JP2001213814A - Hydrocarbon compound and organic electric field light- generating element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electric field light-generating element excellent in light-generating efficiency and generating the light in a high brilliancy. SOLUTION: This organic electric field electric light-generating element is provided by using a compound expressed by the general formula (1-A) (wherein, X1 to X26 are each independently H, a halogen atom, a linear chain, branched or cyclic alkyl group, a linear, branched or cyclic alkoxyl group or a substituted or un-substituted aryl group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent device and a novel hydrocarbon compound which can be suitably used for the device.

[0002]

2. Description of the Related Art Conventionally, an inorganic electroluminescent device has been used as a panel-type light source such as a backlight. However, driving the light emitting device requires a high AC voltage. Recently, an organic electroluminescent device (organic electroluminescent device: organic EL device) using an organic material as a light emitting material has been developed [Appl. Phys. Lett., 51 , 913 (1)
987)]. 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 and recombined to form excitons. (Exciton), and emits light 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, green). 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 light emission luminance, an organic electroluminescent device using, for example, tris (8-quinolinolato) aluminum as a host compound, a coumarin derivative, or a pyran derivative as a guest compound (dopant) has been proposed as a light emitting layer. J. Appl. Phys., 65 , 3610 (198
9)]. Further, as the light emitting layer, for example, bis (2-methyl-8-quinolinolate) (4-phenylphenolate)
An organic electroluminescent device using 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.

[0004]

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. Another object is to provide a novel hydrocarbon compound that can be suitably used for the light-emitting element.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on the organic electroluminescent device, and as a result, have completed the present invention. That is, the present invention relates to a method for preparing bisbenzo [h] fluoreno [9,1,2-c
de: 2 ', 1', 9'-klm] dibenzo [h, rst] An organic electroluminescent device comprising at least one layer containing at least one pentaphene derivative, and bisbenzo [h] fluoreno [9,1, 2-cde: 2 ', 1', 9'-klm]
The layer containing the dibenzo [h, rst] pentaphene derivative is
The organic electroluminescent device as described above, which is a light-emitting layer, bisbenzo [h] fluoreno [9,1,2-cde: 2 ′, 1 ′, 9′-klm]
The layer containing the dibenzo [h, rst] pentaphene derivative is
The organic electroluminescent device according to the above or the above, further comprising a luminescent organometallic complex, bisbenzo [h] fluoreno [9,1,2-cde: 2 ′, 1 ′, 9′-klm]
The layer containing the dibenzo [h, rst] pentaphene derivative is
The organic electroluminescent device according to the above or the above, further comprising a triarylamine derivative, The organic electroluminescent device according to any one of the above to the above, further comprising a hole injection / transport layer between a 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, bisbenzo [h] fluoreno [9,1,2-cde: 2 ′, 1 ′, 9 ′ -klm]
The dibenzo [h, rst] pentaphene derivative has the general formula (1-
A) The organic electroluminescent device according to any one of the above items, which is a compound represented by (Chem. 3).

[0006]

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(Wherein, X _{1 to} X ₂₆ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a substituted or unsubstituted Further, the present invention relates to a compound represented by the general formula (1-A) (Formula 4).

[0008]

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(Wherein X _{1 to} X ₂₆ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a substituted or unsubstituted Represents an aryl group.)

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The organic electroluminescent device of the present invention has a structure in which bisbenzo [h] fluoreno [9,1,2-cde: 2 ′, 1 ′, 9′-kl
At least one layer containing at least one m] dibenzo [h, rst] pentaphene derivative is sandwiched between the layers. Bisbenzo [h] fluoreno [9,1,2-cd according to the present invention
e: 2 ′, 1 ′, 9′-klm] dibenzo [h, rst] pentaphene derivative (hereinafter abbreviated as compound A according to the present invention) is represented by the general formula (1) It represents a compound having a skeleton. The skeleton represented by the general formula (1) may be substituted with various substituents, and the compound A according to the present invention
Is preferably a compound represented by the general formula (1-A).

[0011]

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(Wherein X _{1 to} X ₂₆ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group) Represents a group.)

In the compound represented by the general formula (1-A), X _{1 to} X ₂₆ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkyl group. Represents an alkoxy group or a substituted or unsubstituted aryl group. In the present invention, the aryl group means 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. In the compound represented by the general formula (1-A), X _{1 to} X ₂₆ are preferably a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and a carbon atom having 1 to 20 carbon atoms. Represents a linear, branched or cyclic alkoxy group or a substituted or unsubstituted aryl group having 4 to 20 carbon atoms.

Specific examples of X _{1 to} X ₂₆ in the general formula (1-A) include, for example, a hydrogen atom, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom;
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, te
rt-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-propyl Pentyl 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, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl Linear, branched or cyclic alkyl groups such as groups; for example, methoxy groups, ethoxy groups,
n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, n-pentyloxy group, neopentyloxy group, cyclopentyloxy group, 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, n
Linear, branched or cyclic alkoxy groups such as -octadecyloxy group and n-eicosyloxy group; for example, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl Group, 4
-N-propylphenyl group, 4-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-isopentylphenyl group, 4-tert-pentylphenyl group, 4-n-
Hexylphenyl group, 4-cyclohexylphenyl group,
4-n-heptylphenyl 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,
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, 4-isopropoxyphenyl group , 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, 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-methyl A phenyl group, a 2-methyl-4-methoxyphenyl group, a 3-methyl-4-methoxyphenyl group, a 3-methyl-5-methoxyphenyl group,
2-fluorophenyl group, 3-fluorophenyl group, 4
-Fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 4-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-methoxyphenyl group, 3
-Methoxy-4-fluorophenyl group, 3-methoxy-
4-chlorophenyl group, 3-fluoro-4-methoxyphenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 4- (4′-methylphenyl) phenyl group,
-(4'-methoxyphenyl) 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-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 And substituted or unsubstituted aryl groups.

More preferably, a hydrogen atom, a fluorine atom,
Chlorine atom, C1-C10 alkyl group, C1-C1
An alkoxy group having 0 or an aryl group having 6 to 12 carbon atoms, more preferably a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms,
It is an alkoxy group having 6 or an aryl group having 6 to 10 carbon atoms.

In the organic electroluminescent device of the present invention, at least one bisbenzo [h] fluoreno [9,1,2-cde: 2 ′, 1 ′, 9′-klm] dibenzo [h, rst] pentaphene derivative is used. For example, bisbenzo [h] fluoreno [9,1,2-cde: 2 ′, 1 ′, 9′-klm] dibenzo [h, rst] pentaphene derivative is used as a light emitting component in a light emitting layer. Thus, it is possible to provide an organic electroluminescent element that emits red light with high luminance and excellent durability, which has not existed conventionally. In addition, when a light-emitting layer is formed in combination with another light-emitting component, an organic electroluminescent element that emits white light with high luminance and excellent durability can be provided.

Specific examples of the compound A according to the present invention include:
For example, the following compounds (Chemical Formulas 6 to 34) can be exemplified, but the present invention is not limited thereto.

[0018]

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[0030]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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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 produced, for example, by the following method. That is, for example, 1,4-dihalogeno-9 represented by the general formula (2)
10-bis (benzo [k] fluoranthene-3'-yl)
Anthracene derivatives can be produced by dehydrohalogenation in the presence of a base (eg, potassium hydroxide) and ring closure.

[0048]

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[In the above formula, X _{1 to} X ₂₆ are represented by the general formula (1-
A represents the same meaning as in A), and Z ₁ and Z ₂ represent a halogen atom.]

In the general formula (2), Z ₁ and Z ₂ represent a halogen atom, preferably a chlorine atom, a bromine atom and an iodine atom, more preferably a chlorine atom and a bromine atom. The compound represented by the general formula (2) is
For example, after a 3-halogenobenzo [k] fluoranthene derivative is metallized using magnesium, n-butyllithium, or the like, the compound is reacted with a 1,4-dihalogenoanthraquinone derivative to produce a compound of the general formula (3) ( Chemical 3
6) is converted to an acid (for example, hydroiodic acid)
Can be produced by reduction in the presence of

[0051]

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In the above formula, X _{1 to} X ₂₆ are represented by the general formula (1-
A represents the same meaning as in A), and Z ₁ and Z ₂ represent a halogen atom.]

The 3-halogenobenzo [k] fluoranthene derivatives are described, for example, in J. Chem. Soc., 1555 (1949), J. Am
er. Chem. Soc., 51 , 436 (1951), J. Amer. Chem. Soc., 74 , 1
075 (1952), Indian.J.Chem.Sect.B, 15B , 32 (1977),
J. Org. Chem., 50 , 1948 (1985), J. Org. Chem., 58 , 1415 (19
93). That is, for example, acecyclone derivatives [for example, Chem.R
ev., 65, p. 261 (1965)] and a benzyne derivative, followed by removing carbon monoxide. Further, for example, isobenzofuran derivatives [for example, Advances in Heterocy
clic Chemistry vol 26, p. 135 (1980)] and an acenaphthylene derivative, followed by dehydration.

The compound A according to the present invention may be produced in the form of a solvation with a solvent (for example, an aromatic hydrocarbon solvent such as toluene) used in some cases. The compound A according to the present invention includes such a solvate. Needless to say, a non-solvate containing no solvent is also included. In the organic electroluminescent device of the present invention, not only a non-solvate of the compound A according to the present invention but also such a solvate can be used. When the compound A according to the present invention 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 generally 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 for the light emitting layer has a good hole injection function, a hole transport function and / or an electron injection function, and an electron transport function, the light emitting layer is formed of the hole injection transport layer and / or the electron injection transport layer. The element can also be configured to serve as Needless to say, depending on the case, a structure of a device (single-layer device) in which both the hole injection transport layer and the electron injection transport layer are not provided may be employed. Also,
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, and the hole injecting and transporting layer and the electron injecting and transporting layer may have respective structures. In the 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 injection / transport component, a light emitting component or an electron injection / transport component, and is preferably used for a hole injection / transport component or a light emitting 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 according to 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.
(B) anode / hole injection / transport layer / light emitting layer / cathode device (FIG. 2), (C) anode / light emission Layer / electron injection / transport layer / cathode device (FIG. 3), (D) anode / light-emitting layer / cathode device (FIG. 4), and the like. Further, the device 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 device (FIG. 5).
The element configuration of the (D) type includes an element of a type in which a light-emitting component is sandwiched between a pair of electrodes in a single layer form. Further, for example, (F) a hole injection / transport component, (FIG. 6), and a pair of electrodes in the form of a single layer in which the hole injection / transport component and the light emitting component are mixed. There is an element of the type sandwiched between (FIG. 7) and (H) an element of the type sandwiched between a pair of electrodes (FIG. 8) in the form of a single layer in which a light emitting component and an electron injection transport component are mixed.

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. Can be. In each type of device, between the hole injection transport layer and the light emitting layer,
A mixed layer of a light emitting component and an electron injecting and transporting component may be provided between the light emitting layer and the electron injecting and transporting layer. More preferred configurations of the organic electroluminescent element include (A) type element, (B) type element, (C) type element, (E) type element, (F) type element,
(G) type element or (H) type element, more preferably (A) type element, (B) type element, (C) type element,
(F) type element or (H) type element. As the organic electroluminescent device of the present invention, for example, (A) anode / hole injection / transport layer / emission layer / electron injection / transport layer / cathode device shown in FIG. 1 will be described. (FIG. 1)
Is a substrate, 2 is an anode, 3 is a hole injection / transport layer, 4 is a light emitting layer,
Reference numeral 5 denotes an electron injection / transport layer, 6 denotes a cathode, and 7 denotes a power supply.

The electroluminescent device of the present invention is preferably supported on a substrate 1, and the substrate is not particularly limited, but is preferably transparent or translucent. Plastic sheets (eg, sheets of polyester, polycarbonate, polysulfone, polymethyl methacrylate, polypropylene, polyethylene, etc.), translucent plastic sheets,
Quartz, transparent ceramics, or a composite sheet combining these can be used. Further, on the substrate, for example, a color filter film, a color conversion film,
Emission color can also be controlled by combining dielectric reflection films.

As the anode 2, it is preferable to use a metal, an alloy or an electrically conductive compound having a relatively large work function as an electrode material. As the electrode material used for the anode, for example, gold, platinum, silver, copper, cobalt, nickel,
Palladium, vanadium, tungsten, tin oxide, zinc oxide, ITO (indium tin oxide), polythiophene, polypyrrole, and the like can be given. These electrode substances may be used alone or in combination of two or more. The anode can be formed on a substrate by using such an electrode material by a method such as an evaporation method or a sputtering method. Further, the anode may have a single-layer structure or a multilayer structure. The sheet electric resistance of the anode is preferably several hundred Ω.
/ □ or less, more preferably about 5 to 50Ω / □. The thickness of the anode depends on the material of the electrode substance used, but is generally about 5 to 1000 nm, more preferably,
It is set to about 10 to 500 nm.

The hole injection / transport layer 3 is a layer containing a compound having a function of facilitating the injection of holes (holes) from the anode and a function of transporting the injected holes. The hole injecting and transporting layer is formed of the compound A according to the present invention and / or another compound having a hole injecting and transporting function (for example, phthalocyanine derivative, triarylmethane derivative, triarylamine derivative, oxazole derivative, hydrazone derivative, stilbene derivative) , Pyrazoline derivatives, polysilane derivatives, polyphenylenevinylene and its derivatives,
Polythiophene and a derivative thereof, a poly-N-vinylcarbazole derivative, or the like). The compounds having a hole injection / transport function 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- (diphenyl Amino) phenyl] -N, N′-diphenyl-1,3-diaminobenzene, N, N′-bis [4- (diphenylamino) phenyl] -N, N′-diphenyl-1,4-diaminobenzene, 5 , 5 "-bis [4- (bis [4-methylphenyl] amino) phenyl] -2,2 ': 5',
2 "-terthiophene, 1,3,5-tris (diphenylamino) benzene, 4,4 ', 4" -tris (N-carbazolyyl) triphenylamine, 4,4', 4 "-
Tris [N- (3 ′ ″-methylphenyl) -N-phenylamino] triphenylamine, 4,4 ′, 4 ″ -tris [N, N-bis (4 ′ ″-tert-butylbiphenyl-
4 ""-yl) amino] triphenylamine, 1,3,5
-Tris [N- (4'-diphenylaminophenyl)-
N-phenylamino] benzene, etc.), polythiophene and derivatives thereof, and poly-N-vinylcarbazole derivatives are preferred. When the compound A according to the present invention is used in combination with another compound having a hole injecting and transporting function, the proportion of the compound A according to the present invention in the hole injecting and transporting layer is preferably 0.1 to 40% by weight. Prepare to about.

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 formed of the compound A according to the present invention and / or another compound having a light-emitting function (eg, an acridone derivative, a quinacridone derivative, a diketopyrrolopyrrole derivative, a polycyclic aromatic compound [eg, rubrene, anthracene, tetracene, pyrene). , Perylene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclohexadiene, 9,10-diphenylanthracene, 9,10-bis (phenylethynyl) anthracene, 1,4-bis (9'-ethynylanthracenyl) ) Benzene, 4,4′-bis (9 ″ -ethynylanthracenyl) biphenyl], a triarylamine derivative [for example, the compounds described above as compounds having a hole injecting and transporting function], and organometallic complexes [For example, Tris (8- Rirato) aluminum, bis (10-benzo [h] quinolinolato) beryllium, 2-
Zinc salt of (2′-hydroxyphenyl) benzoxazole, zinc salt of 2- (2′-hydroxyphenyl) benzothiazole, zinc salt of 4-hydroxyacridine,
-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 106, coumarin 138, coumarin 151, coumarin 152, coumarin 153, coumarin 307, coumarin 311, coumarin 314, coumarin 334, coumarin 338, coumarin 343, coumarin 500], pyran derivative [for example, D
CM1, DCM2], oxazone derivative [for example, Nile Red], benzothiazole derivative, benzoxazole derivative, benzimidazole derivative, pyrazine derivative, cinnamate derivative, poly-N-vinylcarbazole 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 its derivatives, polythienylene vinylene and its derivatives) It can be formed using at least one kind. In the organic electroluminescent device of the present invention, the light emitting layer preferably contains the compound A according to 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 0.00
About 1-99.999% by weight, more preferably 0.0
About 1 to 99.99% by weight, more preferably 0.1
It is adjusted to about 99.9% by weight.

As the other compound having a light-emitting function used in the present invention, a light-emitting organometallic complex is preferable. For example, J. Appl. Phys., 65 , 3610 (1989), JP-A-5-21
As described in Japanese Patent No. 4332, the light emitting layer may be composed of a host compound and a guest compound (dopant). The compound A according to the present invention can be used as a host compound to form a light emitting layer, and further can be used as a guest compound to form a light emitting layer. When the compound A according to the present invention is used as a guest compound to form a light-emitting layer, examples of the host compound include the compounds having the other light-emitting functions, such as a light-emitting organometallic complex or Triarylamines are more preferred. In this case, the compound A according to the present invention is preferably used in an amount of about 0.001 to 40% by weight, more preferably about 0.01 to 30% by weight, based on the luminescent organometallic complex or the triarylamine derivative. Particularly preferably, about 0.1 to 20% by weight is used.

The luminous organometallic complex used in combination with the compound A according to the present invention is not particularly limited, but a luminous organoaluminum complex is preferable, and a luminescence having a substituted or unsubstituted 8-quinolinolate ligand. Organic aluminum complexes are more preferred. Preferred luminescent organic metal complexes include, for example, luminescent organic aluminum complexes represented by general formulas (a) to (c). (Q) ₃ -Al (a) (wherein Q represents a substituted or unsubstituted 8-quinolinolate ligand) (Q) ₂ -Al-OL (b) (wherein Q represents substituted 8 Represents a quinolinolate ligand, OL represents a phenolate ligand, and L represents a hydrocarbon group having 6 to 24 carbon atoms including a phenyl moiety.) (Q) ₂ -Al-O-Al- (Q ) ₂ (c) (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-dimethylphenolate) 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-trimethylphenolate) aluminum, bis (2-methyl-8
-Quinolinolate) (2,4,5,6-tetramethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (1-naphtholate) aluminum, bis (2-methyl-8-quinolinolate) (2-naphtholate) ) Aluminum, bis (2,4-dimethyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate)
(3-phenylphenolato) aluminum, bis (2,4-dimethyl-8-quinolinolate) (4-phenylphenolato) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-dimethylphenylphenol Late) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-di-tert-butylphenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) aluminum-μ-oxo-
Bis (2-methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) 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)
-Quinolinolate) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolate) aluminum, bis (2-methyl-5-trifluoromethyl-8-quinolinolate) aluminum-μ-oxo-bis (2 -Methyl-5-trifluoromethyl-8-quinolinolato) aluminum and the like. Of course, the luminescent organometallic complex may be used alone or in combination.

The electron injection / transport layer 5 is a layer containing a compound having a function of facilitating the injection of electrons from the cathode and a function of transporting the injected electrons. The electron injecting / transporting layer is formed of the compound A according to the present invention and / or another compound having an electron injecting / transporting function (eg, an organometallic complex [eg, tris (8-quinolinolate) aluminum, bis (10-benzo [h] quinolinolate) ) Beryllium, 5
Beryllium salt of -hydroxyflavone, aluminum salt of 5-hydroxyflavone], oxadiazole derivative [for example, 1,3-bis [5 ′-(p-tert-butylphenyl) -1,3,4-oxadiazole] -2'-yl] benzene], a triazole derivative [eg, 3-
(4′-tert-butylphenyl) -4-phenyl-5-
(4 "-biphenyl) -1,2,4-triazole],
Triazine derivatives, perylene derivatives, quinoline derivatives,
Quinoxaline derivative, diphenylquinone derivative, nitro-substituted fluorenone derivative, thiopyrandioxide derivative, etc.). When the compound A according to the present invention and another compound having an electron injecting and transporting function are used in combination, the proportion of the compound A according to the present invention in the electron injecting and transporting layer is preferably from 0.1 to 0.1.
It is adjusted to about 40% by weight. In the present invention, the compound A according to the present invention and an organometallic complex [for example, the compounds represented by the general formulas (a) to (c)] are used in combination,
It is preferable to form an electron injection transport layer.

As the cathode 6, it is preferable to use a metal, an alloy or an electrically conductive compound having a relatively small work function as an electrode material. Examples of the electrode material used for the cathode include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, calcium, magnesium, magnesium-silver alloy, magnesium-indium alloy, indium, ruthenium, titanium,
Manganese, yttrium, aluminum, an aluminum-lithium alloy, an aluminum-calcium alloy, an aluminum-magnesium alloy, a graphite thin film, and the like can be given. These electrode substances may be used alone or in combination. The cathode is
Using these electrode substances, for example, a vapor deposition method, a sputtering method, an ionization vapor deposition method, an ion plating method,
It can be formed on the electron injection transport layer by a method such as a cluster ion beam method. Further, the cathode may have a single-layer structure or a multilayer structure. Note that the sheet electric resistance of the cathode is preferably set to several hundred Ω / □ or less. The thickness of the cathode depends on the material of the electrode substance used, but is generally about 5 to 1000 nm,
More preferably, it is set to about 10 to 500 nm.
In order to efficiently extract the light emitted from the organic electroluminescent device, it is preferable that at least one of the anode and the cathode is transparent or translucent, and the transmittance of the emitted light is generally 70% or more. It is more preferable to set the material and thickness of the anode.

The organic electroluminescent device of the present invention may contain a singlet oxygen quencher in at least one layer. The singlet oxygen quencher is not particularly limited and includes, for example, rubrene,
Nickel complexes, diphenylisobenzofuran and the like can be mentioned, and rubrene is particularly preferable. 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.
For example, when a singlet quencher is contained in the hole injecting and transporting layer, the singlet quencher may be contained uniformly in the hole injecting and transporting layer.
(An electron injection / transport layer having a light emitting function). The content of the singlet oxygen quencher is 0.01 to 50% by weight, preferably 0.05 to 3% by weight of the total amount of the contained layer (for example, the hole injection transport layer).
0% by weight, more preferably 0.1 to 20% by weight.

The method for forming the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer is not particularly limited. For example, a vacuum deposition method, an ionization deposition method, a solution coating method (for example, a spin coating method, a Method, dip coating method,
It can be formed by forming a thin film by a bar coating method, a roll coating method, a Langmuir-Brosette method, an inkjet method, or the like. By vacuum evaporation method,
In the case of forming each layer, the conditions of vacuum deposition are not particularly limited, but under a vacuum of about 10 ^-5 Torr, 50 to 6
Boat temperature of about 00 ° C (deposition source temperature), -50 to 30
It is preferable to perform the deposition at a substrate temperature of about 0 ° C. and at a deposition rate of about 0.005 to 50 nm / sec. In this case, each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer,
By continuously forming the organic electroluminescent element under vacuum, an organic electroluminescent device having more excellent various characteristics can be manufactured. When each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer is formed using a plurality of compounds by a vacuum evaporation method,
It is preferred that the temperature of each boat containing the compound be individually controlled and co-evaporated.

When each layer is formed by a solution coating method,
The components forming each layer or the components and the binder resin are dissolved or dispersed in a solvent to form a coating solution. Examples of the binder resin that can be used for each of the hole injection transport layer, the light emitting layer, and the electron injection transport layer include poly-N-vinylcarbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl acrylate, and polymethyl methacrylate. , Polyether, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, polyphenylene oxide, polyethersulfone, polyaniline and its derivatives, polythiophene and its derivatives, polyphenylenevinylene and its derivatives, polyfluorene and its derivatives, polythienyl And high molecular compounds such as lenvinylene and derivatives thereof. The binder resin may be used alone or in combination of two or more. When each layer is formed by a solution coating method, a component forming each layer or the component and a binder resin are mixed 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,
Halogenated hydrocarbon solvents such as trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, for example, ethyl acetate, butyl acetate,
Ester solvents such as amyl acetate, for example, methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, alcohol solvents such as ethylene glycol, for example, dibutyl ether, tetrahydrofuran, dioxane, anisole and the like Ether solvents such as polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, dimethylsulfoxide) and / or Alternatively, a thin film can be formed by various coating methods by dissolving or dispersing in water to form a coating solution.

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

The thicknesses of the hole injecting and transporting layer, the light emitting layer and the electron injecting and transporting layer are not particularly limited, but are generally preferably set to about 5 nm to 5 μm.
A protective layer (sealing layer) may be provided on the manufactured device for the purpose of preventing contact with oxygen or moisture, or the device may be formed of, for example, paraffin, liquid paraffin, silicon oil, fluorocarbon oil, zeolite, or the like. It can be protected by being enclosed in an inert substance such as a contained fluorocarbon oil. Examples of the material used for the protective layer include 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 film, amorphous silica, electrically insulating glass, metal oxide, metal nitride, metal carbide,
Metal sulfide), and a photocurable resin. The material used for the protective layer may be used alone or in combination of two or more. The protective layer may have a single-layer structure or a multilayer structure.

Further, for example, a metal oxide film (for example, an aluminum oxide film) or a metal fluoride film can be provided as a protective layer on the electrode. Also, for example, on the surface of the anode,
For example, an interface layer (intermediate layer) composed of an organic phosphorus compound, polysilane, an aromatic amine derivative, and a phthalocyanine derivative
Can also be provided. Further, electrodes, eg, anodes, can be used by treating the surface with, eg, acid, ammonia / hydrogen peroxide, or plasma.

The organic electroluminescent device of the present invention is generally used as a DC-driven device, but can also be used as a pulse-driven or AC-driven device.
The applied voltage is generally about 2 to 30V. The organic electroluminescent device of the present invention can be used for, for example, a panel light source, various light emitting devices, various display devices, various labels, various sensors, and the like.

[0076]

EXAMPLES The present invention will be described below in more detail with reference to Production Examples and Examples, but it should be understood that the present invention is not limited by these.

Production Example 1 Production of Compound of Exemplified Compound A-1 7.48 g of 1,4-dichloro-9,10-bis (benzo [k] fluoranthene-3'-yl) anthracene and 2.64 g of potassium hydroxide were prepared. Heat and reflux in quinoline (25 ml) for 4 hours. After cooling, the quinoline layer of the reaction mixture was added to a 1 N hydrochloric acid solution (150 ml), and the precipitated crystals were collected by filtration and washed with a 1 N hydrochloric acid solution and water. The crystals were subjected to silica gel column chromatography (eluent: toluene). After the toluene was distilled off under reduced pressure, the residue was recrystallized from a mixed solvent of toluene and acetone to obtain 5.4 g of a compound of Exemplified Compound A-1 as purple crystals. This compound has a melting point of at least 250 ° C.
Sublimation could be performed at 00 ° C. and 10 ⁻⁵ torr. Absorption maximum (in toluene) 627 nm Preparation Examples 2 to 37 In Preparation Example 1, instead of using 1,4-dichloro-9,10-bis (benzo [k] fluoranthene-3′-yl) anthracene, various 1 , 4-Dihalogeno-
According to the method described in Production Example 1, except that a 9,10-bis (benzo [k] fluoranthene-3′-yl) anthracene derivative was used, various bisbenzo [h] fluorenos were used.
[9,1,2-cde: 2 ′, 1 ′, 9′-klm] dibenzo [h, rst] pentaphene derivative was produced. Table 1 (Tables 1 to 8) shows the 1,4-dihalogeno-9,10-bis (benzo [k] fluoranthene-3′-yl) anthracene derivative used and the prepared bisbenzo [h] fluoreno [9]. , 1,2-cde: 2 ',
[1 ', 9'-klm] dibenzo [h, rst] pentaphene derivative is shown by an example compound number. In addition, the absorption maximum in toluene (n
m) is also shown. The produced compound was a purple crystal, and the melting point of the compound was 250 ° C. or higher.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

[Table 3]

[0081]

[Table 4]

[0082]

[Table 5]

[0083]

[Table 6]

[0084]

[Table 7]

[0085]

[Table 8]

Example 1 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) 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) (4-phenylphenolate) aluminum and bisbenzo [h] fluoreno were formed thereon.
[9,1,2-cde: 2 ′, 1 ′, 9′-klm] dibenzo [h, rst] pentaphene (compound of Exemplified Compound No. A-1) was prepared from different evaporation sources at an evaporation rate of 0.2 nm / Co-evaporation (weight ratio 100: 0.5) was performed to a thickness of 50 nm in sec to obtain 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 injecting and transporting layer. Further thereon, magnesium and silver were co-deposited (weight ratio 10: 1) at a deposition rate of 0.2 nm / sec to a thickness of 200 nm to form 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 in a dry atmosphere, the voltage was 54 mA.
/ Cm ² . Red light emission with a luminance of 2420 cd / m ² was confirmed.

Examples 2 to 37 In Example 1, instead of using the compound of Exemplified Compound A-1 in forming the light emitting layer, Exemplified Compound No. A
-2 (Example 2), Exemplified Compound No. A-8 (Example 3), Exemplified Compound No. A-9 (Example 4), Exemplified Compound No. A-10 (Example 5) ), Compound of Exemplified Compound No. A-12 (Example 6),
Compound of Exemplified Compound No. A-13 (Example 7), Compound of Exemplified Compound No. A-17 (Example 8), Compound of Exemplified Compound No. A-25 (Example 9), Exemplified Compound No. A-
26 compound (Example 10), Exemplified Compound No. A-29
(Example 11), compound of Exemplified Compound No. A-34 (Example 12), compound of Exemplified Compound No. A-35 (Example 13), compound of Exemplified Compound No. B-1 (Example 14), Compound of Exemplified Compound No. B-2 (Example 1
5), Compound of Exemplified Compound No. B-3 (Example 16),
Compound of Exemplified Compound No. B-6 (Example 17), Compound of Exemplified Compound No. C-1 (Example 18), Compound of Exemplified Compound No. C-2 (Example 19), Exemplified Compound No. C-
Compound No. 4 (Example 20), Compound No. C-6 (Example 21), Compound No. C-7 (Example 22), Compound No. C-8 (Example 23) Compound of Exemplified Compound No. C-13 (Example 2)
4), Compound of Exemplified Compound No. C-16 (Example 2)
5), Compound of Exemplified Compound No. C-24 (Example 2)
6), Compound of Exemplified Compound No. C-27 (Example 2)
7), Compound of Exemplified Compound No. C-36 (Example 2)
8), Compound of Exemplified Compound No. C-38 (Example 2)
9), Compound of Exemplified Compound No. C-40 (Example 3)
0), Compound of Exemplified Compound No. C-42 (Example 3)
1), Compound of Exemplified Compound No. C-43 (Example 3)
2), Compound of Exemplified Compound No. C-46 (Example 3)
3), the compound of Exemplified Compound No. C-48 (Example 3)
4), Compound of Exemplified Compound No. C-51 (Example 3)
5), Compound of Exemplified Compound No. C-52 (Example 3)
6), Compound of Exemplified Compound No. C-60 (Example 37)
An organic electroluminescent device was produced by the method described in Example 1 except that was used. When a DC voltage of 12 V was applied to each device under a dry atmosphere, red light emission was confirmed. The characteristics were further examined, and the results are shown in Table 2 (Tables 9 to 10).

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

Comparative Example 2 In Example 1, when forming the light emitting layer, instead of using the compound of Exemplified Compound No. A-1, N-methyl-
An organic electroluminescent device was produced by the method described in Example 1 except that 2-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 characteristics,
The results are shown in Table 2.

[0090]

[Table 9]

[0091]

[Table 10]

Example 38 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- (3 ″ -methylphenyl) 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) (4-phenylphenolate) aluminum and the compound of Exemplified Compound No. A-2 were further deposited thereon from different evaporation sources at a deposition rate of 0. 2nm / sec
Co-deposition to a thickness of 50 nm (weight ratio 100: 1.0)
Thus, a light emitting layer was obtained. Next, tris (8-quinolinolato) aluminum is deposited at a deposition rate of 0.2 nm / sec.
It was deposited to a thickness of nm to form an electron injection transport layer. Further thereon, magnesium and silver were deposited at a deposition rate of 0.2 nm / se.
A co-evaporation (weight ratio 10: 1) was carried out to a thickness of 200 nm at c to obtain a cathode, thereby producing an organic electroluminescent device. In addition, evaporation is
The test was performed while maintaining the reduced pressure of the vapor deposition tank. When a DC voltage of 12 V was applied to the produced organic electroluminescent device in a dry atmosphere, a current of 53 mA / cm ² flowed. Brightness 2
Red light emission of 420 cd / m ² was confirmed.

Example 39 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- (3 ″ -methylphenyl) 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, bis (2-methyl-8-quinolinolate) aluminum-μ was formed thereon.
-Oxo-bis (2-methyl-8-quinolinolato) aluminum and the compound of Exemplified Compound No. A-8 were co-deposited from different deposition sources at a deposition rate of 0.2 nm / sec to a thickness of 50 nm (weight ratio: 100: 2.0) 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 injecting and transporting layer. Further thereon, magnesium and silver were co-deposited (weight ratio 10: 1) at a deposition rate of 0.2 nm / sec to a thickness of 200 nm to form an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. In the manufactured organic electroluminescent element,
When a DC voltage of 12 V was applied in a dry atmosphere,
A current of 3 mA / cm ² flowed. Brightness 2420 cd / m ²
Red light emission was confirmed.

Example 40 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) 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 (2,4-dimethyl-8-quinolinolate) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolate) aluminum and Exemplified Compound No. A-9 were formed thereon. Are co-evaporated (weight ratio 100: 4.0) from different evaporation sources to a thickness of 50 nm at an evaporation rate of 0.2 nm / sec.
It was 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 injecting and transporting layer. Further thereon, magnesium and silver were co-deposited (weight ratio 10: 1) at a deposition rate of 0.2 nm / sec to a thickness of 200 nm to form 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 52 mA / cm ² flowed. Brightness 238
Red light emission of 0 cd / m ² was confirmed.

Example 41 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- (3 ″ -methylphenyl) 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, tris (8-quinolinolato) aluminum and the compound of Exemplified Compound No. A-10 were further deposited thereon from different evaporation sources at a deposition rate of 0.1 mm.
Co-deposition to a thickness of 50 nm at 2 nm / sec (weight ratio 10
0: 6.0) to obtain a light emitting layer. Next, tris (8-quinolinolate) aluminum was deposited at a deposition rate of 0.2 nm /
The film was deposited to a thickness of 50 nm in sec to form an electron injection / transport layer. Further thereon, magnesium and silver were co-deposited (weight ratio 10: 1) at a deposition rate of 0.2 nm / sec to a thickness of 200 nm to form an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. The prepared organic electroluminescent device was dried under an atmosphere of 12
When a DC voltage of V was applied, a current of 53 mA / cm ² flowed. Red light emission with a luminance of 2320 cd / m ² was confirmed.

Example 42 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- (3 ″ -methylphenyl) 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, tris (8-quinolinolato) aluminum and the compound of Exemplified Compound No. C-40 were further deposited thereon from different evaporation sources at a deposition rate of 0.
Co-deposition to a thickness of 50 nm at 2 nm / sec (weight ratio 10
0:10) to form a light emitting layer. Next, tris (8-quinolinolate) aluminum was deposited at a deposition rate of 0.2 nm / se.
The film was vapor-deposited to a thickness of 50 nm at c to form an electron injection transport layer.
Further, magnesium and silver were further deposited thereon at a deposition rate of 0.2.
at 200 nm / sec to a thickness of 200 nm (weight ratio: 10:
1) The resultant was used as a cathode to produce an organic electroluminescent device. still,
The 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 59 mA / cm ² flowed. Red light emission with a luminance of 2400 cd / m ² was confirmed.

Example 43 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- (3 ″ -methylphenyl) 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, tris (8-quinolinolato) aluminum and the compound of Exemplified Compound No. C-48 were further deposited thereon from different evaporation sources at a deposition rate of 0.
Co-deposition to a thickness of 50 nm at 2 nm / sec (weight ratio 10
0: 1.0) to obtain a light-emitting layer also serving as an electron injection / transport layer. Further thereon, magnesium and silver were co-deposited (weight ratio 10: 1) at a deposition rate of 0.2 nm / sec to a thickness of 200 nm to form an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. The prepared organic electroluminescent device was dried under an atmosphere of 12
When a DC voltage of V was applied, a current of 57 mA / cm ² flowed. Red light emission with a luminance of 2220 cd / m ² was confirmed.

Example 44 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- (3 ″ -methylphenyl) 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, a compound of Exemplified Compound No. C-48 was further deposited thereon with a deposition rate of 0.2 nm / se.
Evaporated to a thickness of 50 nm at c to obtain a light emitting layer. Then
On top of that, 1,3-bis [5 ′-(p-tert-butylphenyl) -1,3,4-oxadiazol-2′-yl] benzene was deposited at 50 nm at a deposition rate of 0.2 nm / sec.
To form an electron injecting and transporting layer. Further thereon, magnesium and silver were co-deposited (weight ratio 10: 1) at a deposition rate of 0.2 nm / sec to a thickness of 200 nm to form 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 in a dry atmosphere, a current of 44 mA / cm ² flowed. Brightness 196
Red light emission of 0 cd / m ² was confirmed.

Example 45 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, the compound of Exemplified Compound No. A-25 was deposited on the ITO transparent electrode to a thickness of 55 nm at a deposition rate of 0.2 nm / sec to form a light emitting layer. Then, on top of that, 1,3-bis [5 ′-(p-tert-butylphenyl) -1,3,4-
[Oxadiazol-2'-yl] benzene was deposited at a deposition rate of 0.2 nm / sec to a thickness of 75 nm to form an electron injecting and transporting layer. On top of that, magnesium and silver,
A co-deposition (weight ratio: 10: 1) was performed at a deposition rate of 0.2 nm / sec to a thickness of 200 nm 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 in a dry atmosphere, the voltage was 57 mA / cm.
^Two currents flowed. Red light emission with a luminance of 1430 cd / m ² was confirmed.

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 ′, 4 ″ -tris [N
-(3 ′ ″-methylphenyl) -N-phenylamino] triphenylamine at a deposition rate of 0.1 nm / sec.
The first hole injection transport layer was deposited to a thickness of nm. Next, 4,4 ′,-bis [N-phenyl-N- (1 ″ -naphthyl) amino] biphenyl and the compound of Exemplified Compound No. A-1 were deposited from different evaporation sources at an evaporation rate of 0.2 nm / se.
c, co-deposit to a thickness of 20 nm (weight ratio 100: 5),
The light emitting layer also served as the second hole injection / transport layer. Next, tris (8-quinolinolato) aluminum was deposited thereon to a thickness of 50 nm at a deposition rate of 0.2 nm / sec to form an electron injection transport layer. Further thereon, magnesium and silver were co-deposited (weight ratio 10: 1) at a deposition rate of 0.2 nm / sec to a thickness of 200 nm to form an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. In the manufactured organic electroluminescent element,
When a DC voltage of 15 V was applied in a dry atmosphere,
A current of 0 mA / cm ² flowed. Brightness 2660 cd / m ²
Red light emission was confirmed.

Examples 47 to 59 In Example 46, instead of using the compound of Exemplified Compound No. A-1, the compound of Exemplified Compound No. A-2 (Example 47) and the compound of Exemplified Compound No. A-8 (Example 47) Example 4
8), Compound of Exemplified Compound No. A-12 (Example 4)
9), Compound of Exemplified Compound No. A-17 (Example 5)
0), Compound of Exemplified Compound No. A-29 (Example 5)
1), Compound of Exemplified Compound No. A-34 (Example 5)
2), compound of Exemplified Compound No. B-3 (Example 53),
Compound of Exemplified Compound No. B-6 (Example 54), Compound of Exemplified Compound No. C-8 (Example 55), Compound of Exemplified Compound No. C-27 (Example 56), Exemplified Compound No. C
-38 compound (Example 57), Exemplified compound number C-4
An organic electroluminescent device was produced by the method described in Example 46, except that the compound of Example 2 (Example 58) and the compound of Exemplified Compound No. C-52 (Example 59) were used. When a DC voltage of 12 V was applied to each device under a dry atmosphere, red light emission was confirmed. The characteristics were further examined, and the results are shown in Table 3 (Table 11).

[0102]

[Table 11]

Example 60 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, poly-N-vinylcarbazole (weight average molecular weight 1
50000), 1,1,4,4, -tetraphenyl 1,
3-butadiene (blue light-emitting component), coumarin 6 ["3
-(2'-benzothiazolyl) -7-diethylaminocoumarin "(green light-emitting component)] and the compound of Exemplified Compound No. A-10 at a weight ratio of 100: 5: 3:
Using a 3% by weight dichloroethane solution containing 2 parts by weight, a 400 nm light emitting layer was formed by dip coating. Next, after fixing the glass substrate having the light emitting layer to the substrate holder of the vapor deposition apparatus, the vapor deposition tank was set to 3 × 10
^The pressure was reduced to ^-6 Torr. Further, on the light emitting layer, 3- (4 ′
-Tert-butylphenyl) -4-phenyl-5- (4 "
-Biphenyl) 1,2,4-triazole was deposited at a deposition rate of 0.2 nm / sec to a thickness of 20 nm, and tris (8-quinolinolate) aluminum was further deposited thereon at a deposition rate of 0.2 nm / sec. Evaporation was performed to a thickness of 30 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 at 200 nm.
And a cathode was formed by co-evaporation (weight ratio: 10: 1) to obtain an organic electroluminescent device. When a DC voltage of 12 V was applied to the produced organic electroluminescent device in a dry atmosphere, a current of 64 mA / cm ² flowed. Luminance 1320cd
/ M ² was confirmed.

Examples 61-66 Instead of using the compound of Exemplified Compound No. A-10 in Example 60, the compound of Exemplified Compound No. A-13 (Example 61) and the compound of Exemplified Compound No. A-34 (Example Example 62), a compound of Exemplified Compound No. C-4 (Example 6)
3), Compound of Exemplified Compound No. C-16 (Example 6)
4), Compound of Exemplified Compound No. C-27 (Example 6)
5), Compound of Exemplified Compound No. C-48 (Example 66)
An organic electroluminescent device was produced by the method described in Example 60, except that was used. When a DC voltage of 12 V was applied to each device under a dry atmosphere, white light emission was observed. The characteristics were further examined, and the results are shown in Table 4 (Table 12).

[0105]

[Table 12]

Example 67 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, 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. A-2 were formed by dip coating using a 3% by weight dichloroethane solution containing 100: 30: 3 by weight to form a 300 nm light emitting layer. 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. The prepared organic electroluminescent device was dried under a dry atmosphere for 15 minutes.
When a DC voltage of V was applied, a current of 71 mA / cm ² flowed. Red light emission with a luminance of 1320 cd / m ² was confirmed.

Comparative Example 3 The procedure of Example 67 was repeated except that 1,1,4,4-tetraphenyl-1,3-butadiene was used instead of the compound of Exemplified Compound No. A-2 in forming the light emitting layer. ,
An organic electroluminescent device was produced by the method described in Example 67. 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 750 cd / m ² was confirmed.

Example 68 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-
Quinolinolate) aluminum-μ-oxo-bis (2
-Methyl-8-quinolinolate) aluminum and the compound of Exemplified Compound No. C-8 were each added at a weight ratio of 10
Using a 3% by weight dichloroethane solution containing 0: 40: 60: 1 at a ratio of 30% by a dip coating method.
A 0 nm light emitting layer was formed. Next, after fixing the glass substrate having the light emitting layer to a substrate holder of a vapor deposition device,
The pressure in the evaporation tank was reduced to 3 × 10 ⁻⁶ Torr. Further, on the light emitting layer, magnesium and silver were deposited at a deposition rate of 0.2 nm / sec.
Then, co-evaporation (weight ratio: 10: 1) was performed to a thickness of 200 nm to form a cathode, thereby producing an organic electroluminescent device. When a DC voltage of 15 V was applied to the produced organic electroluminescent device in a dry atmosphere, a current of 63 mA / cm ² flowed. Brightness 89
Red light emission of 0 cd / m ² was confirmed.

[0109]

According to the present invention, it has become possible to provide an organic electroluminescent device having excellent light emission luminance. Further, it has become possible to provide a hydrocarbon compound suitable for the light-emitting element.

[Brief description of the drawings]

FIG. 1 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 2 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 3 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 4 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 5 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 6 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 7 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 8 is a schematic structural diagram of an example of an organic electroluminescent device.

[Explanation of symbols]

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 43/225 C07C 43/225 C C09K 11/06 610 C09K 11/06 610 660 660 H05B 33/14 H05B 33 / 14 B 33/22 33/22 D B F term (reference) 3K007 AB02 AB03 AB04 BB06 CA01 CA02 CA06 CB01 DA00 DB03 EB00 FA01 FA03 4H006 AA01 AA03 AB92 EA43 GP03

Claims (8)

[Claims] A layer containing at least one derivative of bisbenzo [h] fluoreno [9,1,2-cde: 2 ′, 1 ′, 9′-klm] dibenzo [h, rst] pentaphene between a pair of electrodes. , An organic electroluminescent device comprising at least one layer sandwiched therebetween. 2. Bisbenzo [h] fluoreno [9,1,2-cde:
The organic electroluminescent device according to claim 1, wherein the layer containing a 2 ', 1', 9'-klm] dibenzo [h, rst] pentaphene derivative is a light emitting layer. 3. Bisbenzo [h] fluoreno [9,1,2-cde:
3. The organic electroluminescence according to claim 1, wherein the layer containing a 2 ', 1', 9'-klm] dibenzo [h, rst] pentaphene derivative further contains a luminescent organometallic complex. element. 4. Bisbenzo [h] fluoreno [9,1,2-cde:
3. The organic electroluminescent device according to claim 1, wherein the layer containing a 2 ', 1', 9'-klm] dibenzo [h, rst] pentaphene 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. Bisbenzo [h] fluoreno [9,1,2-cde:
The 2 ', 1', 9'-klm] dibenzo [h, rst] pentaphene derivative is a compound represented by the general formula (1-A) (formula 1). Organic electroluminescent device. Embedded image (Wherein X _{1 to} X ₂₆ each independently represent a hydrogen atom, a halogen atom, a straight-chain, branched or cyclic alkyl group, a straight-chain,
Represents a branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group. ) 8. A compound represented by the general formula (1-A): Embedded image (Wherein X _{1 to} X ₂₆ each independently represent a hydrogen atom, a halogen atom, a straight-chain, branched or cyclic alkyl group, a straight-chain,
Represents a branched or cyclic alkoxy group, or a substituted or unsubstituted aryl group. )