. After completion of the reaction, the reaction solution was cooled with ice water, and the precipitated crystals were collected by filtration, washed with 50 ml of methanol and 50 ml of acetone in this order to obtain 4.1 g of a yellow powder. It has NMR, IR and FD
The compound ((A1): Ad = 2-adamantane) was identified by the measurement of -MS (yield 50%).

Synthesis Example 3 Synthesis of Compound (A6) Compound (A6) was synthesized as follows.

Embedded image 0.8 g (33 mmol) of magnesium was placed in a 500 ml three-necked flask equipped with a condenser under a stream of argon.
A small piece of iodine, 50 ml of THF was added. After stirring at room temperature for 30 minutes, 5.3 g of exo-2-norbornene
(30 mmol) / 100 ml of THF solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour to prepare a Grignard reagent. Under a stream of argon, with cooling tube 50
In a 0 ml three-necked flask, 3.1 g of intermediate b
(10 mmol), 0.4 g (5 mol%) of dichlorobis (triphenylphosphine) palladium, 1 ml of diisobutylaluminum hydride / toluene solution (1 M, 1 mmol) and 100 ml of THF were added. After the above Grignard reagent was added dropwise at room temperature, the mixture was heated and stirred overnight. After completion of the reaction, the reaction solution was cooled with ice water, and the precipitated crystals were collected by filtration, washed with 50 ml of methanol and 50 ml of acetone in this order to obtain 4.2 g of a yellow powder. It has NMR, IR and FD
The powder was identified as Compound (A6) by -MS measurement (yield: 60%).

Synthesis Example 4 Synthesis of Compound (B2: Ad = 1-adamantane) A compound (B2: Ad = 1-adamantane) was synthesized as follows.

Embedded image Under an argon stream, 3.12 g of quinacridone (10 mmo
1) and 50 ml of dry THF were slowly added with 2 g (67 mmol) of 80% sodium hydride. Subsequently, 6.5 g of 1-bromoadamantane (30 mmol
After l) was added slowly, the reaction solution was heated to reflux overnight.
After completion of the reaction, methanol was added, and the precipitated crystals were separated by filtration to obtain 3.2 g of a yellow powder. These are NMR, I
By measurement of R and FD-MS, compound (B2: Ad =
1-adamantane) (55% yield).

Example 1 A glass substrate (manufactured by Geomatic) having a thickness of 25 mm × 75 mm × 1.1 mm with an ITO transparent electrode was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes and then to UV ozone cleaning for 30 minutes. . Attach the glass substrate with the transparent electrode line after cleaning to the substrate holder of the vacuum evaporation device,
First, a 60 nm-thick N, N'-bis (N, N'-diphenyl-4-aminophenyl)-is formed on the surface on the side where the transparent electrode line is formed so as to cover the transparent electrode.
N, N'-diphenyl-4,4'-diamino-1,1 '
-A biphenyl film (hereinafter, TPD232 film) was formed.
This TPD232 film functions as a hole injection layer. Next, a 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl film (hereinafter, referred to as an NPD film) having a thickness of 20 nm was formed on the TPD232 film. This NPD film functions as a hole transport layer. Further, the compound (A1) was deposited to a thickness of 40 nm on the NPD film to form a film. This compound (A1) film functions as a light emitting layer. On this film, a 20 nm-thick tris (8-quinolinol) aluminum film (hereinafter, Alq film) was formed. This Alq film is
Functions as an electron injection layer. Thereafter, Li as a reducing dopant (Li source: manufactured by Saes Getter Co.) and Alq were binary deposited to form an Alq: Li film as an electron injection layer (cathode). Metallic Al was vapor-deposited on this Alq: Li film to form a metal cathode to produce an organic EL device. The device emitted blue-violet light with a luminance of 150 cd / m ² , a maximum luminance of 43000 cd / m ² and a luminous efficiency of 2.0 cd / A at a DC voltage of 6 V. Also, the initial luminance is 500 cd / m
^When a life test was performed with constant current driving as No. ² , the half life was as long as 1100 hours.

Examples 2 to 8 Organic EL devices were prepared in the same manner as in Example 1 except that the compound shown in Table 1 was used instead of the compound (A1) as the light-emitting layer. Luminance, luminous efficiency and half-life were measured by voltage, and the luminescent color was observed. Table 1 shows the results. Comparative Example 1 In Example 1, the following compound (B) described in JP-A-3070600 was used in place of the compound (A1) as the light-emitting layer.
A)

Embedded image In the same manner, an organic EL device was prepared, and the luminous brightness, luminous efficiency, and half-life were measured at the DC voltage shown in Table 1, and the luminescent color was observed. Table 1 shows the results.

[0051]

[Table 1]

As shown in Table 1, the organic EL device using the novel compound of the present invention has a specific substituent.
Long life and high luminous efficiency.

Example 9 In Example 9, the above compound (A1) and the following aromatic compound (11) having a styryl group were used as the light emitting layer.

Embedded image Was formed in the same manner except that the film was formed by vapor deposition at a molar ratio of 2: 1. This element has a DC voltage of 6V
Emission luminance of 320 cd / m ² , maximum emission luminance of 83,000
It emitted blue-green light with cd / m ² and luminous efficiency of 6.0 cd / A. When a life test was performed by driving at a constant current with an initial luminance of 500 cd / m ² , the half life was 4100.
It was long time.

Example 10 The same procedures as in Example 1 were carried out except that the compound (A1) and the aromatic compound (8) having a styryl group were vapor-deposited at a molar ratio of 5: 1 to form a light-emitting layer. Then, an organic EL device was produced. This device has a light emission luminance of 240 cd / m ² and a maximum light emission luminance of 51000 cd / m at a DC voltage of 6 V.
^2. Blue light emission with a luminous efficiency of 4.0 cd / A. When a life test was performed by driving at a constant current with an initial luminance of 500 cd / m ² , the half life was as long as 2100 hours.

Example 11 In Example 1, the light-emitting layer was formed by using the above compound (A1) and the following arylamine compound (12).

Embedded image Was formed in the same manner as above except that a film was formed by vapor deposition at a molar ratio of 40: 2. This element has a DC voltage of 6V
Emission luminance 140 cd / m ² , maximum emission luminance 61000
It emitted blue light with cd / m ² and luminous efficiency of 5.0 cd / A. When a life test was performed by driving at a constant current with an initial luminance of 500 cd / m ² , the half life was as long as 1800 hours.

Example 12 In Example 1, the light-emitting layer was made of Alq and the compound (B).
Same as 1) except that 1) was deposited at a molar ratio of 40: 2 to form a film.
Thus, an organic EL device was produced. This element is a DC voltage
Emission luminance 250 cd / m at 6V^Two, Maximum emission brightness 120
00 cd / m^TwoGreen light emission with luminous efficiency of 12.5 cd / A
Met. Also, the initial luminance is 1500 cd / m^TwoAs
When the life test was performed with constant current drive, the half life was 5
It was as long as 600 hours. Comparative Example 2 The same procedure as in Example 12 was repeated except that the compound (B1) was replaced with the above compound.
In general formula (2), R ₁'~ R₈'And X₁~ X_TwoAll of
Similarly, except that a compound that is a hydrogen atom was used,
An organic EL device was manufactured. This element emits at DC voltage 6V
Light luminance 120 cd / m^Two, Maximum light emission luminance 50000cd
/ M^TwoAnd green light emission with a luminous efficiency of 6.2 cd / A.
Also, the initial luminance is 1500 cd / m^TwoConstant current drive as
And a life test, the half life was 530 hours.
It was short. Comparative Example 3 The same procedure as in Example 12 was repeated, except that the compound (B1) was replaced with the above compound.
In general formula (2), R ₁'~ R₈'Is a hydrogen atom and X₁~ X_Two
Is the same except that a compound in which is a methyl group is used.
Thus, an organic EL device was manufactured. This element has a DC voltage of 6V
And emission luminance of 120 cd / m^Two, Maximum light emission brightness 50,000
cd / m^TwoGreen light with a luminous efficiency of 8.2 cd / A.
Was. Also, the initial luminance is 1500 cd / m^TwoAs constant current
When the life test was performed by driving, the half life was 3500.
Time was shorter than in Example 12.

[0057]

As described in detail above, the organic electroluminescence device using the novel compound of the present invention has a long life and is practically high in luminous efficiency. For this reason, the organic electroluminescence element of the present invention is useful as a light source such as a flat light emitter of a wall-mounted television or a backlight of a display.

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Claims (12)

[Claims] 1. An organic electroluminescence device having an organic thin film layer comprising at least a single layer or a plurality of organic layers having at least a light emitting layer between a pair of electrodes, wherein at least one of the organic thin film layers is a polycyclic alicyclic compound. An organic electroluminescence device comprising a compound having a light-emitting molecular skeleton substituted with at least one hydrocarbon group. 2. The organic electroluminescent device according to claim 1, wherein the light emitting molecular skeleton is a polycyclic aromatic ring or a derivative thereof. 3. The light-emitting molecular skeleton is biphenyl, fluorene, anthracene, bisanthracene, naphthacene, pentacene, perylene, pyrene, chrysene, picene, rubicene, rubrene, fluoranthene, acenaphthofluoranthene, or a derivative thereof. The organic electroluminescence device according to claim 2, wherein 4. The method according to claim 1, wherein the luminescent molecular skeleton is anthracene,
Bisanthracene, naphthacene, pentacene, perylene, pyrene, chrysene, picene, rubicene, rubrene,
3. The organic electroluminescent device according to claim 2, wherein the organic electroluminescent device is an amino-substituted product of fluoranthene or acenaphthofluoranthene. 5. The luminescent molecular skeleton is quinacridone,
The organic electroluminescent device according to claim 1, wherein the organic electroluminescent device is oxazine, phenoxazone, cyanine, merocyanine, acridone, or thioxanthene. 6. The compound having a light-emitting molecular skeleton substituted with at least one polycyclic alicyclic hydrocarbon group is a novel compound represented by the following general formula (1). 4. The organic electroluminescent device according to any one of 1 to 3, Embedded image (Wherein, R _{1 to} R ₁₈ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, or a substituted or unsubstituted carbon atom having 1 to 30 carbon atoms. Alkyl group, substituted or unsubstituted alkenyl group having 3 to 40 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 40 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substitution Or an unsubstituted aromatic hydrocarbon group having 5 to 40 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 2 to 40 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, Substituted or unsubstituted 6 to 3 carbon atoms
0 represents an aryloxy group, a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms or a carboxyl group. However, at least one of R _{1 to} R ₁₈ is a polycyclic alicyclic hydrocarbon group. ) 7. The compound having a luminescent molecular skeleton substituted with at least one polycyclic alicyclic hydrocarbon group is a novel quinacridone dye compound represented by the following general formula (2). The organic electroluminescence device according to claim 1, wherein Embedded image (Wherein R ₁ ′ to R ₈ ′ each independently represent a hydrogen atom, a halogen atom, a straight-chain, branched or cyclic substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a straight-chain, branched or A cyclic substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, X _{1 to} X ₂ each independently represent a hydrogen atom, A branched or cyclic substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms. Where R
₁ at least one of 'to R _8' and X ₁ to X ₂ is a polycyclic alicyclic hydrocarbon group. ) 8. An organic electroluminescence device having an organic thin film layer comprising at least a single layer or a plurality of layers having at least a light emitting layer between a pair of electrodes, wherein the organic thin film layer is according to claim 6 or 7. An organic electroluminescence device comprising an electron transport layer and / or a hole transport layer containing a compound. 9. An organic electroluminescence device having at least a single layer or a plurality of organic thin film layers having a light emitting layer between a pair of electrodes, wherein the light emitting layer is in any one of claims 1 to 7. An organic electroluminescence device comprising a compound of the formula (1) and an arylamine compound. 10. An organic electroluminescence device having at least a single layer or a plurality of organic thin film layers having a light emitting layer between a pair of electrodes, wherein the light emitting layer is in any one of claims 1 to 7. And an aromatic compound having a styryl group. 11. A novel compound represented by the following general formula (1). Embedded image (Wherein, R _{1 to} R ₁₈ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, or a substituted or unsubstituted carbon atom having 1 to 30 carbon atoms. Alkyl group, substituted or unsubstituted alkenyl group having 3 to 40 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 40 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substitution Or an unsubstituted aromatic hydrocarbon group having 5 to 40 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 2 to 40 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, Substituted or unsubstituted 6 to 3 carbon atoms
0 represents an aryloxy group, a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms or a carboxyl group. However, at least one of R _{1 to} R ₁₈ is a polycyclic alicyclic hydrocarbon group. ) 12. A novel quinacridone dye compound represented by the following general formula (2). Embedded image (Wherein R ₁ ′ to R ₈ ′ each independently represent a hydrogen atom, a halogen atom, a straight-chain, branched or cyclic substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a straight-chain, branched or A cyclic substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, X _{1 to} X ₂ each independently represent a hydrogen atom, A branched or cyclic substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms. Where R
₁ at least one of 'to R _8' and X ₁ to X ₂ is a polycyclic alicyclic hydrocarbon group. )