JP2002343569A - Organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element that is excellent in luminous efficiency and has a high luminance. SOLUTION: The electroluminescent element comprises between a pair of electrodes at least one layer of a layer which contains at least one kind of a 2,9-diazadibenzo[cd,lm]perylene derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an organic electroluminescent device.

[0002]

2. Description of the Related Art Conventionally, an inorganic electroluminescent element has been used as a panel-type light source such as a backlight. However, driving the light emitting element requires a high AC voltage.

[0003] Recently, an organic electroluminescent device (organic electroluminescent device: organic EL device) using an organic material as a light emitting material has been developed [Appl. Phys. Lett.,
51 , 913 (1987)]. An organic electroluminescent element has a structure in which a thin film containing a fluorescent organic compound is sandwiched between an anode and a cathode, and electrons and holes are injected into the thin film.
An exciton is generated by recombination, and light is emitted using light emitted when the exciton is deactivated. The organic electroluminescent element can emit light at a low DC voltage of about several volts to several tens of volts, and various colors (for example, red, blue, and green) can be obtained by selecting the type of the fluorescent organic compound. ) Is possible. Organic electroluminescent devices having such characteristics are expected to be applied to various light emitting devices, display devices, and the like. However, in general, the emission luminance is low and is not practically sufficient.

As a method for improving the light emission luminance, for example, an organic electroluminescent device using tris (8-quinolinolato) aluminum as a host compound, a coumarin derivative, and a pyran derivative as a guest compound (dopant) as a light emitting layer has been proposed. J. Appl. Phys., 65 , 361
0 (1989)]. Further, as a light emitting layer, for example, a screw (2
An organic electroluminescent device using -methyl-8-quinolinolate) (4-phenylphenolate) aluminum as a host compound and an acridone derivative (for example, N-methyl-2-methoxyacridone) as a guest compound has been proposed ( JP-A-8-67873). However, it is difficult to say that these light emitting elements also have sufficient light emission luminance. At present, an organic electroluminescent device that emits light with higher luminance is desired.

The organic electroluminescent device of the present invention comprises a 2,9-
Diazadibenzo [cd, lm] perylene derivatives include 5,
6,12,13-Tetraphenoxy-2,9-diazadibenzo [cd, lm] perylene is known [for example, Ange
w. Chem. Int. Ed., 39 , 1243 (2000)]. However, the applicability of the compound to an organic electroluminescent device is not known.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electroluminescent device which is excellent in luminous efficiency and emits light with high luminance.

[0007]

The present inventors have conducted intensive studies on an organic electroluminescent device and a compound used in the device. It has been found that when used as, it is excellent in luminous efficiency and emits light with high luminance, and has completed the present invention.

That is, the present invention provides an organic electroluminescent device comprising at least one layer containing at least one kind of a 2,9-diazadibenzo [cd, lm] perylene derivative sandwiched between a pair of electrodes. 2,9-diazadibenzo [cd, lm], an organic electroluminescent device according to the above, wherein the layer containing at least one kind of diazadibenzo [cd, lm] perylenetetrabenzo [a, cd, j, lm] perylene derivative is a light emitting layer. The organic electroluminescent device, wherein the layer containing at least one kind of perylene derivative further contains a luminescent organometallic complex, and the layer containing at least one kind of 2,9-diazadibenzo [cd, lm] perylene derivative, Organic electroluminescent device containing or described triarylamine derivative,

[0009] The organic electroluminescent device according to any one of [1] to [3], further comprising a hole injection / transport layer between the pair of electrodes. The organic electroluminescent device according to any one of the above, further comprising an electron injection / transport layer between the pair of electrodes, wherein the 2,9-diazadibenzo [cd, lm] perylene derivative is represented by the general formula (1-A). The present invention relates to the organic electroluminescent device according to any one of the above-mentioned items, which is a compound.

[0010]

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(Wherein, X 1 to X 8 each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, or a substituted Or an unsubstituted aryloxy group.)

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The organic electroluminescent device of the present invention comprises at least one layer containing at least one kind of 2,9-diazadibenzo [cd, lm] perylene derivative sandwiched between a pair of electrodes.

The 2,9-diazadibenzo [cd,
lm] A perylene derivative (hereinafter abbreviated as compound A according to the present invention) represents a compound having a skeleton represented by the general formula (1). And may have various substituents, and is preferably a compound represented by the general formula (1-A).

[0015]

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[0016]

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(Wherein X 1 to X 8 each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, Or an unsubstituted aryloxy group.) In the compound represented by the general formula (1-A), X 1 to X
8 independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group .

In the present invention, the aryl group refers to a carbocyclic aromatic group such as a phenyl group and a naphthyl group, and a heterocyclic aromatic group such as a furyl group, a thienyl group and a pyridyl group. , Preferably a carbocyclic aromatic group.

In the compound represented by the general formula (1-A), more preferably, X1 to X8 each represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, A straight-chain, branched or cyclic alkoxy group having from 24 to 24 carbon atoms; a substituted or unsubstituted aryl group having 4 to 24 carbon atoms;

Specific examples of X 1 to X 8 in the general formula (1-A) include a hydrogen atom, for example, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, for example, a methyl group, an ethyl group, an n-propyl group. Group, isopropyl group, n-
Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl Group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group,
1-methylhexyl group, cyclohexylmethyl group, n-
Octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group,
n-nonyl group, 2,2-dimethylheptyl group, 2,6-
Dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-
Hexylheptyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group,
n-octadecyl group, n-eicosyl group, n-tricosyl group, n-tetracosyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-tert-
Butylcyclohexyl group, cycloheptyl group, a linear, branched or cyclic alkyl group such as cyclooctyl group,

For example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, n-pentyloxy, neopentyloxy, cyclopentyloxy,
n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2
-Ethylhexyloxy group, n-nonyloxy group, n-
Decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group Linear chains such as n-octadecyloxy group, n-eicosyloxy group, n-tricosyloxy group, n-tetracosyloxy group;
A branched or cyclic alkoxy group,

For example, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3
-Ethylphenyl group, 4-ethylphenyl group, 4-n-
Propylphenyl group, 4-isopropylphenyl group, 4
-N-butylphenyl group, 4-isobutylphenyl group,
4-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group, 4-cyclohexylphenyl group, 4-n-heptyl Phenyl group,
4-n-octylphenyl group, 4-n-nonylphenyl group, 4-n-decylphenyl group, 4-n-undecylphenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-n-hexadecylphenyl group, 4-n-octadecylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-
Dimethylphenyl group, 2,6-dimethylphenyl group,
3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3
5,6-tetramethylphenyl group, 5-indanyl group,
1,2,3,4-tetrahydro-5-naphthyl group, 1,
2,3,4-tetrahydro-6-naphthyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 4-n-propoxyphenyl group A 4-isopropoxyphenyl group, a 4-n-butoxyphenyl group,
4-isobutoxyphenyl group, 4-n-pentyloxyphenyl group, 4-n-hexyloxyphenyl group, 4-
Cyclohexyloxyphenyl group, 4-n-heptyloxyphenyl group, 4-n-octyloxyphenyl group,
4-n-nonyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-undecyloxyphenyl group,
4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-n-hexadecyloxyphenyl group, 4-n-octadecyloxyphenyl group,

2,3-dimethoxyphenyl group, 2,4-
Dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 2-methoxy-4-methylphenyl group, 2-methoxy -5-methylphenyl group, 3-methoxy-4-methylphenyl group, 2-methyl-4-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 2-fluoro Phenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group,
4-bromophenyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2,4-difluorophenyl group, 2,4-dichlorophenyl group,
3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-methyl-4-chlorophenyl group, 2-chloro-4-methylphenyl group, 3-chloro-4-methylphenyl group, 2-chloro-4-methoxy Phenyl group, 3-methoxy-4-fluorophenyl group, 3-methoxy-4-
Chlorophenyl group, 3-fluoro-4-methoxyphenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4′-methylphenyl) phenyl group, 4- (4′-methoxy) Phenyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 4-methyl-1-naphthyl group, 4-ethoxy-1-naphthyl group,
6-n-butyl-2-naphthyl group, 6-methoxy-2-
Substituted or unsubstituted aryl groups such as naphthyl group, 7-ethoxy-2-naphthyl group, 2-furyl group, 2-thienyl group, 3-thienyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group ,

For example, phenyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, 3-ethylphenyloxy,
4-ethylphenyloxy group, 4-n-propylphenyloxy group, 4-isopropylphenyloxy group, 4-
n-butylphenyloxy group, 4-isobutylphenyloxy group, 4-tert-butylphenyloxy group, 4-n
-Pentylphenyloxy group, 4-isopentylphenyloxy group, 4-tert-pentylphenyloxy group, 4
-N-hexylphenyloxy group, 4-cyclohexylphenyloxy group, 4-n-heptylphenyloxy group, 4-n-octylphenyloxy group, 4-n-nonylphenyloxy group, 4-n-decylphenyloxy group A 4-n-undecylphenyloxy group, a 4-n-dodecylphenyloxy group, a 4-n-tetradecylphenyloxy group, a 4-n-hexadecylphenyloxy group,
4-n-octadecylphenyloxy group, 2,3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethyl Phenyloxy group, 3,5-dimethylphenyloxy group, 3,4
5-trimethylphenyloxy group, 2,3,5,6-tetramethylphenyloxy group, 5-indanyloxy group, 1,2,3,4-tetrahydro-5-naphthyloxy group, 1,2,3 4-tetrahydro-6-naphthyloxy group,

2-methoxyphenyloxy group, 3-methoxyphenyloxy group, 4-methoxyphenyloxy group, 3-ethoxyphenyloxy group, 4-ethoxyphenyloxy group, 4-n-propoxyphenyloxy group,
4-isopropoxyphenyloxy group, 4-n-butoxyphenyloxy group, 4-isobutoxyphenyloxy group, 4-n-pentyloxyphenyloxy group, 4-n
-Hexyloxyphenyloxy group, 4-cyclohexyloxyphenyloxy group, 4-n-heptyloxyphenyloxy group, 4-n-octyloxyphenyloxy group, 4-n-nonyloxyphenyloxy group, 4-n
-Decyloxyphenyloxy group, 4-n-undecyloxyphenyloxy group, 4-n-dodecyloxyphenyloxy group, 4-n-tetradecyloxyphenyloxy group, 4-n-hexadecyloxyphenyloxy group, 4-n-octadecyloxyphenyloxy group,
2,3-dimethoxyphenyloxy group, 2,4-dimethoxyphenyloxy group, 2,5-dimethoxyphenyloxy group, 3,4-dimethoxyphenyloxy group, 3,5
-Dimethoxyphenyloxy group, 3,5-diethoxyphenyloxy group, 2-methoxy-4-methylphenyloxy group, 2-methoxy-5-methylphenyloxy group,
3-methoxy-4-methylphenyloxy group, 2-methyl-4-methoxyphenyloxy group, 3-methyl-4-
Methoxyphenyloxy group, 3-methyl-5-methoxyphenyloxy group,

2-fluorophenyloxy, 3-fluorophenyloxy, 4-fluorophenyloxy, 2-chlorophenyloxy, 3-chlorophenyloxy, 4-chlorophenyloxy, 4-bromophenyloxy, 4 -Trifluoromethylphenyloxy group, 3-trifluoromethylphenyloxy group, 2,
4-difluorophenyloxy group, 2,4-dichlorophenyloxy group, 3,4-dichlorophenyloxy group,
3,5-dichlorophenyloxy group, 2-methyl-4-
Chlorophenyloxy group, 2-chloro-4-methylphenyloxy group, 3-chloro-4-methylphenyloxy group, 2-chloro-4-methoxyphenyloxy group, 3-
Methoxy-4-fluorophenyloxy group, 3-methoxy-4-chlorophenyloxy group, 3-fluoro-4-
Methoxyphenyloxy group, 4-phenylphenyloxy group, 3-phenylphenyloxy group, 2-phenylphenyloxy group, 4- (4′-methylphenyl) phenyloxy group, 4- (4′-methoxyphenyl) phenyloxy Group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 4-ethoxy-1-naphthyloxy group, 6-n-butyl-2-naphthyloxy group, 6-methoxy- 2-naphthyloxy group, 7
-Ethoxy-2-naphthyloxy group, 2-furyloxy group, 2-thienyloxy group, 3-thienyloxy group, 2
-Substituted or unsubstituted aryloxy groups such as -pyridyloxy group, 3-pyridyloxy group, and 4-pyridyloxy group;

More preferably, a hydrogen atom, a fluorine atom,
A chlorine atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or A substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, A linear, branched or cyclic alkoxy group having 16 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms.

In the general formula (1-A), X 1, X 2,
Compounds in which X5 and X6 are hydrogen atoms are particularly preferred.

In the organic electroluminescent device of the present invention,
It is characterized in that at least one kind of 2,9-diazadibenzo [cd, lm] perylene derivative is used.
-Use of diazadibenzo [cd, lm] perylene derivative in the light-emitting layer as a light-emitting component makes it possible to provide an organic electroluminescent device that emits green to yellow-green light with high luminance and excellent durability. Become.

When the light-emitting layer is formed in combination with other light-emitting components, it is possible to provide an organic electroluminescent device that emits white light with high luminance and excellent durability.

Specific examples of the compound A according to the present invention include:
For example, the following compounds can be mentioned, but the present invention is not limited thereto.

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The compound A according to the present invention, for example, the compound represented by the general formula (1-A) can be prepared by a method known per se [for example, Angew. Chem. Int. Ed., 39 , 1243 (2000)].
And the method described in [1].

That is, for example, the compound represented by the general formula (1-A) is obtained by reducing the compound represented by the general formula (2) in the presence of lithium aluminum hydride and aluminum chloride. The compound is represented by the formula (3). Then, the compound represented by the general formula (1-A) can be produced by reacting the compound represented by the general formula (3) with palladium / carbon in, for example, diphenyl ether.

[0101]

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[0102]

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[Wherein, Bz represents a benzyl group;
1 to X8 have the same meaning as in formula (1-A). ]

The compound represented by the general formula (2) can be prepared by a method known per se [eg, Liebigs Ann., 1229 (199)
5), Chem. Ber., 115 , 2927 (1982), Special Table 2000
-514747].

The compound A according to the present invention, for example, the compound represented by the general formula (1-A) may be a solvent (eg, an aromatic hydrocarbon solvent such as toluene) used in some cases.
May be produced in a form that forms a solvate with
The organic electroluminescent device of the present invention includes the compound A according to the present invention.
Such a solvate can be used as well as a non-solvate.

When the compound A according to the present invention, for example, the compound represented by the general formula (1-A) is used in an organic electroluminescent device, a recrystallization method, a column chromatography method,
It is preferable to use a purification method such as a sublimation purification method, or a compound having an increased purity by using these methods in combination.

The organic electroluminescent device usually has at least one light-emitting layer containing at least one light-emitting component sandwiched between a pair of electrodes. In consideration of the functional levels of hole injection and hole transport, electron injection and electron transport of the compound used in the light emitting layer, a hole injection transport layer containing a hole injection transport component and / or An electron injection / transport layer containing an injection / transport component can also be provided.

For example, when the compound used in the light emitting layer has a good hole injecting function, a hole transporting function and / or an electron injecting function, and an electron transporting function, the light emitting layer is formed of the hole injecting and transporting layer and / or the electron injecting function. A structure of a device also serving as an injection / transport layer can be provided. Of course, depending on the case, a structure of a device (single-layer device) without both the hole injection transport layer and the electron injection transport layer may be employed.

Each of the hole injecting and transporting layer, the electron injecting and transporting layer, and the light emitting layer may have a single-layer structure or a multilayer structure. In each layer, a layer having an injection function and a layer having a transport function may be separately provided.

In the organic electroluminescent device of the present invention, the compound A according to the present invention is preferably used for a hole injecting and transporting component, a light emitting component or an electron injecting and transporting component. Is more preferable,
It is particularly preferable to use it for a light emitting component.

In the organic electroluminescent device of the present invention, the compound A of the present invention may be used alone or in combination.

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

The organic electroluminescent device of the present invention is not limited to these device configurations, and each type of device may be provided with a plurality of hole injection / transport layers, light emitting layers, and electron injection / transport layers. it can. In each type of device, a light emitting component is provided between the hole injecting and transporting layer and the light emitting layer, and / or a mixed layer of the hole injecting and transporting component and the light emitting component and / or between the light emitting layer and the electron injecting and transporting layer. And a mixed layer of an electron injection and transport component.

A more preferable structure of the organic electroluminescent device is as follows.
(A) element, (B) element, (C) element, (E) element, (F) element, (G) element or (H) element, and more preferably (A) element. ) Type element, (B) type element, (C) type element or (F) type element.

As the organic electroluminescent device of the present invention, for example, (A) anode / hole injection / transport layer / light emitting layer / electron injection / transport layer / cathode device shown in FIG. 1 will be described.

In FIG. 1, 1 is a substrate, 2 is an anode,
Reference numeral 3 denotes a hole injection / transport layer, 4 denotes a light emitting layer, 5 denotes an electron injection / transport layer, 6 denotes a cathode, and 7 denotes a power supply.

The organic electroluminescent device of the present invention is preferably supported on a substrate 1. The substrate is not particularly limited, but is preferably transparent or translucent. Transparent plastic sheet (for example, polyester, polycarbonate, polysulfone, polymethyl methacrylate, polypropylene,
A sheet made of polyethylene or the like), a translucent plastic sheet, quartz, a transparent ceramic, or a composite sheet combining these.

Further, the emission color can be controlled by combining, for example, a color filter film, a color conversion film, and a dielectric reflection film on the substrate.

As the anode 2, it is preferable to use a metal, an alloy or an electrically conductive compound having a relatively large work function as an electrode material.

Examples of the electrode material used for the anode include gold, platinum, silver, copper, cobalt, nickel, palladium, vanadium, tungsten, tin oxide, zinc oxide,
TO (indium tin oxide), polythiophene, polypyrrole, and the like can be given. These electrode substances may be used alone or in combination of two or more.

The anode can be formed on a substrate by using such an electrode material by, for example, a vapor deposition method, a sputtering method or the like.

The anode may have a single-layer structure or a multilayer structure.

The sheet electric resistance of the anode is preferably set to several hundred Ω / □ or less, more preferably, about 5 to 50 Ω / □.

Although the thickness of the anode depends on the material of the electrode substance to be used, it is generally set to about 5 to 1000 nm, more preferably about 10 to 500 nm.

The hole injecting / transporting layer 3 is a layer containing a compound having a function of facilitating the injection of holes (holes) from the anode and a function of transporting the injected holes.

The hole injecting and transporting layer is formed of the compound A according to the present invention.
And / or other compounds having a hole injection / transport function (for example, phthalocyanine derivative, triarylmethane derivative, triarylamine derivative, oxazole derivative, hydrazone derivative, stilbene derivative, pyrazoline derivative, polysilane derivative, polyphenylenevinylene and derivatives thereof, Polythiophene and a derivative thereof, a poly-N-vinylcarbazole derivative, and the like).

The compound having a hole injection / transport function is
They may be used alone or in combination.

Other compounds having a hole injection / transport function used in the present invention include triarylamine derivatives (for example, 4,4′-bis [N-phenyl-N- (4 ″)).
-Methylphenyl) amino] biphenyl, 4,4'-bis [N-phenyl-N- (3 "-methylphenyl) amino] biphenyl, 4,4'-bis [N-phenyl-N-
(3 "-methoxyphenyl) amino] biphenyl, 4,
4'-bis [N-phenyl-N- (1 "-naphthyl) amino] biphenyl, 3,3'-dimethyl-4,4'-bis [N-phenyl-N- (3" -methylphenyl) amino] Biphenyl, 1,1-bis [4 ′-[N, N-di (4 ″ -methylphenyl) amino] phenyl] cyclohexane, 9,10-bis [N- (4′-methylphenyl) -N- (4 "-N-butylphenyl) amino] phenanthrene, 3,8-bis (N, N-diphenylamino) -6-phenylphenanthridine, 4-methyl-
N, N-bis [4 ″, 4 ″ ′-bis [N ′, N′-di (4-methylphenyl) amino] biphenyl-4-yl] aniline, N, N′-bis [4- (diphenylamino) ) Phenyl) -N, N'-diphenyl-1,3-diaminobenzene, N, N'-bis [4- (diphenylamino) phenyl] -N, N'-diphenyl-1,4-diaminobenzene, 5, 5 ″ -bis [4- (bis [4-methylphenyl] amino) phenyl] -2,2 ′: 5 ′,
2 "-terthiophene, 1,3,5-tris (diphenylamino) benzene, 4,4 ', 4" -tris (N-carbazolyyl) triphenylamine, 4,4', 4 "-
Tris [N- (3 "'-methylphenyl) -N-phenylamino) triphenylamine, 4,4', 4" -tris [N, N-bis (4 ""-tert-butylbiphenyl-
4 ""-yl) amino] triphenylamine, 1,3
5-tris [N- (4'-diphenylaminophenyl)
-N-phenylaminobenzene), polythiophene and derivatives thereof, and poly-N-vinylcarbazole derivatives are more preferred.

When the compound A according to the present invention and another compound having a hole injecting and transporting function are used in combination, the proportion of the compound A according to the present invention in the hole injecting and transporting layer is preferably
It is adjusted to about 0.1 to 40% by weight.

The light emitting layer 4 has a hole and electron injection function,
This is a layer containing a compound having a transport function thereof and a function of generating excitons by recombination of holes and electrons.

The light emitting layer is composed of the compound A according to the present invention and / or
Or a compound having another light-emitting function (eg, acridone derivative, quinacridone derivative, diketopyrrolopyrrole derivative, polycyclic aromatic compound [eg, rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenylcyclo) Pentadiene, pentaphenylcyclopentadiene, 9,10-
Diphenylanthracene, 9,10-bis (phenylethynyl) anthracene, 1,4-bis (9′-ethynylanthracenyl) benzene, 4,4′-bis (9 ″ -ethynylanthracenyl) biphenyl], triaryl Amine derivatives (for example, the compounds described above as compounds having a hole injecting and transporting function), organometallic complexes (for example, tris (8-quinolinolato) aluminum, bis (10-benzo [h] quinolinolato) beryllium, Zinc salt of 2- (2'-hydroxyphenyl) benzoxazole, 2- (2'-hydroxyphenyl)
Benzothiazole zinc salt, 4-hydroxyacridine zinc salt, 3-hydroxyflavone zinc salt, 5-hydroxyflavone beryllium salt, 5-hydroxyflavone aluminum salt], stilbene derivatives [for example,
1,1,4,4-tetraphenyl-1,3-butadiene, 4,4′-bis (2,2-diphenylvinyl) biphenyl, 4,4′-bis [(1,1,2-triphenyl) Ethenyl] biphenyl],

Coumarin derivatives [for example, coumarin 1, coumarin 6, coumarin 7, coumarin 30, coumarin 10
6, Coumarin 138, Coumarin 151, Coumarin 15
2, Coumarin 153, Coumarin 307, Coumarin 31
1. Coumarin 314, Coumarin 334, Coumarin 33
8, coumarin 343, coumarin 500], pyran derivatives [eg, DCM1, DCM2], oxazone derivatives [eg, Nile Red], benzothiazole derivatives,
Benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamate derivatives, poly-
N-vinyl carbazole and its derivatives, polythiophene and its derivatives, polyphenylene and its derivatives, polyfluorene and its derivatives, polyphenylene vinylene and its derivatives, polybiphenylene vinylene and its derivatives, polyterphenylene vinylene and its derivatives, polynaphthylene vinylene and Derivatives, polythienylenevinylene and its derivatives)
Can be formed by using at least one kind of

In the organic electroluminescent device of the present invention, it is preferable that the light emitting layer contains the compound A of the present invention.

When the compound A according to the present invention and a compound having another light emitting function are used in combination, the ratio of the compound A according to the present invention in the light emitting layer is preferably 0.001 to 9
9.999% by weight, more preferably 0.01 to 9% by weight.
About 9.99% by weight, more preferably 0.1 to 9%
It is adjusted to about 9.9% by weight.

As the other compound having a light emitting function used in the present invention, a light emitting organic metal complex or a triarylamine derivative is more preferable.

For example, J. Appl. Phys., 65 , 3610 (198
9), as described in JP-A-5-214332,
The light emitting layer may be composed of a host compound and a guest compound (dopant).

The light emitting layer can be formed by using the compound A according to the present invention as a host compound, and further can be formed by using the compound A as a guest compound.

When the compound A according to the present invention is used as a guest compound to form a light-emitting layer, the host compound is more preferably a light-emitting organometallic complex or the above triarylamine derivative.

In this case, the compound represented by the general formula (1) is preferably used in an amount of about 0.001 to 40% by weight, more preferably about 0.1 to 40% by weight, based on the luminescent organometallic complex or the triarylamine derivative. It is used in an amount of about 01 to 30% by weight, particularly preferably about 0.1 to 20% by weight.

The luminescent organometallic complex used in combination with the compound A according to the present invention is not particularly limited, but a luminescent organoaluminum complex is preferable, and a luminescent organometallic complex having a substituted or unsubstituted 8-quinolinolate ligand is preferable. Organic aluminum complexes are more preferred.

Preferred luminescent organic metal complexes include, for example, luminescent organic aluminum complexes represented by formulas (a) to (c).

(Q) 3 -Al (a) (wherein Q represents a substituted or unsubstituted 8-quinolinolate ligand) (Q) 2 -Al-OL (b) (wherein Q represents a substituted 8-quinolinolate ligand;
-L is a phenolate ligand, and L represents a C6-C24 hydrocarbon group containing a phenyl moiety. ) (Q) 2-Al-O-Al- (Q) 2 (c) (wherein Q represents a substituted 8-quinolinolate ligand.)

Specific examples of the luminescent organometallic complex include, for example, tris (8-quinolinolate) aluminum, tris (4-methyl-8-quinolinolate) aluminum, tris (5-methyl-8-quinolinolate) aluminum, tris ( 3,4-dimethyl-8-quinolinolate) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, tris (4,6-dimethyl-8-quinolinolate) aluminum, bis (2-methyl-8-quinolinolate) (Phenolate) aluminum, bis (2-methyl-8-quinolinolate) (2-
Methylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-methylphenolate) aluminum, bis (2-methyl-8-quinolinolate)
(4-methylphenolate) aluminum, bis (2-
Methyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-phenylphenolate) aluminum,

Bis (2-methyl-8-quinolinolate)
(4-phenylphenolate) aluminum, bis (2
-Methyl-8-quinolinolate) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,6-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolate)
(3,4-dimethylphenolato) aluminum, bis (2-methyl-8-quinolinolate) (3,5-dimethylphenolate) aluminum, bis (2-methyl-8
-Quinolinolate) (3,5-di-tert-butylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolate)
(2,4,6-triphenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2
4,6-trimethylphenolato) aluminum, bis (2-methyl-8-quinolinolate) (2,4,5,6
-Tetramethylphenolate) aluminum, bis (2
-Methyl-8-quinolinolate) (1-naphtholate)
Aluminum, bis (2-methyl-8-quinolinolate) (2-naphtholate) aluminum, bis (2,4
-Dimethyl-8-quinolinolate) (2-phenylphenolato) aluminum, bis (2,4-dimethyl-8)
-Quinolinolate) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-
Dimethylphenolate) aluminum, bis (2,4-
Dimethyl-8-quinolinolate) (3,5-di-tert-
Butyl phenolate) aluminum,

Bis (2-methyl-8-quinolinolate)
Aluminum-μ-oxo-bis (2-methyl-8-quinolinolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolate) aluminum, Bis (2-methyl-4-ethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-
4-ethyl-8-quinolinolate) aluminum, bis (2-methyl-4-methoxy-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8-quinolinolate) aluminum, bis (2-
Methyl-5-cyano-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-
Quinolinolate) aluminum, bis (2-methyl-5)
-Trifluoromethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum.

Of course, the luminescent organometallic complex may be used alone or in combination.

The triarylamine derivative used in combination with the compound A according to the present invention is not particularly limited, and examples thereof include the compounds described above as compounds having a hole injection / transport function. Of course, the triarylamine derivatives may be used alone or in combination.

The electron injecting / transporting layer 5 is a layer containing a compound having a function of facilitating the injection of electrons from the cathode and a function of transporting the injected electrons.

The electron injecting and transporting layer is made of the compound A according to the present invention.
And / or other compounds having an electron injecting and transporting function (eg, organometallic complexes [eg, tris (8-quinolinolate) aluminum, bis (10-benzo [h] quinolinolate)) beryllium, beryllium salt of 5-hydroxyflavone, 5 -Hydroxyflavone aluminum salt], an oxadiazole derivative [eg, 1,3-bis [5 ′-(p-tert-butylphenyl) -1,3,4-
Oxadiazol-2'-yl] benzene], a triazole derivative [for example, 3- (4'-tert-butylphenyl) -4-phenyl-5- (4 "-biphenyl) -1,
2,4-triazole], a triazine derivative, a perylene derivative, a quinoline derivative, a quinoxaline derivative, a diphenylquinone derivative, a nitro-substituted fluorenone derivative, a thiopyrandioxide derivative, etc.).

When the compound A according to the present invention is used in combination with another compound having an electron injecting and transporting function, the proportion of the compound A according to the present invention in the electron injecting and transporting layer is preferably
It is adjusted to about 0.1 to 40% by weight.

In the present invention, the compound A according to the present invention
It is preferable to form an electron injecting and transporting layer by using a combination of an organic metal complex [for example, compounds represented by the above general formulas (a) to (c)].

As the cathode 6, it is preferable to use a metal, an alloy or an electrically conductive compound having a relatively small work function as an electrode material.

Examples of the electrode material used for the cathode include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, calcium, magnesium, magnesium-silver alloy, magnesium-indium alloy, indium, ruthenium, titanium, manganese, and the like. Examples include yttrium, aluminum, an aluminum-lithium alloy, an aluminum-calcium alloy, an aluminum-magnesium alloy, and a graphite thin film. These electrode substances may be used alone or in combination of two or more.

The cathode can be formed on the electron injecting and transporting layer by using any of these electrode materials by a method such as a vapor deposition method, a sputtering method, an ionization vapor deposition method, an ion plating method, and a cluster ion beam method. .

Further, the cathode may have a single-layer structure or a multilayer structure.

The sheet electric resistance of the cathode is several hundred Ω / □.
It is preferable to set the following.

Although the thickness of the cathode depends on the material of the electrode substance to be used, it is generally set to about 5 to 1000 nm, more preferably about 10 to 500 nm.

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

Further, in the organic electroluminescent device of the present invention, at least one layer may contain a singlet oxygen quencher.

The singlet oxygen quencher is not particularly limited, and includes, for example, rubrene, a nickel complex, diphenylisobenzofuran and the like, with rubrene being particularly preferred.

The layer containing the singlet oxygen quencher is not particularly limited, but is preferably a light emitting layer or a hole injection transport layer, and more preferably a hole injection transport layer. . When a singlet oxygen quencher is contained in the hole injecting and transporting layer, for example, the singlet oxygen quencher may be uniformly contained in the hole injecting and transporting layer, and a layer adjacent to the hole injecting and transporting layer (for example, a light emitting layer, (Electron injection / transport layer having a light emitting function).

The content of the singlet oxygen quencher is from 0.01 to 50% by weight, preferably from 0.0 to 50% by weight of the total amount of the contained layer (for example, the hole injection transport layer).
5 to 30% by weight, more preferably 0.1 to 20% by weight
It is.

The method of forming the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer is not particularly limited. For example, a vacuum evaporation method, an ionization evaporation method, a solution coating method (for example, spin coating, casting) Method, dip coating method,
It can be manufactured by forming a thin film by a bar coating method, a roll coating method, a Langmuir-Brosette method, an inkjet method, or the like.

When forming each layer by a vacuum deposition method,
The conditions for vacuum deposition are not particularly limited,
Under a vacuum of about ^-5 Torr or less, a boat temperature (deposition source temperature) of about 50 to 600 ° C., a substrate temperature of about −50 to 300 ° C., and a deposition rate of about 0.005 to 50 nm / sec. Is preferred.

In this case, the layers such as the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer are continuously formed under vacuum to produce an organic electroluminescent device having more excellent properties. Can be.

When the layers such as the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer are formed using a plurality of compounds by the vacuum evaporation method, the temperature of each boat containing the compounds is controlled individually. Co-evaporation is preferred.

When each layer is formed by a solution coating method,
The components forming each layer or the components and a binder resin or the like are dissolved or dispersed in a solvent to form a coating liquid.

Examples of the binder resin usable for each of the hole injection transport layer, the light emitting layer and the electron injection transport layer include, for example,
Poly-N-vinylcarbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl acrylate, polymethyl methacrylate, polyether, polycarbonate, polyamide, polyimide, polyamide imide, polyparaxylene, polyethylene, polyethylene ether, polypropylene ether, polyphenylene High molecular compounds such as oxide, polyethersulfone, polyaniline and its derivatives, polythiophene and its derivatives, polyphenylenevinylene and its derivatives, polyfluorene and its derivatives, and polythienylenevinylene and its derivatives can be given. The binder resin may be used alone or in combination.

When each layer is formed by a solution coating method,
The components forming each layer or the components and a binder resin are combined with a suitable organic solvent (for example, hexane, octane,
Decane, toluene, xylene, ethylbenzene, hydrocarbon solvents such as 1-methylnaphthalene, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, for example, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, Halogenated hydrocarbon solvents such as tetrachloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene, for example, ethyl acetate, butyl acetate, ester solvents such as amyl acetate, for example, methanol, ethanol, propanol, butanol, pentanol, hexanol, Alcohol-based solvents such as cyclohexanol, methyl cellosolve, ethyl cellosolve, and ethylene glycol, for example, dibutyl ether, tetrahydrofuran, dioxane Down, ether solvents anisole, for example, N, N-dimethylformamide, N, N-
Dimethylacetamide, 1-methyl-2-pyrrolidone,
A polar solvent such as 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide) and / or dissolved or dispersed in water to form a coating solution, and a thin film can be formed by various coating methods. .

The method of dispersing is not particularly limited, but for example, it can be dispersed in fine particles using a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer or the like.

The concentration of the coating solution is not particularly limited, and can be set to a concentration range suitable for producing a desired thickness depending on a coating method to be performed. %, Preferably about 1 to 30% by weight.

When a binder resin is used, the amount of the binder resin used is not particularly limited. However, in general, the components used for forming each layer (when forming a single-layer element, 5-99. Based on the total amount of components).
It is set to about 9% by weight, preferably about 10 to 99% by weight, and more preferably about 15 to 90% by weight.

The thicknesses of the hole injecting and transporting layer, the light emitting layer and the electron injecting and transporting layer are not particularly limited, but are generally preferably set to about 5 nm to 5 μm.

For the purpose of preventing the fabricated device from contacting oxygen, moisture, etc., a protective layer (sealing layer) may be provided or the device may be formed of, for example, paraffin, liquid paraffin, silicon oil, fluorocarbon, or the like. It can be protected by being enclosed in an inert substance such as oil or zeolite-containing fluorocarbon oil.

As the material used for the protective layer, for example,
Organic polymer materials (for example, fluorinated resin, epoxy resin, silicone resin, epoxy silicone resin, polystyrene, polyester, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, polyphenylene oxide), inorganic materials (for example, diamond) Thin films, amorphous silica, electrically insulating glass, metal oxides, metal nitrides, metal carbides, metal sulfides), and furthermore, photocurable resins, and the like. They may be used, or a plurality of them may be used in combination. The protective layer may have a single-layer structure or a multilayer structure.

Also, a metal oxide film (for example, an aluminum oxide film) or a metal fluoride film can be provided as a protective film on the electrode.

For example, an interface layer (intermediate layer) made of, for example, an organic phosphorus compound, polysilane, an aromatic amine derivative, a phthalocyanine derivative (eg, copper phthalocyanine), or carbon may be provided on the surface of the anode.

Further, an electrode such as an anode can be used by treating its surface with, for example, acid, ammonia / hydrogen peroxide, or plasma.

Although the organic electroluminescent device of the present invention is generally used as a DC-driven device, it can also be used as a pulse-driven or AC-driven device.

The applied voltage is generally about 2 to 30 V.

The organic electroluminescent device of the present invention can be used, for example, as a panel type light source, various light emitting devices, various display devices, various labels, various sensors, and the like.

[0182]

The present invention will be described in more detail with reference to the following examples, which, of course, are not intended to limit the scope of the present invention.

Example 1 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using a nitrogen gas, was further subjected to UV / ozone cleaning, it was fixed on a substrate holder of the vapor deposition apparatus, followed by vacuum vapor deposition tank 3 × 10 ^-6 Torr. First, 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl was vapor-deposited on the ITO transparent electrode to a thickness of 75 nm at a vapor deposition rate of 0.2 nm / sec. Next, bis (2-methyl-8-quinolinolate) (4-phenylphenolate) aluminum and the compound of Exemplified Compound No. 1 were further deposited thereon from a different evaporation source at a deposition rate of 0.2 nm. 5 / sec
It was co-evaporated to a thickness of 0 nm (weight ratio: 100: 0.5) to form a light emitting layer. Next, tris (8-quinolinolato) aluminum was deposited at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form an electron injection transport layer. Further on that,
Magnesium and silver are deposited at a deposition rate of 0.2 nm / sec for 20
A cathode was formed by co-evaporation (weight ratio: 10: 1) to a thickness of 0 nm to produce an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 12 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 55 mA / cm ² flowed. Brightness 267
Green light emission of 0 cd / m ² was confirmed.

Examples 2 to 45 In Example 1, instead of using the compound of Exemplified Compound No. 1 in forming the light emitting layer, Exemplified Compound No. 4 was used.
(Example 2), the compound of Exemplified Compound No. 8 (Example 3), the compound of Exemplified Compound No. 12 (Example 4),
Compound of Exemplified Compound No. 19 (Example 5), Compound of Exemplified Compound No. 23 (Example 6), Compound of Exemplified Compound No. 30 (Example 7), Compound of Exemplified Compound No. 33 (Example 8), Exemplified Compound Compound No. 37 (Example 9),
Compound of Exemplified Compound No. 46 (Example 10), Compound of Exemplified Compound No. 49 (Example 11), Exemplified Compound No. 5
Compound No. 9 (Example 12), Compound No. 67 (Example 13), Compound No. 70 (Example 14), Compound No. 78 (Example 1)
5), Exemplified Compound No. 84 (Example 16), Exemplified Compound No. 96 (Example 17), Exemplified Compound No. 106 (Example 18), Exemplified Compound No. 1
Compound No. 10 (Example 19), Compound No. 114 (Example 20), Compound No. 123 (Example 21), Compound No. 131 (Example 22), Compound No. 133 Compound (Example 2
3), compound of Exemplified Compound No. 137 (Example 24),
Compound of Exemplified Compound No. 141 (Example 25), Compound of Exemplified Compound No. 145 (Example 26), Compound of Exemplified Compound No. 156 (Example 27), Exemplified Compound No. 16
Compound No. 2 (Example 28), Compound No. 175 (Example 29), Compound No. 178 (Example 30), Compound No. 183 (Example 31), Compound No. 188 Compound (Example 3
2), a compound of Exemplified Compound No. 192 (Example 33),
Compound of Exemplified Compound No. 196 (Example 34), Compound of Exemplified Compound No. 198 (Example 35), Compound of Exemplified Compound No. 204 (Example 36), Exemplified Compound No. 20
Compound No. 7 (Example 37), Compound No. 216 (Example 38), Compound No. 221 (Example 39), Compound No. 226 (Example 40), Compound No. 233 Compound (Example 4
1), compound of Exemplified Compound No. 238 (Example 42),
Except for using the compound of Exemplified Compound No. 247 (Example 43), the compound of Exemplified Compound No. 254 (Example 44) and the compound of Exemplified Compound No. 260 (Example 45), the organic compound was prepared by the method described in Example 1. An electroluminescent device was manufactured. When a DC voltage of 12 V was applied to each device under a dry atmosphere, green to yellow-green light emission was confirmed. The characteristics were further examined, and the results are shown in Table 1.

Comparative Example 1 In Example 1, when forming the light-emitting layer, the compound of Exemplified Compound No. 1 was not used and bis (2-methyl-8-
An organic electroluminescent device was prepared by the method described in Example 1, except that quinolinolate) (4-phenylphenolate) aluminum alone was used to form a light emitting layer by vapor deposition to a thickness of 50 nm. This device was exposed to a 12 V
As a result, blue light emission was confirmed. The characteristics were further examined, and the results are shown in Table 1.

Comparative Example 2 In Example 1, when forming the light emitting layer, instead of using the compound of Exemplified Compound No. 1, N-methyl-2-
An organic electroluminescent device was manufactured by the method described in Example 1 except that methoxyacridone was used. When a DC voltage of 12 V was applied to this device under a dry atmosphere, blue light emission was confirmed. Further investigate its properties,
The results are shown in Table 1.

[0187]

[Table 1]

[0188]

[Table 2]

[0189]

[Table 3]

Example 46 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned with a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4′-bis [N-phenyl-N- (1 ″ -naphthyl) amino] biphenyl was deposited on the ITO transparent electrode to a thickness of 75 nm at a deposition rate of 0.2 nm / sec. Next, bis (2-methyl-8-quinolinolate) (2-phenylphenolate) aluminum and the compound of Exemplified Compound No. 116 were further formed thereon.
50n at a deposition rate of 0.2nm / sec from different deposition sources
m to give a light emitting layer by co-evaporation (weight ratio: 100: 1.0). Next, tris (8-quinolinolate) aluminum was deposited at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form an electron injection transport layer. Further, magnesium and silver are further deposited thereon at a deposition rate of 0.2 nm / sec for 200 n.
An organic electroluminescent device was prepared by co-evaporating the resultant to a thickness of 10 m (weight ratio: 10: 1) to form a cathode. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 12 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 58 mA / cm ² flowed. Brightness 2670c
Green light emission of d / m ² was confirmed.

Example 47 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4′-bis [N-phenyl-N- (1 ″ -naphthyl) amino] biphenyl is vapor-deposited on an ITO transparent electrode to a thickness of 75 nm at a vapor deposition rate of 0.2 nm / sec. Next, bis (2-methyl-8-quinolinolate) (4-phenylphenolate) aluminum and a compound of Exemplified Compound No. 200 were further placed thereon.
50n at a deposition rate of 0.2nm / sec from different deposition sources
m was co-evaporated (weight ratio: 100: 2.0) to obtain a light emitting layer. Next, tris (8-quinolinolate) aluminum was deposited at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form an electron injection transport layer. Further, magnesium and silver are further deposited thereon at a deposition rate of 0.2 nm / sec for 200 n.
An organic electroluminescent device was prepared by co-evaporating the resultant to a thickness of 10 m (weight ratio: 10: 1) to form a cathode. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 12 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 57 mA / cm ² flowed. Brightness 2620c
Green light emission of d / m ² was confirmed.

Example 48 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4′-bis [N-phenyl-N- (1 ″ -naphthyl) amino] biphenyl was deposited on the ITO transparent electrode to a thickness of 75 nm at a deposition rate of 0.2 nm / sec. Then, a bis (2,4) was formed thereon.
-Dimethyl-8-quinolinolato) aluminum-μ-
Oxo-bis (2,4-dimethyl-8-quinolinolate) aluminum and the compound of Exemplified Compound No. 237 were
50n at a deposition rate of 0.2nm / sec from different deposition sources
m was co-deposited (weight ratio: 100: 4.0) to form a light emitting layer. Next, tris (8-quinolinolato) aluminum was deposited at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form an electron injection transport layer. Further, magnesium and silver are further deposited thereon at a deposition rate of 0.2 nm / sec for 200 n.
An organic electroluminescent device was prepared by co-evaporating the resultant to a thickness of 10 m (weight ratio: 10: 1) to form a cathode. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 12 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 60 mA / cm ² flowed. Brightness 2660c
green light emission of d / m ² was observed.

Example 49 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4 ′, 4 ″ -tris [N
-(3 "'-methylphenyl) -N-phenylamino]
Triphenylamine at a deposition rate of 0.1 nm / sec.
Evaporation was performed to a thickness of 0 nm to form a first hole injection transport layer. Then, 4,4'-bis [N-phenyl-N-
(3 ″ -Methylphenyl) amino] biphenyl was deposited at a deposition rate of 0.2 nm / sec to a thickness of 45 nm to form a second hole injecting and transporting layer.
Methyl-8-quinolinolate) (4-phenylphenolate) aluminum and the compound of Exemplified Compound No. 115 were obtained from different evaporation sources at a deposition rate of 0.2 nm / sec.
It was co-evaporated to a thickness of 0 nm (weight ratio: 100: 1.0) to form a light emitting layer. Further, tris (8-quinolinolate) aluminum was further deposited thereon at a deposition rate of 0.2 nm / sec.
Evaporation was performed to a thickness of 0 nm to form an electron injection transport layer. Further thereon, magnesium and silver were deposited at a deposition rate of 0.2 nm /
A co-evaporation (weight ratio: 10: 1) was performed to a thickness of 200 nm in sec to form an organic electroluminescent device as a cathode. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 12 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 58 mA / cm ² flowed.
Green light emission luminance 2940cd / m ² was observed.

Example 50 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4′-bis [N-phenyl-N- (1 ″ -naphthyl) amino] biphenyl was deposited on the ITO transparent electrode to a thickness of 75 nm at a deposition rate of 0.2 nm / sec. Then, a tris (8-
Quinolinolate) aluminum and Exemplified Compound No. 143
From a different evaporation source at a deposition rate of 0.2 nm /
Co-deposition to a thickness of 50 nm in sec (weight ratio 100: 4.
0) to form a light-emitting layer also serving as an electron injection / transport layer. Further thereon, magnesium and silver were deposited at a deposition rate of 0.2 nm /
A co-evaporation (weight ratio: 10: 1) was performed to a thickness of 200 nm in sec to form an organic electroluminescent device as a cathode. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 14 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 52 mA / cm ² flowed.
Green light emission with a luminance of 2230 cd / m ² was confirmed.

Example 51 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using a nitrogen gas, was further subjected to UV / ozone cleaning, it was fixed on a substrate holder of the vapor deposition apparatus, followed by vacuum vapor deposition tank 3 × 10 ^-6 Torr. First, 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl was vapor-deposited on the ITO transparent electrode to a thickness of 75 nm at a vapor deposition rate of 0.2 nm / sec. Then, tris (8-quinolinolate) aluminum and the compound of Exemplified Compound No. 206 were deposited thereon from different evaporation sources at a deposition rate of 0.2.
Co-deposition to a thickness of 50 nm at nm / sec (weight ratio 100:
1.0) to form a light emitting layer. Then, on top of that,
-Bis [5 '-(p-tert-butylphenyl) -1,
3,4-oxadiazol-2'-yl] benzene,
Deposit to a thickness of 50 nm at a deposition rate of 0.2 nm / sec.
An electron injection transport layer was used. Further, magnesium and silver were co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to form a cathode, thereby producing an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 14 V was applied to the produced organic electroluminescent device under a dry atmosphere, the voltage was 48 m.
A / cm ² current flowed. Green light emission with a luminance of 2250 cd / m ² was confirmed.

Example 52 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4′-bis [N-phenyl-N- (1 ″ -naphthyl) amino] biphenyl was deposited on the ITO transparent electrode to a thickness of 75 nm at a deposition rate of 0.2 nm / sec. Next, the compound of Exemplified Compound No. 240 was further deposited thereon at a deposition rate of 0.2 nm / sec for 50 hours.
The layer was deposited to a thickness of nm to form a light emitting layer. Next, 1,3-bis [5 ′-(p-tert-butylphenyl) -1,3,4-oxadiazol-2′-yl] benzene was deposited thereon at a deposition rate of 0.2 nm / sec. Evaporation was performed to a thickness of 50 nm to form an electron injection transport layer. Further, magnesium and silver were further deposited thereon at a deposition rate of 0.2 nm / sec for 200 nm.
Co-deposit (weight ratio 10: 1) to a thickness of nm to form a cathode,
An organic electroluminescent device was manufactured. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 14 V was applied to the produced organic electroluminescent device in a dry atmosphere, a current of 48 mA / cm ² flowed. Brightness 1270c
A yellow-green emission of d / m ² was observed.

Example 53 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4 ′, 4 ″ -tris [N
-(3 "'-methylphenyl) -N-phenylamino] triphenylamine at 50 nm at a deposition rate of 0.1 nm / sec.
m to form a first hole injection / transport layer. Next, 4,4′-bis [N-phenyl-N- (1 ″ -naphthyl) amino] biphenyl and the compound of Exemplified Compound No. 1 were obtained from different evaporation sources at an evaporation rate of 0.2 nm / sec.
Co-evaporation (weight ratio: 100: 5) was performed to a thickness of 20 nm to form a light emitting layer also serving as a second hole injection / transport layer. Next, tris (8-quinolinolate) aluminum was co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 50 nm (weight ratio: 100: 1.0) to form an electron injection transport layer. Furthermore, magnesium and silver were further deposited thereon at a deposition rate of 0.2 nm.
/ Sec to co-evaporate to a thickness of 200nm (weight ratio 10: 1)
This was used as a cathode to produce an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 15 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 65 mA / cm ² flowed.
Green light emission with a luminance of 3350 cd / m ² was confirmed.

Examples 54 to 60 Instead of using the compound of Exemplified Compound No. 1 in Example 53, replacing the compound of Exemplified Compound No. 13 (Example 5)
4), Compound of Exemplified Compound No. 124 (Example 55),
Compound of Exemplified Compound No. 149 (Example 56), Compound of Exemplified Compound No. 187 (Example 57), Compound of Exemplified Compound No. 215 (Example 58), Exemplified Compound No. 24
An organic electroluminescent device was produced by the method described in Example 53 except that the compound of Example 5 (Example 59) and the compound of Exemplified Compound No. 256 (Example 60) were used. When a DC voltage of 12 V was applied to each element under a dry atmosphere, green to yellow-green light emission was confirmed. The characteristics were further examined, and the results are shown in Table 2.

[0199]

[Table 4]

Example 61 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas and further washed with UV / ozone. Next, on the ITO transparent electrode, poly-N-vinylcarbazole (weight average molecular weight 1
50000), 1,1,4,4-tetraphenylbutadiene (blue light-emitting component), the compound of Exemplified Compound No. 16, and DCM-1 ["4- (dicyanomethylene)-
2-methyl-6- (4'-dimethylaminostyryl)-
4H-pyran "(orange light-emitting component)] at a weight ratio of 100: 5: 3: 2.
A light-emitting layer having a thickness of 400 nm was formed by dip coating using a dichloroethane solution. Next, after fixing the glass substrate having the light emitting layer to a substrate holder of a vapor deposition device, the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. Further, 3- (4′-tert-butylphenyl) -4-phenyl-5- (4 ″ -biphenyl)-is formed on the light emitting layer.
1,2,4-triazole is deposited at a deposition rate of 0.2 nm / se.
After vapor deposition to a thickness of 20 nm by c, tris (8-quinolinolate) aluminum was further vapor-deposited thereon to a thickness of 30 nm at a vapor deposition rate of 0.2 nm / sec to form an electron injection transport layer. Further, magnesium and silver were co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to form a cathode, thereby producing an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. When a DC voltage of 12 V was applied to the produced organic electroluminescent device under a dry atmosphere, the voltage was 74 mA / c.
m ² of current flowed. White light emission with a luminance of 1350 cd / m ² was confirmed.

Examples 62 to 68 In Example 61, instead of using the compound of Exemplified Compound No. 16, the compound of Exemplified Compound No. 26 (Example 62) and the compound of Exemplified Compound No. 120 (Example 6)
3), compound of Exemplified Compound No. 129 (Example 64),
Compound of Exemplified Compound No. 160 (Example 65), Compound of Exemplified Compound No. 201 (Example 66), Compound of Exemplified Compound No. 229 (Example 67), Exemplified Compound No. 24
Example 6 except that the compound of Example 2 (Example 68) was used.
An organic electroluminescent device was produced by the method described in 1. When a DC voltage of 12 V was applied to each element under a dry atmosphere, white light emission was confirmed. The characteristics were further examined, and the results are shown in Table 3.

[0202]

[Table 5]

Example 69 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas and further washed with UV / ozone. Next, on the ITO transparent electrode, poly-N-vinylcarbazole (weight average molecular weight 1
50000), 1,3-bis [5 '-(p-tert-butylphenyl) -1,3,4-oxadiazole-2'-
[Il] benzene and a compound of Exemplified Compound No. 203 were each formed into a light-emitting layer having a thickness of 300 nm by dip coating using a 3% by weight dichloroethane solution containing 100: 30: 1 by weight. . Next, after fixing the glass substrate having the light emitting layer to a substrate holder of a vapor deposition device, the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. Further, on the light emitting layer, magnesium and silver were co-deposited (weight ratio: 10: 1) to a thickness of 200 nm at a deposition rate of 0.2 nm / sec to form an organic electroluminescent device. When a DC voltage of 15 V was applied to the produced organic electroluminescent device under a dry atmosphere, the voltage was 76 mA / c.
m ² of current flowed. Green light emission with a luminance of 1360 cd / m ² was confirmed.

Comparative Example 3 In Example 69, when forming the light emitting layer, instead of using the compound of Exemplified Compound No. 203, 1,1, 1
Except for using 4,4-tetraphenylbutadiene,
An organic electroluminescent device was manufactured by the method described in Example 69. In a dry atmosphere, add 1
When a DC voltage of 5 V was applied, a current of 86 mA / cm ² flowed. Blue light emission with a luminance of 720 cd / m ² was confirmed.

Example 70 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas and further washed with UV / ozone. Next, on the ITO transparent electrode, polycarbonate (weight average molecular weight: 50,000),
4,4'-bis [N-phenyl-N- (3 "-methylphenyl) amino] biphenyl, bis (2-methyl-8-
3 containing quinolinolate) (4-phenylphenolato) aluminum and the compound of Exemplified Compound No. 239 in a weight ratio of 100: 40: 60: 1, respectively.
A light emitting layer having a thickness of 300 nm was formed by a dip coating method using a weight% dichloroethane solution. next,
After fixing the glass substrate having the light emitting layer to the substrate holder of the vapor deposition device, the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. Further, on the light emitting layer, magnesium and silver were co-deposited (weight ratio: 10: 1) to a thickness of 200 nm at a deposition rate of 0.2 nm / sec to form an organic electroluminescent device. In a dry atmosphere, add 1
When a DC voltage of 5 V was applied, a current of 66 mA / cm ² flowed. Green light emission with a luminance of 920 cd / m ² was confirmed.

[0206]

According to the present invention, it has become possible to provide an organic electroluminescent device having excellent light emission luminance.

[Brief description of the drawings]

FIG. 1 is a schematic structural view of an example (A) of an organic electroluminescent element.

FIG. 2 is a schematic structural diagram of an example (B) of an organic electroluminescent element.

FIG. 3 is a schematic structural view of an example (C) of an organic electroluminescent element.

FIG. 4 is a schematic structural diagram of an example (D) of an organic electroluminescent element.

FIG. 5 is a schematic structural diagram of an example (E) of an organic electroluminescent element.

FIG. 6 is a schematic structural diagram of an example (F) of an organic electroluminescent element.

FIG. 7 is a schematic structural diagram of an example (G) of an organic electroluminescent element.

FIG. 8 is a schematic structural view of an example (H) of an organic electroluminescent element.

[Explanation of symbols]

 1: substrate 2: anode 3: hole injection / transport layer 3a: hole injection / transport component 4: light-emitting layer 4a: light-emitting component 5: electron injection / transport layer 5 ″: electron injection / transport layer 5a: electron injection / transport component 6: cathode 7: Power supply

 ──────────────────────────────────────────────────続 き Continued on front page (72) Inventor Yoshimitsu Tanabe 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals Co., Ltd. (72) Inventor Yoshiyuki Toya 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals Co., Ltd. F-term (Reference) 3K007 AB02 AB03 AB04 CA01 CB01 DA01 DB03 EB00

Claims (7)

[Claims] 1. An organic electroluminescent device comprising at least one layer containing at least one 2,9-diazadibenzo [cd, lm] perylene derivative sandwiched between a pair of electrodes. 2. The organic electroluminescence according to claim 1, wherein the layer containing at least one kind of 2,9-diazadibenzo [cd, lm] perylenetetrabenzo [a, cd, j, lm] perylene derivative is a light emitting layer. element. 3. The organic electroluminescent device according to claim 1, wherein the layer containing at least one kind of 2,9-diazadibenzo [cd, lm] perylene derivative further contains a luminescent organometallic complex. 4. The organic electroluminescent device according to claim 1, wherein the layer containing at least one kind of 2,9-diazadibenzo [cd, lm] perylene derivative further contains a triarylamine derivative. 5. The organic electroluminescent device according to claim 1, further comprising a hole injection / transport layer between the pair of electrodes. 6. The organic electroluminescent device according to claim 1, further comprising an electron injection / transport layer between the pair of electrodes. 7. The organic electroluminescent device according to claim 1, wherein the 2,9-diazadibenzo [cd, lm] perylene derivative is a compound represented by the general formula (1-A). Embedded image (Wherein X1 to X8 each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group; Represents an aryloxy group.)