JP2002069044A - Organic electroluminescence element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescence element having a high heat resistance, and high luminous efficiency, and further to provide a new hydrocarbon compound usable for achieving the element. SOLUTION: This new hydrocarbon compound is represented by the general formula (1): Xn-Ar1, wherein, Ar1 is a substituted or unsabstituted 6-40C aromatic ring group, a substituted or unsabstituted 6-40C arylamino group, a substituted or unsabstituted 6-60C diaminoaryl group, a substituted or unsabstituted 6-60C triaminoaryl group, a substituted or unsabstituted 3-40C heterocyclic group or a substituted or unsabstituted ethenylene; X is a monovalent group having a fluoranthene structure; and n is an integer of 2-4. The organic electroluminescence element has at least one layer of an organic compound layer having a luminous layer, containing the new hydrocarbon compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel hydrocarbon compound and an organic electroluminescent device.
The present invention relates to an organic electroluminescent device having high heat resistance and high luminous efficiency, and a novel hydrocarbon compound realizing the same.

[0002]

2. Description of the Related Art An organic electroluminescent (EL) device using an organic substance is used as a light source such as a flat light-emitting body of a wall-mounted television or a backlight of a display.
It is being actively developed. In particular, recently, an organic electroluminescence device having both high heat resistance and high efficiency and a compound for realizing the same have been developed. For example, Japanese Patent Application Laid-Open No. 8-12600 discloses a phenylanthracene compound and a device using the same, in which the heat resistance is improved by setting the glass transition temperature to 140 ° C. or higher. The luminous efficiency calculated by is as low as about 2 cd / A, and improvement has been required. Also, Japanese Patent Application Laid-Open No. H10-72579 discloses an aminoanthracene compound and a device using the same, which have improved luminous efficiency but insufficient heat resistance. Further, Japanese Patent Application Laid-Open No. 10-189247 discloses an element using a fluoranthene-based compound. However, since the element is a compound comprising a monomer of a fluoranthene-based compound, improvement in heat resistance is insufficient. .

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and provides an organic electroluminescent device having high heat resistance and high luminous efficiency, and a novel hydrocarbon compound realizing the same. It is intended to do so.

[0004]

The present inventors have conducted intensive studies to develop an organic electroluminescent device (hereinafter, referred to as an organic EL device) having the above-mentioned preferable properties. As a result, an aryl structure is bonded to a fluoranthene structure. It has been found that when the novel hydrocarbon compound is added to the organic compound film, the heat resistance of the organic electroluminescence device is improved, and the hole transporting property and the electron transporting property are improved to achieve high luminous efficiency. Reached.

That is, the present invention provides a novel hydrocarbon compound represented by the following general formula (1): X _n -Ar ₁ (1) wherein Ar ₁ is a substituted or unsubstituted carbon atom Number 6
To 40 aromatic ring groups, substituted or unsubstituted arylamino groups having 6 to 40 carbon atoms, substituted or unsubstituted diaminoaryl groups having 6 to 60 carbon atoms, substituted or unsubstituted carbon atoms having 6 to 60 carbon atoms 60 triaminoaryl groups,
A substituted or unsubstituted heterocyclic group having 3 to 40 carbon atoms or a substituted or unsubstituted ethenylene, X is a monovalent group having a fluoranthene structure, and n is an integer of 2 to 4. )
Is provided. Further, the present invention relates to an organic electroluminescence element (organic EL element) having an organic compound film composed of a single layer or a plurality of layers having at least a light emitting layer between a pair of electrodes, wherein at least one of the organic compound films is formed. Another object of the present invention is to provide an organic electroluminescent device containing the novel hydrocarbon compound.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The novel hydrocarbon compound of the present invention comprises
It is represented by the general formula (1). In the formula, Ar ₁ is a substituted or unsubstituted aromatic ring group having 6 to 40 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 40 carbon atoms, a substituted or unsubstituted 6 to 40 carbon atoms. 60 diaminoaryl groups, substituted or unsubstituted 6 to 6 carbon atoms
0 is a triaminoaryl group, a substituted or unsubstituted heterocyclic group having 3 to 40 carbon atoms, or a substituted or unsubstituted ethenylene. X is a monovalent group having a fluoranthene structure, and n is an integer of 2 to 4.

The X is preferably a monovalent group of a compound having a structure represented by the following general formulas [1] to [3].

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In the general formulas [1] to [3], X ^{1 to} X
¹⁶ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted straight-chain, branched or cyclic alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted straight-chain, branched or cyclic carbon atom number; 1 to 30 alkoxy groups,
A substituted or unsubstituted straight-chain, branched or cyclic alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted straight-chain, branched or cyclic alkenyl group having 2 to 30 carbon atoms, Chain, branched or cyclic alkenyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted linear, branched or cyclic carbon atom having 2 to 30 carbon atoms
30 alkenylthio groups, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted aralkyloxy groups having 7 to 30 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms A thio group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 20 carbon atoms, Or 2 to 30 carbon atoms which are unsubstituted
Amino group, a cyano group, a hydroxyl group, -COOR ¹ group (wherein, R ¹ represents a hydrogen atom, a linear substituted or unsubstituted, branched or cyclic alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted Represents a straight-chain, branched or cyclic alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) , -COR
² groups (wherein R ² is a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted linear, branched or cyclic carbon atom having 2 carbon atoms) 30 alkenyl group, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or an amino group), - OCOR ³ group (wherein , R ³ are a substituted or unsubstituted linear, branched or cyclic C 1 -C 3
0 alkyl group, substituted or unsubstituted linear, branched or cyclic alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted carbon atom Represents an aryl group of 6 to 30), and among X ^{1 to} X ¹⁶ , an adjacent group and a substituent of each group may be bonded to each other to form a substituted or unsubstituted carbon ring. Good.

The organic EL device of the present invention is an organic electroluminescent device having an organic compound film comprising at least a single layer or a plurality of layers having a light emitting layer between a pair of electrodes, wherein at least one of the organic compound films is provided. The novel hydrocarbon compound is contained. It is preferable that the light emitting layer contains the novel hydrocarbon compound. It is also preferable that the electron injection layer or the hole injection layer contains the novel hydrocarbon compound. An inorganic compound layer may be provided between the light emitting layer and the electrode. More preferably, the light emitting layer contains a condensed polycyclic aromatic derivative as a light emitting center. The heat resistance and the luminous efficiency are improved when the novel hydrocarbon compound is contained in at least one layer of the organic compound film,
This is because the fluoranthene structure has high fluorescence, and the glass transition temperature of the compound represented by the general formula (1) is increased by setting n = 2 to 4 in the compound.

Hereinafter, typical examples (A1) to (A24) of the novel hydrocarbon compound of the present invention will be illustrated, but the present invention is not limited to these typical examples.

[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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The organic EL device of the present invention is a device in which a single-layer or multilayer organic compound film is formed between an anode and a cathode. In the case of a single layer type, a light emitting layer is provided between an anode and a cathode. The light-emitting layer contains a light-emitting material and may further contain a hole-injection material or an electron-injection material for transporting holes injected from an anode or electrons injected from a cathode to the light-emitting material. However, it is preferable that the light emitting material has extremely high fluorescence quantum efficiency, high hole transport ability and electron transport ability, and forms a uniform thin film. The multilayer type organic EL device includes (anode / hole injection layer / light emitting layer / cathode), (anode / light emitting layer / electron injection layer / cathode), (anode / hole injection layer / light emitting layer / electron injection layer / (Cathode).

In the light emitting layer, if necessary, further known light emitting materials, doping materials, hole injection materials and electron injection materials can be used in addition to the novel hydrocarbon compound of the present invention. As a preferred use of the novel hydrocarbon compound, it is added to any one of the light emitting layer, the electron injection layer, the hole transport layer and the hole injection layer at a concentration of 0.5 to 50% by weight. More preferably, the concentration is 1 to 20% by weight.
When the organic EL element has a multilayer structure, it is possible to prevent a decrease in luminance and life due to quenching. If necessary, a combination of a light emitting material, another doping material, a hole injection material and an electron injection material can be used. Further, with other doping materials, emission luminance and emission efficiency can be improved, and red and white light can be obtained. Further, each of the hole injection layer, the light emitting layer, and the electron injection layer may be formed in a layer structure of two or more layers. In this case, in the case of a hole injection layer, a layer for injecting holes from the electrode is a hole injection layer, and a layer for receiving holes from the hole injection layer and transporting holes to the light emitting layer is a hole transport layer. Call. Similarly, in the case of an electron injection layer, a layer that injects electrons from the electrode is called an electron injection layer, and a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer is called an electron transport layer. Each of these layers is selected and used depending on factors such as the energy level of the material, heat resistance, and adhesion to an organic compound film or a metal electrode.

The light-emitting material or host material which can be used in the organic compound film together with the above-mentioned novel hydrocarbon compound includes condensed polycyclic aromatics, such as anthracene, naphthalene, phenanthrene, pyrene, tetracene, pentacene, coronene, chrysene, fluorescein, and the like. Perylene,
There are rubrene and their derivatives. Further, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline Metal complexes, imines,
Diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, merocyanine, imidazole chelated oxinoid compound,
Examples include, but are not limited to, quinacridone, rubrene, stilbene derivatives, and fluorescent dyes.

The hole injecting material has the ability to transport holes, has the effect of injecting holes from the anode, and has an excellent hole injecting effect on the light emitting layer or the light emitting material. A compound that prevents excitons from migrating to the electron injection layer or the electron injection material and has excellent thin film forming ability is preferable.
Specifically, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acylhydrazone, polyaryl Alkanes, stilbene, butadiene, benzidine-type triphenylamine, styrylamine-type triphenylamine,
Diamine-type triphenylamine and the like, derivatives thereof,
And polymer materials such as polyvinyl carbazole, polysilane, and conductive polymers, but are not limited thereto.

Among the hole injection materials that can be used in the organic EL device of the present invention, more effective hole injection materials are
It is an aromatic tertiary amine derivative or a phthalocyanine derivative. Specific examples of the aromatic tertiary amine derivative include triphenylamine, tolylamine, tolylphenylamine, N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4 '-Diamine, N, N, N', N '-(4-methylphenyl)-
1,1′-phenyl-4,4′-diamine, N, N,
N ', N'-(4-methylphenyl) -1,1'-biphenyl-4,4'-diamine, N, N'-diphenyl-
N, N'-dinaphthyl-1,1'-biphenyl-4,
4'-diamine, N, N '-(methylphenyl) -N,
N '-(4-n-butylphenyl) -phenanthrene-
9,10-diamine, N, N-bis (4-di-4-tolylaminophenyl) -4-phenyl-cyclohexane, and the like, or oligomers or polymers having an aromatic tertiary amine skeleton. However, the present invention is not limited to this. Specific examples of the phthalocyanine (Pc) derivative include H ₂ Pc, CuPc, CoPc, NiPc, Zn
Pc, PdPc, FePc, MnPc, ClAlPc,
ClGaPc, ClInPc, ClSnPc, Cl ₂ S
iPc, (HO) AlPc, (HO) GaPc, VOP
c, TiOPc, MoOPc, GaPc-O-GaPc
Phthalocyanine derivatives and naphthalocyanine derivatives, but are not limited thereto.

The electron injecting material has the ability to transport electrons, has the effect of injecting electrons from the cathode, and has an excellent electron injecting effect on the light emitting layer or the light emitting material. Compounds that prevent migration to the hole injection layer and have excellent thin film forming ability are preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole,
Triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane,
Examples include, but are not limited to, anthrones and their derivatives. Further, the charge injecting property can be improved by adding an electron accepting substance to the hole injecting material and an electron donating substance to the electron injecting material.

In the organic EL device of the present invention, a more effective electron injecting material is a metal complex compound or a nitrogen-containing five-membered ring derivative. A specific example of the metal complex compound is 8-
Lithium hydroxyquinolinato, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc , Bis (2-methyl-8-
Quinolinato) chlorogallium, bis (2-methyl-8)
-Quinolinato) (o-cresolate) gallium, bis (2-methyl-8-quinolinato) (1-naphtholate) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholate) gallium, and the like,
It is not limited to these.

The nitrogen-containing five-membered derivative is preferably an oxazole, thiazole, oxadiazole, thiadiazole or triazole derivative. In particular,
2,5-bis (1-phenyl) -1,3,4-oxazole, dimethyl POPOP, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1-phenyl) ) -1,3,4-oxadiazole, 2- (4 ′
-Tert-butylphenyl) -5- (4 "-biphenyl) 1,3,4-oxadiazole, 2,5-bis (1
-Naphthyl) -1,3,4-oxadiazole, 1,4
-Bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene], 2- (4 '
-Tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1
-Naphthyl) -1,3,4-thiadiazole, 1,4-
Bis [2- (5-phenylthiadiazolyl)] benzene, 2- (4'-tert-butylphenyl) -5- (
4 "-biphenyl) -1,3,4-triazole, 2,
5-bis (1-naphthyl) -1,3,4-triazole, 1,4-bis [2- (5-phenyltriazolyl)
], But not limited thereto. In the present invention, an inorganic compound layer may be provided between the light emitting layer and the electrode for improving the charge injection property.
Examples of such an inorganic compound layer include an alkali metal compound (such as a fluoride and an oxide) and an alkaline earth metal compound. Specifically, LiF, Li ₂ O, BaO, and Sr
O, BaF ₂ , SrF _{2 and the} like.

As the conductive material used for the anode of the organic EL element, those having a work function of more than 4 eV are suitable, such as carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, and platinum. , Palladium and their alloys, tin oxide used for ITO substrate, NESA substrate, metal oxide such as indium oxide,
Further, an organic conductive resin such as polythiophene or polypyrrole is used. As the conductive material used for the cathode, those having a work function smaller than 4 eV are suitable, and magnesium, calcium, tin, lead, titanium,
Yttrium, lithium, ruthenium, manganese, aluminum and the like and alloys thereof are used, but not limited thereto. Representative examples of the alloy include magnesium / silver, magnesium / indium, and lithium / aluminum, but are not limited thereto. The ratio of the alloy is controlled by the temperature, atmosphere, degree of vacuum, and the like of the evaporation source, and is selected to be an appropriate ratio. The anode and the cathode may be formed by two or more layers if necessary.

In the organic EL device, in order to efficiently emit light, it is desirable that at least one surface is sufficiently transparent in the emission wavelength region of the device. Further, it is desirable that the substrate is also transparent. The transparent electrode is set using the above-described conductive material so as to secure a predetermined translucency by a method such as vapor deposition or sputtering. The electrode on the light emitting surface desirably has a light transmittance of 10% or more. The substrate is not limited as long as it has mechanical and thermal strength and transparency, and examples thereof include a glass substrate and a transparent resin film. Transparent resin films include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, and polyetheretherketone. , Polysulfone,
Polyether sulfone, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinylidenefluor Ride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide, polyimide, polypropylene and the like.

In the organic EL device of the present invention, a protective layer can be provided on the surface of the device, or the entire device can be protected by silicon oil, resin, or the like in order to improve stability against temperature, humidity, atmosphere, and the like. It is. Each layer of the organic EL element is formed by a dry film forming method such as vacuum evaporation, sputtering, plasma, ion plating, spin coating, or the like.
Any of wet film forming methods such as dipping and flow coating can be applied. The film thickness is not particularly limited, but needs to be set to an appropriate film thickness. If the film thickness is too large, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too small, pinholes and the like are generated, and sufficient light emission luminance cannot be obtained even when an electric field is applied. Normal thickness is 5nm to 10μ
The range of m is suitable, but the range of 10 nm to 0.2 μm is more preferable.

In the case of the wet film forming method, the material forming each layer is made of ethanol, chloroform, tetrahydrofuran,
The thin film is formed by dissolving or dispersing in a suitable solvent such as dioxane, and any solvent may be used. In any of the organic thin film layers, a suitable resin or additive may be used for improving film forming properties, preventing pinholes in the film, and the like. Examples of usable resins include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, and copolymers thereof, and poly-N-vinyl. Examples thereof include photoconductive resins such as carbazole and polysilane, and conductive resins such as polythiophene and polypyrrole.
In addition, examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.

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

[0029]

The present invention will be described below in more detail with reference to Synthesis Examples and Examples. Synthesis Example 1 (Compound (A1)) Compound (A1) was produced by the following reaction route.

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(1) Synthesis of 7,10-diphenylfluoranthene-3-boronic acid Under an argon atmosphere, 3-bromo-7,10-diphenylfluoranthene (25 g, 58 mmol) was added to anhydrous ether (150 ml).
And cooled to −35 ° C. in a dry ice / methanol bath. The n-butyllithium / hexane solution (1.50m
ol / l, 43 ml, 65 mmol) was added dropwise, and the mixture was stirred at -20 ° C for 1 hour. The reaction mixture was cooled to -70 ° C and triisopropoxysilane (37 ml, 0.16 mol, 2.8 eq) in anhydrous ether (30 ml)
Was added, and the mixture was stirred at -65 ° C for 1 hour and at room temperature for 2 hours, and left overnight. A 10% aqueous hydrochloric acid solution (150 ml) was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour.
0 ml), dried over anhydrous magnesium sulfate, and the solvent obtained by evaporating the solvent was washed with hexane to give a white solid (19 g, 48 m
mol, yield 83%).

(2) 1,4'-bis (3- (7,10-
Synthesis of diphenyl) fluoranthenyl) benzene (A1) Under an argon atmosphere, 7,10-diphenylfluoranthene-3-boronic acid (18 g, 45 mmol, 2.8 eq), 1,4-dibromobenzene (3.8 g, 16 mmol) , Tetrakis (triphenylphosphine) palladium (0) (0.37 g, 0.32 mmol, 2% Pd) were suspended in toluene (200 ml), and an aqueous sodium carbonate solution (10
g, 94 mmol, 5.8 eq / 48 ml), refluxed for 10 hours, and left overnight. The reaction mixture was filtered off, washed with water, methanol and acetone to obtain a gray solid (11 g, 14 mmol, yield 88%), and further purified by sublimation to obtain a yellow solid (9.1 g, 11 mmol). The obtained solid was subjected to measurement of 400 MHz NMR spectrum, proton NMR spectrum, and FD-MS (field desorption mass spectrum) to obtain compound (A1).
Was confirmed.

Synthesis Example 2 (Compound (A2)) Compound (A2) was produced according to the following reaction route.

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(1) Synthesis of N, N'-bis (7,10-diphenyl-3-fluoranttoyl) hydrazine In a flask, hydrazine sulfate (2.2 g, 17 mmol) was added.
Was added to distilled water (40 ml), and further sodium hydroxide (1.5 g,
(38 mmol) was stirred while cooling in an ice bath. Next, sodium hydroxide (1.6 g, 40 mmol) was added to distilled water (30 m
l) and a solution of 7,10-diphenyl-3-fluorantyl chloride (15 g, 36 mmol) was added dropwise to the flask over 1 hour. After stirring at 10 ° C. for 2 hours, the mixture was filtered to obtain a white residue. 50% of this residue
Wash with aqueous acetone, filter and dry again to give a white solid
(8.7 g, 11 mmol, 65% yield).

(2) Synthesis of 2,5-bis (3- (7,10-diphenyl) fluoranthenyl) -1,3,4-thiadiazole (A2) Phosphora pentasulfide (3.2
g, 14 mmol), N, N'-bis (7,10-diphenyl-
3-Fluorantyl) hydrazine (8.7 g, 11 mmol) was added to anhydrous chloroform (50 ml) and refluxed for 40 hours. Then, after washing twice with a 10% aqueous potassium hydroxide solution (50 ml), washing twice with distilled water, drying with magnesium sulfate, distilling off the solvent and purifying by column chromatography, yellow crystals (4.0 g, 5.0 mmol, yield 45%). The resulting crystals are
It was confirmed to be Compound (A2) by measurement of 400 MHz NMR spectrum, proton NMR spectrum and FD-MS.

Synthesis Example 3 (Compound (A3)) Compound (A3) was produced according to the following reaction route.

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(1) Synthesis of 4,7-bis (3- (7,10-diphenyl) fluoranthenyl) -2,1,3-benzothiazole (A3) 7,10-diphenylfluoran under an argon atmosphere Ten-3-boronic acid (18 g, 45 mmol, 2.8 eq), 4,7-dibromo-2,1,3-benzothiazole (4.7 g, 16 mmol), tetrakis (triphenylphosphine) palladium (0) (0.
37 g, 0.32 mmol, 2% Pd) was suspended in toluene (200 ml), an aqueous sodium carbonate solution (10 g, 94 mmol, 5.8 eq / 48 ml) was added, the mixture was refluxed for 10 hours, and left overnight. The reaction mixture is filtered off,
The solid was washed with water, methanol and acetone, and purified by column chromatography to obtain a brown solid (9.7 g, 12 mmol, yield 72%). The obtained solid was confirmed to be the compound (A3) by measurement of a 400 MHz NMR spectrum, a proton NMR spectrum, and FD-MS.

Synthesis Example 4 (Compound (A6)) Compound (A6) was produced according to the following reaction route.

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(1) Synthesis of fluoranthene-3-boronic acid Under an argon atmosphere, 3-bromofluoranthene (15 g, 53 m
mol) in anhydrous ether (120 ml) and dry ice /
Cooled to −35 ° C. in a methanol bath. An n-butyllithium / hexane solution (1.50 mol / l, 38 ml, 58 mmol) was added dropwise thereto, and the mixture was stirred at -20 ° C for 1 hour. The reaction mixture was cooled to -70 ° C and triisopropoxysilane (28 ml, 0.12 mol, 2.3 eq)
Of anhydrous ether (25 ml) was added at -65 ° C for 1 hour,
Stirred at room temperature for 2 hours and left overnight. 10% in the reaction mixture
An aqueous hydrochloric acid solution (120 ml) was added, and the mixture was stirred at room temperature for 1 hour. The organic layer was separated, washed with saturated saline (40 ml), dried over anhydrous magnesium sulfate, and the solvent was distilled off. Washing gave a white solid (11 g, 45 mmol, 85% yield).

(2) Synthesis of 1,3,5-tris (3-fluoranthenyl) benzene (A6) Fluoranthene-3-boronic acid (10
g, 41 mmol, 3.8 eq), 1,3,5-tribromobenzene (3.
5g, 11mmol), tetrakis (triphenylphosphine)
Palladium (0) (0.29 g, 0.25 mmol, 2.3% Pd) was dissolved in toluene (150
sodium carbonate aqueous solution (9 g, 86 mmol, 7.8 eq).
/ 43 ml) and refluxed for 10 hours and left overnight. The reaction mixture was separated by filtration, washed with water, methanol and acetone to obtain a gray solid (6.5 g, 9.6 mmol, yield 87%), and further purified by sublimation to obtain a yellow solid (4.3 g, 6.4 mmol). The resulting solid is 4
It was confirmed to be Compound (A6) by measurement of 00 MHz NMR spectrum, proton NMR spectrum and FD-MS.

Synthesis Example 5 (Compound (A9)) Compound (A9) was produced according to the following reaction route.

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(1) Synthesis of 9,10-bis (3-fluoranthenyl) anthracene (A9) Fluoranthene-3-boronic acid (10
g, 41 mmol, 2.2 eq), 9,10-dibromoanthracene (6.
3g, 19mmol), tetrakis (triphenylphosphine)
Palladium (0) (0.44 g, 0.38 mmol, 2% Pd) was dissolved in toluene (150 m
l), and aqueous sodium carbonate solution (8.6 g, 82 mmol, 4.4 e
(q / 40 ml), and the mixture was refluxed for 10 hours and left overnight. The reaction mixture was filtered off, washed with water, methanol and acetone to obtain a gray solid (10 g, 17 mmol, yield 91%), and further purified by sublimation to obtain a yellow solid (8.4 g, 14 mmol). The resulting solid is 4
It was confirmed to be Compound (A9) by measurement of 00 MHz NMR spectrum, proton NMR spectrum and FD-MS.

Synthesis Example 6 (Compound (A15)) Compound (A15) was produced according to the following reaction route.

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(1) N, N'-bis (3- (7,10-
Synthesis of diphenyl) fluoranthenyl) aniline (A15) Under an argon atmosphere, 3-bromo-7,10-diphenylfluoranthene (5 g, 12 mmol), palladium acetate (2) (0.06
g, 0.3 mmol), tri-t-butylphosphine (0.23 g, 1.1 mm
ol), sodium t-butoxy (1.6 g, 16 mmol) and aniline (0.5 g, 6 mmol) were added to anhydrous toluene (50 ml), stirred at room temperature for 30 minutes, and refluxed for 7 hours. The precipitated crystals were collected by filtration, washed with toluene and water, and dried under reduced pressure to obtain a yellow solid. Further purified by column chromatography, a pale yellow solid
(4.5 g, 5.7 mmol, 96% yield). The resulting solid is 40
It was confirmed to be Compound (A15) by measurement of 0 MHz NMR spectrum, proton NMR spectrum and FD-MS.

Synthesis Example 7 (Compound (A16)) Compound (A16) was produced according to the following reaction route.

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(1) Synthesis of 3,6-bis (3- (7,10-diphenyl) fluoranthenyl) -9-phenylcambazole (A16) 7,10-diphenylfluoranthene-3 under an argon atmosphere -Boronic acid (9 g, 22 mmol, 2.4 eq), 3,6-dibromo-9-cambazole (3.7 g, 9.2 mmol), tetrakis (triphenylphosphine) palladium (0) (0.21 g, 0.18 mmol
1,2% Pd) was suspended in toluene (100 ml), an aqueous sodium carbonate solution (6.9 g, 65 mmol, 7.0 eq / 33 ml) was added, the mixture was refluxed for 14 hours, and left overnight. The reaction mixture was filtered, washed with water, methanol and acetone, and purified by column chromatography to obtain a pale yellow solid (8.1 g, 8.5 mmol, yield 92%). The obtained solid was confirmed to be the compound (A16) by measurement of a 400 MHz NMR spectrum, a proton NMR spectrum, and FD-MS.

Synthesis Example 8 (Compound (A18)) Compound (A18) was produced according to the following reaction route.

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(1) Synthesis of fluoranthene-8-boronic acid Under an argon atmosphere, 8-bromofluoranthene (15 g, 53 m
mol) in anhydrous ether (120 ml) and dry ice /
Cooled to −35 ° C. in a methanol bath. An n-butyllithium / hexane solution (1.50 mol / l, 38 ml, 58 mmol) was added dropwise thereto, and the mixture was stirred at -20 ° C for 1 hour. The reaction mixture was cooled to -70 ° C and triisopropoxysilane (28 ml, 0.12 mol, 2.3 eq)
Of anhydrous ether (25 ml) was added at -65 ° C for 1 hour,
Stirred at room temperature for 2 hours and left overnight. 10% in the reaction mixture
An aqueous hydrochloric acid solution (120 ml) was added, and the mixture was stirred at room temperature for 1 hour. The organic layer was separated, washed with saturated saline (40 ml), dried over anhydrous magnesium sulfate, and the solid obtained by evaporating the solvent was washed with hexane. This gave a white solid (12 g, 49 mmol, 92% yield).

(2) Synthesis of 1,4-bis (8-fluoranthenyl) benzene (A18) Under an argon atmosphere, fluoranthene-8-boronic acid (9 g,
37 mmol, 2.3 eq), 1,4-dibromobenzene (3.8 g, 16 mm
ol) and tetrakis (triphenylphosphine) palladium (0) (0.37 g, 0.32 mmol, 2% Pd) were suspended in toluene (200 ml), and an aqueous sodium carbonate solution (10 g, 94 mmol, 5.8 eq / 48 ml) was added. Reflux for hours and leave overnight. The reaction mixture was filtered off, washed with water, methanol and acetone to give a gray solid (7.4
g, 15 mmol, yield 94%), and further purified by sublimation to obtain a pale yellow solid (6.0 g, 12 mmol). The resulting solid is 400M
It was confirmed to be Compound (A18) by measurement of Hz NMR spectrum, proton NMR spectrum and FD-MS.

Synthesis Example 9 (Compound (A20)) Compound (A20) was produced according to the following reaction route.

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(1) Synthesis of 3-N, N'-diphenylaminofluoranthene-8-boronic acid Under an argon atmosphere, 3-N, N'-diphenylaminofluoranthene (12 g, 27 mmol) was treated with anhydrous ether ( 100 ml) and cooled to -35 ° C in a dry ice / methanol bath. Add n-butyllithium / hexane solution (1.50mol
/ l, 19 ml, 29 mmol) was added dropwise, and the mixture was stirred at -20 ° C for 1 hour.
The reaction mixture was cooled to -70 ° C, triisopropoxysilane (14 ml, 60 mmol, 2.2 eq) in anhydrous ether (20 ml) was added, and the mixture was stirred at -65 ° C for 1 hour, at room temperature for 3 hours, and left overnight. did. A 10% aqueous hydrochloric acid solution (100 ml) was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour.
, Dried over anhydrous magnesium sulfate, and the solid obtained by evaporating the solvent was washed with hexane to give a white solid (9.2 g, 23 mmo).
l, yield 85%).

(2) 1,4-bis (8- (3-N, N ')
-Diphenylamino) fluoranthenyl) benzene (A
Synthesis of 20) Under an argon atmosphere, 3-N, N′-diphenylaminofluoranthene-8-boronic acid (9 g, 22 mmol, 2.2 eq), 1,
4-dibromobenzene (2.4 g, 10 mmol), tetrakis (triphenylphosphine) palladium (0) (0.23 g, 0.20 mmo
1,2% Pd) was suspended in toluene (150 ml), an aqueous sodium carbonate solution (6.4 g, 60 mmol, 6.0 eq / 31 ml) was added, the mixture was refluxed for 12 hours, and left overnight. The reaction mixture was filtered and washed with water, methanol and acetone to give a gray solid (6.9 g, 8.5 mmol, yield 85).
%), And further purified by sublimation to give a pale yellow solid (5.2 g, 6.4 mmo).
l) was obtained. The obtained solid was confirmed to be the compound (A20) by measurement of a 400 MHz NMR spectrum, a proton NMR spectrum, and FD-MS.

Example 1 A 25 mm × 75 mm × 1.1 mm thick glass substrate with an ITO transparent electrode (manufactured by Geomatic Co., Ltd.) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes and then UV ozone cleaning for 30 minutes. The glass substrate with the transparent electrode lines after cleaning is mounted on a substrate holder of a vacuum evaporation apparatus, and first, N, N having a film thickness of 60 nm is coated on the surface on the side where the transparent electrode lines are formed so as to cover the transparent electrodes. A '-bis (N, N'-diphenyl-4-aminophenyl) -N, N'-diphenyl-4,4'-diamino-1,1'-biphenyl film (hereinafter, TPD232 film) was formed. This TPD232 film functions as a hole injection layer. Next, a 20 nm-thick 4,4′-bis [N- (1-naphthyl) is formed on the TPD232 film.
-N-phenylamino] biphenyl film (hereinafter referred to as NPD
Film) was formed. This NPD film functions as a hole transport layer. Further, the compound (A) having a thickness of 40 nm is formed on the NPD film.
1) was deposited to form a film. This film functions as a light emitting layer. Tris (8-quinolinol) having a thickness of 20 nm is formed on this film.
An aluminum film (hereinafter, Alq film) was formed. This A
The lq film functions as an electron injection layer. After this, Li (L
i source: manufactured by Saes Getter Co.) and Alq
An Alq: Li film was formed as an electron injection layer (cathode).
Metallic Al was vapor-deposited on this Alq: Li film to form a metal cathode to produce an organic EL device. This element is DC voltage 6V
As a result, blue light emission having an emission luminance of 150 cd / m ² , a maximum emission luminance of 43000 cd / m ² , and an emission efficiency of 3.0 cd / A was obtained.

Examples 2 to 8 Organic EL devices were prepared in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of the compound (A1). The luminous efficiency and the glass transition temperature were measured, the luminescent color was observed, and as a heat resistance test, after storing at a temperature of 85 ° C. for 500 hours, the rate of decrease in luminescence from the initial luminance was measured. Table 1 shows the results.

Comparative Example 1 In Example 1, 7,1 was used in place of compound (A1).
An organic EL device was manufactured in the same manner except that 0-diphenylfluoranthene (DPF) was used.
At 5 V, measure the emission brightness and emission efficiency, observe the emission color,
Further, as a heat resistance test, after storing at a temperature of 85 ° C. for 500 hours, the luminescence reduction rate from the initial luminance was measured. Table 1 shows the results.

[0055]

[Table 1]

As shown in Table 1, the organic EL device using the novel hydrocarbon compound of the present invention has high luminous efficiency,
Excellent heat resistance. This is because the glass transition temperature of the novel hydrocarbon compound of the present invention is as high as 100 ° C. or more, and the fluorescent property in the blue to green region is maintained.

Example 9 A 25 mm × 75 mm × 1.1 mm thick glass substrate with an ITO transparent electrode (manufactured by Geomatic) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then to UV ozone cleaning for 30 minutes. The glass substrate with the transparent electrode lines after cleaning is mounted on a substrate holder of a vacuum evaporation apparatus. First, a TPD232 film having a thickness of 60 nm is coated on the surface on the side where the transparent electrode lines are formed so as to cover the transparent electrodes. A film was formed. This TPD232 film functions as a hole injection layer. next,
A film made of the compound (A15) was formed on the TPD232 film to a thickness of 20 nm. This (A15) film functions as a hole transport layer. Further, on the (A15) film, a 40 nm thick A
lq and rubrene were deposited at a weight ratio of 30: 1 to form a film. This film functions as a light emitting layer. An Alq film having a thickness of 20 nm was formed on this film. This Alq film functions as an electron injection layer. Thereafter, Li (Li source: manufactured by SAES Getter Co.) and Alq were binary deposited to form an Alq: Li film as an electron injection layer (cathode). Metallic Al was vapor-deposited on this Alq: Li film to form a metal cathode to produce an organic EL device. This device emitted yellow light with extremely high luminous efficiency of 150 cd / m ² , maximum luminous luminance of 73000 cd / m ² and luminous efficiency of 10.0 cd / A at a DC voltage of 6 V. Also, set the initial brightness to 1000
When a life test was performed by driving at a constant current of cd / m ² , the half life was 6200 hours, which was extremely long. From the above, the novel hydrocarbon compound of the present invention is extremely excellent as a hole transporting compound.

Example 10 A glass substrate (manufactured by Geomatic) having a thickness of 25 mm × 75 mm × 1.1 mm with an ITO transparent electrode was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning for 30 minutes. The glass substrate with the transparent electrode lines after cleaning is mounted on a substrate holder of a vacuum evaporation apparatus. First, a TPD232 film having a thickness of 60 nm is coated on the surface on the side where the transparent electrode lines are formed so as to cover the transparent electrodes. A film was formed. This TPD232 film functions as a hole injection layer. next,
An NPD film having a thickness of 20 nm was formed on the TPD232 film. This NPD film functions as a hole transport layer. Furthermore, NP
Alq and rubrene having a thickness of 40 nm were put on the D film at a weight ratio of 30:
1 and deposited. This film functions as a light emitting layer. On this film, a film made of the compound (A3) having a thickness of 20 nm was formed. This (A3) film functions as an electron injection layer. Thereafter, a 1 nm-thick Li film was formed as an inorganic compound film.
An F film was formed. Metallic Al was deposited on this LiF film to form a metal cathode, thereby producing an organic EL device. This device has a luminance of 250 cd / m ² at a DC voltage of 5.5 V and a maximum luminance of 93000 c.
Yellow light emission with extremely high luminous efficiency of d / m ² and luminous efficiency of 12.0 cd / A was obtained. When the life test was performed by driving at a constant current with an initial luminance of 1000 cd / m ² , the half life was extremely long at 5,000 hours. From the above, the novel hydrocarbon compound of the present invention is extremely excellent as a compound having an electron transporting property.

Example 11 In Example 10, instead of forming the inorganic compound film of the LiF film, an electron transporting compound and a reducing compound in which the above compound (A3) and Cs (cesium) were mixed at a molar ratio of 1: 1. An organic EL device having a mixed type electron injection layer was prepared. This element becomes a further low-voltage driving and the light-emitting luminance 1020 cd / m ² at a direct current voltage 4.5V, the maximum emission luminance 123000cd / m ^2,
Luminous efficiency was as high as 13.0 cd / A, and yellow luminescence with extremely high luminous efficiency was obtained. A life test was performed with a constant current drive at an initial luminance of 1000 cd / m ² , and the half life was extremely long at 5800 hours.

[0060]

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 11/06 650 C09K 11/06 650 655 655 H05B 33/14 H05B 33/14 B 33/22 33/22 BDZ

Claims (7)

[Claims] 1. A novel hydrocarbon compound represented by the following general formula (1). X _n -Ar ₁ (1) (wherein, Ar ₁ is a substituted or unsubstituted carbon atom having 6 carbon atoms)
To 40 aromatic ring groups, substituted or unsubstituted arylamino groups having 6 to 40 carbon atoms, substituted or unsubstituted diaminoaryl groups having 6 to 60 carbon atoms, substituted or unsubstituted carbon atoms having 6 to 60 carbon atoms 60 triaminoaryl groups,
A substituted or unsubstituted heterocyclic group having 3 to 40 carbon atoms or a substituted or unsubstituted ethenylene, X is a monovalent group having a fluoranthene structure, and n is an integer of 2 to 4. ) 2. The novel hydrocarbon compound according to claim 1, wherein X is a monovalent group having a structure represented by the following general formulas [1] to [3]. Embedded image [In the formulas [1] to [3], X ^{1 to} X ¹⁶ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl having 1 to 30 carbon atoms. Group, substituted or unsubstituted straight-chain, branched or cyclic alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted straight-chain, branched or cyclic alkylthio group having 1 to 30 carbon atoms, substituted or unsubstituted Linear, branched or cyclic alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted linear, branched or cyclic carbon atom having 2 carbon atoms
To 30 alkenyloxy groups, substituted or unsubstituted straight-chain, branched or cyclic alkenylthio groups having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted 7 to 3 carbon atoms
0 aralkyloxy group, substituted or unsubstituted aralkylthio group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms An oxy group, a substituted or unsubstituted arylthio group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group having 2 to 30 carbon atoms, a cyano group, a hydroxyl group, a —COOR ¹ group (wherein R ¹ is hydrogen Atom, substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted linear, branched or cyclic alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted An aralkyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted 6 to 6 carbon atoms
30 represents an aryl group), a —COR ² group (in the group, R ²
Is a hydrogen atom, a substituted or unsubstituted straight-chain, branched or cyclic alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted straight-chain, branched or cyclic carbon atom having 2 to 30 carbon atoms.
An alkenyl group, substituted or unsubstituted having 7 to 7 carbon atoms
30 represents an aralkyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or an amino group), -OC
OR ³ group (wherein R ³ is a substituted or unsubstituted straight-chain,
A branched or cyclic alkyl group having 1 to 30 carbon atoms,
A substituted or unsubstituted linear, branched or cyclic alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl having 6 to 30 carbon atoms Represents a group), and among X ^{1 to} X ¹⁶ , an adjacent group and a substituent of each group may be bonded to each other to form a substituted or unsubstituted carbon ring. ] 3. An organic electroluminescence device having an organic compound film composed of at least a single layer or a plurality of layers having a light emitting layer between a pair of electrodes, wherein at least one of the organic compound films is according to claim 1 or 2. An organic electroluminescence device comprising the novel hydrocarbon compound described above. 4. An organic electroluminescent device having an organic compound film comprising at least a single layer or a plurality of layers having at least a light-emitting layer between a pair of electrodes, wherein the light-emitting layer is a novel carbonization element according to claim 1 or 2. An organic electroluminescence device comprising a hydrogen compound. 5. An organic electroluminescence device having an organic compound film comprising at least a single layer or a plurality of layers having a light emitting layer between a pair of electrodes, wherein the electron injection layer or the hole injection layer is provided. An organic electroluminescent device comprising the novel hydrocarbon compound described in 1. above. 6. The organic electroluminescence device according to claim 4, wherein an inorganic compound layer is provided between the light emitting layer and the electrode. 7. The light emitting layer according to claim 3, wherein the light emitting layer contains a condensed polycyclic aromatic derivative as a light emitting center.
The organic electroluminescent device according to any one of the above.