JP3509383B2 - Organic electroluminescent device material and organic electroluminescent device using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting material for an organic electroluminescence (EL) element used for a flat light source or a display and a high brightness light emitting element.

[0002]

2. Description of the Related Art An EL element using an organic substance is expected to be used as a solid-state light emitting type inexpensive large area full color display element, and many developments have been made. Generally EL
Is composed of a light emitting layer and a pair of counter electrodes sandwiching the light emitting layer. In light emission, when an electric field is applied between both electrodes, electrons are injected from the cathode side and holes are injected from the anode side. Further, this is a phenomenon in which the electrons are recombined with holes in the light emitting layer, and energy is emitted as light when the energy level returns from the conduction band to the valence band.

A conventional organic EL element has a higher driving voltage and lower emission brightness and emission efficiency than an inorganic EL element.
In addition, the deterioration of the characteristics was remarkable and it was not put to practical use.
In recent years, an organic EL in which thin films containing an organic compound having a high fluorescence quantum efficiency that emits light at a low voltage of 10 V or less are laminated
The device has been reported and is of great interest (see Applied Physics Letters, 51, 913, 1987). In this method, a metal chelate complex is used for a phosphor layer and an amine compound is used for a hole injecting layer to obtain high-luminance green light emission, and the luminance is several thousand at a DC voltage of 6 to 7V.
It has cd / m ² and a maximum luminous efficiency of 1.5 lm / W, which is close to the practical range.

However, the organic EL devices to date have been improved in the emission intensity due to the improved structure, but still do not have sufficient emission brightness. Further, it has a big problem that it is inferior in stability when repeatedly used. In order to improve the light emission efficiency of an organic EL device, a technique for forming a light emitting layer by doping a host substance, which is a light emitting material, with a guest substance has been disclosed. For example, an organic EL device in which a tris (8-hydroxyquinoline) aluminum complex is used as a host substance in a light emitting layer and a coumarin dye or a DCM dye is doped as a fluorescent guest substance (Journal of Applied Physics, vol. 65, page 3610). ,
1989), but the luminous efficiency of these organic EL devices was not sufficient. Further, an organic EL device in which a tris (8-hydroxyquinoline) aluminum complex is used as a host substance and a quinacridone or a quinazoline compound is doped as a fluorescent guest substance in a light emitting layer is disclosed (Japanese Patent Laid-Open No. 05-70773). However, although these organic EL elements have improved initial light emission efficiency, they have a serious problem in practical use due to remarkable deterioration when continuously emitting light. This is because it is difficult to do the technique of doping a small amount of the fluorescent guest substance to the light emitting layer, and in the disclosed quinacridone or quinazoline compound, the pigment molecules are strongly aggregated with each other, so that it is uniform in the light emitting layer. Is difficult to dope. For these reasons, it is desired to develop a fluorescent guest material that can be easily uniformly doped in the light emitting layer, and an organic EL element having higher light emitting efficiency and excellent stability during repeated use. Is the current situation.

[0005]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an organic E having high luminous efficiency and excellent stability in repeated use.
It is to provide the L element. As a result of intensive studies by the present inventors,
The present inventors have found that an organic EL device using at least one organic EL device material of the compound represented by the general formula [1] has a high luminous efficiency and is excellent in stability even after repeated use. It was

[0006]

That is, the present invention is an organic electroluminescent device material comprising a compound represented by the following general formula [1].

General formula [1]

[Chemical 4] [In the formula, R ¹ and R ² represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic ring group. R ³
To R ¹² are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted thioalkoxy group, a cyano group, an amino group, a mono- or di-substituted amino group, a hydroxyl group, Represents a mercapto group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted aromatic ring group, a substituted or unsubstituted heterocyclic group, respectively. (By forming a substituted or unsubstituted alkyl ring, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic aromatic ring, or a substituted or unsubstituted heterocycle by combining adjacent substituents with each other. Is also good). ]

Furthermore, the present invention is an organic electroluminescent device in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes, and at least one layer is a layer containing the organic electroluminescent device material. It is a certain organic electroluminescence element.

Furthermore, the present invention is an organic electroluminescence device having a light emitting layer or a plurality of organic compound thin films including a light emitting layer formed between a pair of electrodes, wherein the light emitting layer comprises a metal complex compound and the above organic electroluminescent device material. It is an organic electroluminescence element which is a layer to be contained.

Further, the present invention provides an organic electroluminescence device having a light emitting layer or a plurality of organic compound thin films including a light emitting layer formed between a pair of electrodes, wherein the light emitting layer has an aromatic tertiary amine compound and the above organic electroluminescence. It is an organic electroluminescence device which is a layer containing a device material.

Further, the present invention is an organic electroluminescent device, wherein the aromatic tertiary amine derivative is a compound represented by the following general formula [2]. General formula [2]

[Chemical 5] [In the formula, B ^{1 to} B ⁴ each independently represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. G represents a substituted or unsubstituted arylene group. ]

Furthermore, the present invention is an organic electroluminescence device having a light emitting layer or a plurality of organic compound thin films including a light emitting layer formed between a pair of electrodes, wherein the electron injection layer is a metal complex compound and the above organic electroluminescence device material. It is an organic electroluminescent element which is a layer containing.

Further, the present invention is the above organic electroluminescent device, wherein the metal complex compound is a compound represented by the following general formula [3]. General formula [3]

[Chemical 6] [In the formula, Q¹And Q²Are each independently replaced
Or unsubstituted hydroxyquinoline derivative, substituted or
Represents an unsubstituted hydroxybenzoquinoline derivative, L
Is a halogen atom, a substituted or unsubstituted alkyl group,
A substituted or unsubstituted cycloalkyl group, substituted or
An aryl group which may contain an unsubstituted nitrogen atom, -OR
(R is a hydrogen atom, a substituted or unsubstituted alkyl group,
Substituted or unsubstituted cycloalkyl group, substituted or unsubstituted
An aryl group that may contain a substituted nitrogen atom. ),
-O-Ga-Q³(Q^Four) (Q³And Q^FourIs Q¹Oh
And Q ²Means the same as. ) Represents a ligand represented by
You ]

DETAILED DESCRIPTION OF THE INVENTION

The substituted or unsubstituted alkyl group represented by R ^{1 to} R ^{2 in} the compound represented by the general formula [1] of the present invention includes a methyl group, an ethyl group, a propyl group, a butyl group, and se.
c-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloromethyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group, 1,3-cyclohexadienyl group, Examples include 2-cyclopenten-1-yl group and 2,4-cyclopentadiene-1-yridenyl group. As the substituted or unsubstituted aromatic ring group, a phenyl group, a biphenylenyl group, a triphenylenyl group, a tetraphenylenyl group, a 3-nitrophenyl group, a 4-methylthiophenyl group, a 3,5-dicyanophenyl group, o-, m- and p
-Tolyl group, xylyl group, o-, m- and p-cumenyl group, mesityl group, pentalenyl group, indenyl group, naphthyl group, azulenyl group, heptanenyl group, acenaphthylenyl group, phenalenyl group, fluorenyl group, anthryl group, anthraquinonyl group A 3-methylanthryl group,
Phenanthryl group, triphenylenyl group, pyrenyl group,
Chrysenyl group, 2-ethyl-1-chrysenyl group, picenyl group, perylenyl group, 6-chloroperylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group,
Hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group,
Examples thereof include a heptaenyl group, a pyrantrenyl group, and an ovarenyl group.

Representative examples of R ^{3 to} R ¹² of the compound represented by the general formula [1] of the present invention are the following substituents. Fluorine, chlorine, bromine, iodine as a hydrogen atom and a halogen atom, and a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyl as a substituted or unsubstituted alkoxy group. There are oxy group, hexyloxy group, stearyloxy group, trifluoromethoxy group and the like. Examples of the substituted or unsubstituted thioalkoxy group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group,
There are hexylthio group, heptylthio group, octylthio group and the like.

The mono- or di-substituted amino group includes methylamino group, dimethylamino group, ethylamino group, diethylamino group, dipropylamino group, dibutylamino group, diphenylamino group, bis (acetooxymethyl) group.
Examples include an amino group, a bis (acetooxyethyl) amino group, a bis (acetooxypropyl) amino group, a bis (acetooxybutyl) amino group, and a dibenzylamino group. Examples of the substituted or unsubstituted aryloxy group include a phenoxy group, a p-tert-butylphenoxy group and a 3-fluorophenoxy group. Examples of the substituted or unsubstituted arylthio group include a phenylthio group and a 3-fluorophenylthio group.

As the substituted or unsubstituted heterocyclic group,
Thionyl group, furyl group, pyrrolyl group, imidazolyl group,
Pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolyl group, quinolyl group, isoquinolyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, carbazolyl group, acridinyl group, phenazinyl group, furfuryl group, isothiazolyl group, isoxazolyl group , A flazanyl group, a phenoxazinyl group, a benzothiazolyl group, a benzoxazolyl group, a benzimidazolyl group, a 2-methylpyridyl group, a 3-cyanopyridyl group, and the like, but the substituents are not specifically limited.

The method for synthesizing the quinacridone compound of the general formula [1] of the present invention is a method of substituting an unsubstituted quinacridone represented by the general formula [4] with an alkyl halide or an aryl halide (Nishi et al., Dye and Chemicals). , 13 volumes, 8
1 page 1968), but is not limited to this. General formula [4]

[Chemical 3] [In the formula, R ^{3 to} R ¹² have the same meanings as described above. ]

Representative examples of the quinacridone compound of the present invention are specifically shown in Table 1, but the present invention is not limited thereto.

[0020]

[Table 1]

[0021]

[0022]

[0023]

Specific examples of B ^{1 to} B ⁴ of the compound represented by the general formula [2] in the present invention are substituted or unsubstituted aryl groups having 6 to 20 carbon atoms. Specifically, it is an aryl group which may contain a nitrogen atom, such as a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group and a pyrenyl group, and each aryl group is substituted. It may have a group. G is a divalent arylene group, a phenylene group,
Biphenylene group, terphenylene group, naphthylene group, anthrylene group, phenanthrylene group, fluorenylene group, a divalent arylene group which may contain a nitrogen atom such as pyrenylene group, each aryl group has a substituent Is also good.

Specific examples of the compound of the general formula [2] of the present invention which is an effective light emitting material and other materials are specifically shown in Table 2 below, which is a representative example of the present invention. It is not limited to.

[0026]

[Table 2]

[0027]

[0028]

[0029]

The compound represented by the general formula [3] in the present invention
Q of compound¹, Q²Is 8-hydroxyquinoline, 8-hi
Droxyquinaldine, 8-hydroxy-2-phenyl key
Norrin, 8-hydroxy-5-methylquinoline, 8-hi
Hydrides such as droxy-3,5,7-trifluoroquinoline
Roxyquinoline derivative, L is a halogen atom,
Or unsubstituted alkyl group, substituted or unsubstituted cyclo
Even if it contains an alkyl group or a substituted or unsubstituted nitrogen atom
Good aryl group, -OR (R is hydrogen atom, substituted or
Unsubstituted alkyl group, substituted or unsubstituted cycloal
It may contain a kill group or a substituted or unsubstituted nitrogen atom.
It is an aryl group. ), -O-Ga-Q ³(Q^Four) (Q
³And Q^FourIs Q¹And Q²Means the same as. )
Indicates. Here, a halogen atom, an alkyl group, a cycloalkyl group
Alkyl group, aryl group optionally containing nitrogen atom, and
, An alkyl group of R of the —OR group, a cycloalkyl group, a nitrogen group
The aryl group which may contain an elementary atom has the above general formula
R described in [1]¹~ R¹²Represents the same group as.

The typical examples of the compound of the general formula [3] and the typical examples of the electron injecting material used in the organic EL device of the present invention are specifically shown in Table 3 below. It is not limited to the example.

[0032]

[Table 3]

[0033]

[0034]

[0035]

[0036]

The compound represented by the general formula [1] of the present invention is a compound having strong fluorescence in the solid state, and is also excellent in electroluminescence. Further, since it has both excellent hole injecting property and hole transporting property from the metal electrode or the organic thin film layer, and excellent electron injecting property and electron transporting property from the metal electrode or the organic thin film layer, it can be used as a light emitting material. It can be effectively used, and other hole transporting material, electron transporting material or doping material may be used.

The organic EL element is an element in which a single-layer or multi-layer organic thin film is formed between an anode and a cathode. In the case of the single layer type, a light emitting layer is provided between the anode and the cathode. The light emitting layer contains a light emitting material, and may further contain a hole transport material or an electron transport material for transporting holes injected from the anode or electrons injected from the cathode to the light emitting material. The multilayer type is (anode / hole injection layer / light emitting layer /
There is an organic EL device having a multi-layer structure of (cathode), (anode / light emitting layer / electron injection layer / cathode), and (anode / hole injection layer / light emitting layer / electron injection layer / cathode). Since the quinacridone compound of the general formula [1] is an electron transporting compound, it can be used for an electron injecting layer, an electron transporting layer, an electron transporting light emitting layer and the like by utilizing its electron transporting property. Further, since this compound has strong fluorescence, it can be used as a light emitting material. However, when it is doped as an doping material at an optimum ratio in the light emitting layer, high luminous efficiency and light emission can be obtained. Optimal wavelength selection is now possible.

A metal complex such as tris (8-hydroxyquinoline) aluminum complex is used as a light emitting material (host substance) of the light emitting layer, and a compound of the general formula [1] is used as a doping material (guest substance) to obtain high emission brightness. Thus, it is possible to obtain an organic EL element having excellent stability during repeated use. The compound of the general formula [1] is preferably contained in the light emitting layer in an amount of 0.001% by weight to 50% by weight, more preferably 0.01% by weight.
A range of up to 5% by weight is effective. The quinacridone compound of the general formula [1] of the present invention can also be used as an electron transporting material. For example, it can be used as an electron transporting material in the light emitting layer or as a material constituting the electron injecting layer. The quinacridone compound of the general formula [1] of the present invention has a nitrogen atom and a substituent bonded to each other in place of the N—H bond of the quinacridone molecule in the chemical structure, as defined by the general formula [1]. In the wet film forming method such as the spin coating method, the solubility in the solvent is high and it is possible to make the layers uniformly exist. Therefore, even when the light emitting material is doped in the light emitting layer, the carriers injected from the respective electrodes can be recombined uniformly in the light emitting layer, and an organic EL device having high brightness and long life can be obtained. It is extremely effective for making.

In the light emitting layer, in addition to the light emitting material and the light emitting auxiliary material, a hole transporting material or an electron transporting material can be used if necessary.

When the organic EL element has a multi-layered structure, it is possible to prevent deterioration in brightness and life due to quenching. Further, if necessary, two or more kinds of a light emitting material, a doping material, a hole transporting material for carrying carriers and an electron transporting material can be used in combination. Also,
The hole injecting layer, the light emitting layer, and the electron injecting layer may each be formed of a layer structure of two or more layers, and a device structure in which holes or electrons are efficiently injected from the electrode and transported in the layer is selected. It

The conductive material used for the anode of the organic EL device is preferably one having a work function larger than 4 eV, such as carbon, aluminum, vanadium, iron, cobalt,
Nickel, tungsten, silver, gold, platinum, palladium and their alloys, ITO substrates, metal oxides such as tin oxide and indium oxide called NESA substrates, and organic conductive resins such as polythiophene and polypyrrole are used. . The conductive material used for the cathode is preferably one having a work function smaller than 4 eV, such as magnesium, calcium, tin, lead, titanium, yttrium,
Lithium, ruthenium, manganese and the like and alloys thereof are used, but not limited to these. The anode and the cathode may be formed in a layered structure of two or more layers if necessary.

In the organic EL device, it is desirable that at least one of them is sufficiently transparent in the emission wavelength region of the device in order to emit light efficiently. It is also desirable that the substrate is transparent. The transparent electrode is set using the above-mentioned conductive material so as to ensure a predetermined translucency by a method such as vapor deposition or sputtering. The electrode on the light emitting surface preferably has a light transmittance of 10% or more. The substrate has mechanical and thermal strength and is not limited as long as it is transparent, but examples thereof include a transparent resin such as a glass substrate, a polyethylene plate, a polyether sulfone plate, and a polypropylene plate. .

For forming each layer of the organic EL device according to the present invention, any of dry film forming methods such as vacuum deposition and sputtering and wet film forming methods such as spin coating and dipping can be applied. The film thickness is not particularly limited, but each layer needs to be set to an appropriate film thickness. If the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too thin, pinholes and the like will occur, and even if an electric field is applied, sufficient emission brightness cannot be obtained. Normal film thickness is 5nm to 10μ
The range of m is preferred, but the range of 10 nm to 0.2 μm is more preferred.

In the case of the wet film forming method, the material forming each layer is dissolved or dispersed in a suitable solvent such as chloroform, tetrahydrofuran, dioxane to form a thin film.
The solvent may be any. Further, in any of the thin films, an appropriate resin or additive may be used in order to improve the film forming property and prevent pinholes in the film. Examples of such a resin include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethylmethacrylate, polymethylacrylate and cellulose, and poly-N-
Examples thereof include photoconductive resins such as vinylcarbazole and polysilane, and conductive resins such as polythiophene and polypyrrole. Examples of the additives include antioxidants, ultraviolet absorbers, plasticizers and the like.

Examples of the light emitting material or doping material that can be used in the organic EL device of the present invention include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone,
Naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran , Thiopyran, polymethine, merocyanine, imidazole chelated oxinoid compounds, quinacridone, rubrene and the like, and derivatives thereof, but are not limited thereto. A more effective light emitting material is the compound of the general formula [2] of the present invention.

The hole-transporting material has a capability of transporting holes, has an excellent hole-injecting effect on the light-emitting layer or the light-emitting material, and has an electron-injecting layer or electrons for excitons generated in the light-emitting layer. Examples thereof include compounds that prevent migration to transport materials and have excellent thin film forming ability. Specifically, phthalocyanine compounds, naphthalocyanine compounds, porphyrin compounds, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acylhydrazone, poly Aryl alkane, stilbene, butadiene,
Benzidine-type triphenylamine, styrylamine-type triphenylamine, diamine-type triphenylamine, and their derivatives, and polyvinylcarbazole,
There are polymer materials such as polysilane and conductive polymers,
It is not limited to these.

The electron-transporting material has the ability to transport electrons, has an excellent electron-injecting effect on the light-emitting layer or the light-emitting material, and excites generated in the light-emitting layer in the hole-injecting layer or hole-transporting layer. Examples thereof include compounds that prevent transfer to the material and have excellent thin film forming ability. For example, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxadiazole, thiadiazole, tetrazole, perylene tetracarboxylic acid, fluorenylidene methane, anthraquinodimethane, anthrone, etc. It can be used as a material, and preferred examples include tris (8-hydroxyquinoline) aluminum, bis (8-hydroxyquinoline) zinc, bis (8
-Hydroxyquinoline) magnesium, bis (benzo (f) -8-hydroxyquinoline) copper, bis (2-methyl-8-hydroxyquinoline) aluminum oxide, tris (8-hydroxyquinoline) gallium, tris (8-hydroxyquinoline) Indium, Tris (5
-Methyl-8-hydroxyquinoline) aluminum, 8
-Lithium hydroxyquinoline, tris (5-chloro-
8-hydroxyquinoline) aluminum, bis (10-
Hydroxybenzo [H] quinolinate) beryllium, bis (10-hydroxybenzo [H] quinolinate) 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-naphtholato) gallium and the like can be mentioned, but the invention is not limited thereto. A more effective light emitting material is the compound of the general formula [3] of the present invention. Further, an electron accepting substance may be added to the hole transporting material and an electron donating substance may be added to the electron transporting material to sensitize.

The compound of the general formula [1] of the present invention is preferably used as a light emitting material or as a doping material in a light emitting layer.
At least one of a hole transport material and an electron transport material may be contained in the same layer. In addition, since the compound of the general formula [1] has an electron transporting ability, it can be used in the electron injection layer.

In order to improve the stability of the organic EL device obtained by the present invention against temperature, humidity, atmosphere, etc., a protective layer is provided on the surface of the device or silicon oil or the like is enclosed to protect the entire device. It is also possible to do so.

As described above, in the present invention, since the compound of the general formula [1] is used for the organic EL device, the luminous efficiency can be increased. In addition, this device is extremely stable against heat and current, and because it can obtain practically usable light emission brightness at low voltage, deterioration and light emission time that have been a big problem until now Was greatly improved, and it was possible to contribute to the improvement of the life of the organic EL element. . The organic EL device of the present invention is a flat panel display such as a wall-mounted TV,
As a plane light emitter, it can be considered to be applied to a light source of a copying machine or a printer, a light source of a liquid crystal display or instruments, a display plate, a marker lamp, etc., and its industrial value is very large.

[0052]

The present invention will be described in more detail based on the following examples. Method for synthesizing compound (1) 2.4 parts of compound (2) and 50 parts of benzene, 150 parts of 50% aqueous sodium hydroxide solution, 2.1 parts of benzyltriethylammonium chloride, and 57.2 parts of ethyl iodide are used.
The mixture was heated and stirred at 0 ° C. for 12 hours, and the precipitated crystals were separated by filtration, washed with methanol, and dried to obtain 2.5 parts of orange crystals. It was confirmed to be the compound (1) by elemental analysis, molecular weight analysis and NMR spectrum. The infrared absorption spectrum (KBr tablet method) of this compound is shown in FIG.
The fluorescence spectrum is shown in FIG.

Examples 1 to 2, 4 to 16 N, N '-(4
-Methylphenyl) -N, N '-(4-n-butylphenyl) -phenanthrene-9,10-diamine was vacuum-deposited to obtain a hole injection layer having a film thickness of 50 nm. Then, the tris (8-quinolinato) aluminum complex and the compounds shown in Table 4 were co-evaporated in vacuum at a weight ratio of 50: 1 to form a light-emitting layer having a thickness of 50 nm, and magnesium and silver were added thereon in an amount of 10: 1. An electrode having a thickness of 150 nm was formed from the alloy mixed in the ratio of 1: to obtain an organic EL device. The hole injection layer, the light emitting layer and the cathode were vapor-deposited in a vacuum of 10 ⁻⁶ Torr and at a substrate temperature of room temperature. With this device, the emission luminance shown in Table 4 was obtained at a DC voltage of 5V.

[0054]

[Table 4]

Comparative Examples 1 to 3 Organic EL devices were prepared in the same manner as in Examples 1 to 16 except that the quinacridone compound was replaced with the quinacridone compound shown in Table 3 to measure the emission luminance.
With this device, the emission luminance shown in Table 5 was obtained at a DC voltage of 5V.

[0056]

[Table 5]

Example 17 N, N '-(4
-Methylphenyl) -N, N '-(4-n-butylphenyl) -phenanthrene-9,10-diamine was vacuum-deposited to obtain a hole injection layer having a film thickness of 50 nm. Then, the quinacridone compound (14) was dissolved and dispersed in chloroform to obtain a light emitting layer having a film thickness of 50 nm by spin coating. An electrode having a film thickness of 150 nm was formed on it with an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain an organic EL element. The hole injection layer and the cathode were vapor-deposited under the conditions of a substrate temperature of room temperature in a vacuum of 10 ⁻⁶ Torr. This device provided a light emission luminance of 20 (cd / m ² ) at a DC voltage of 5V.

Example 18 Tris (8-quinolinato) aluminum complex, quinacridone compound (1), N, N'-diphenyl-N, N '-(3-methylphenyl) -on a washed glass plate with an ITO electrode. 1,1′-biphenyl-4,4′-diamine, poly-N-vinylcarbazole 3: 0.05:
It was dissolved and dispersed in chloroform at a ratio of 2: 5, and a light emitting layer having a film thickness of 100 nm was obtained by a spin coating method. An electrode having a film thickness of 150 nm was formed on it with an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain an organic EL element.
The light emitting layer and the cathode were vapor-deposited under the conditions of a substrate temperature of room temperature in a vacuum of 10 ⁻⁶ Torr. This element has a DC voltage of 5V
The emission luminance of 540 (cd / m ² ) was obtained.

Comparative Example 4 An organic EL device was prepared in the same manner as in Example 18 except that the quinacridone compound was omitted, and the emission brightness was measured. This device provided a light emission luminance of 180 (cd / m ² ) at a DC voltage of 5V.

[0060]

Example 20 A method similar to that of Example 19 except that a bis (2-methyl-8-quinolinato) (1-naphtholate) gallium complex was used as the light emitting material instead of the tris (8-quinolinato) aluminum complex. Then, an organic EL device was prepared. This device provided a light emission luminance of 250 (cd / m ² ) at a DC voltage of 5V.

Example 21 N, N '-(4
-Methylphenyl) -N, N '-(4-n-butylphenyl) -phenanthrene-9,10-diamine was vacuum-deposited to obtain a hole injection layer having a film thickness of 30 nm. Then, the tris (8-hydroxyquinoline) aluminum complex and the quinacridone compound (10) are vapor-deposited at a weight ratio of 50: 1 to form a light-emitting layer having a film thickness of 30 nm, and further [2- ( 4-tert-butylphenyl)-
5- (biphenyl) -1,3,4-oxadiazole]
An electron injection layer having a thickness of 20 nm was obtained. On top of that, an alloy in which magnesium and silver are mixed in a ratio of 10: 1 has a film thickness of 150 nm.
An electrode was formed to obtain an organic EL device. Hole injection layer, light emitting layer, an electron injection layer and the cathode, in a vacuum of 10- ⁶ Torr, was deposited under the conditions of a substrate temperature of room temperature. With this device, a light emission luminance of about 1450 (cd / m ² ) was obtained at a DC voltage of 5V.

[0063]

Example 23 N, N '-(4
-Methylphenyl) -N, N '-(4-n-butylphenyl) -phenanthrene-9,10-diamine was vacuum-deposited to obtain a hole injection layer having a film thickness of 30 nm. Then, the compound (A-8) in Table 2 was vacuum-deposited to form a light emitting layer having a film thickness of 30 nm, and the compound (B-12) in Table 3 was formed thereon.
And quinacridone compound (10) were vapor-deposited at a weight ratio of 50: 1 to obtain an electron injection layer having a film thickness of 30 nm. An electrode having a film thickness of 150 nm was formed on it with an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain an organic EL element. The hole injection layer, the light emitting layer, the electron injection layer and the cathode are 10 ⁻⁶ To.
Deposition was carried out in a vacuum of rr at a substrate temperature of room temperature. With this device, a light emission luminance of about 1450 (cd / m ² ) was obtained at a DC voltage of 5V.

Example 24 The compound (B-3) shown in Table 3 and the quinacridone compound (16) were vapor-deposited on the electron injection layer at a weight ratio of 50: 1 to obtain a film thickness of 30.
An organic EL device was prepared in the same manner as in Example 20 except that an electron injection layer having a thickness of 20 nm was prepared, and the emission luminance was measured. This device provided a light emission luminance of 1510 (cd / m ² ) at a DC voltage of 5V.

When all the organic EL elements shown in this example were made to continuously emit light at 3 (mA / cm ² ),
Although stable light emission could be observed for 10,000 hours or more, the organic EL element of Comparative Example manufactured under the same conditions was 500
When the light emission time is less than or equal to the time, it becomes less than half of the initial light emission luminance, and the effect of the organic EL device of the present invention was clear. The organic EL device of the present invention achieves improved luminous efficiency, improved luminous brightness and long life.
The doping material, the hole transport material, the electron transport material, the sensitizer, the resin, the electrode material, and the like, and the element manufacturing method are not limited.

[0067]

According to the present invention, it is possible to obtain an organic EL device having higher luminous efficiency, higher luminance and longer life than ever before. This is because by using the compound shown in the present invention in an organic EL device, wet and dry film formation methods are easy, the compound is uniformly present in the light emitting material, and the decrease in light emission efficiency due to concentration quenching can be solved. , Organic E with high luminous efficiency
It has become possible to easily manufacture an L element.

[Brief description of drawings]

1] Infrared absorption spectrum of Compound 1

FIG. 2 Fluorescence spectrum of Compound 1

Continuation of front page (56) Reference JP-A-6-122277 (JP, A) JP-A-3-255190 (JP, A) JP-A-5-70773 (JP, A) JP-A-6-346049 (JP , A) JP-A-6-240248 (JP, A) JP-A-9-176630 (JP, A) JP-A-10-511991 (JP, A) International Publication 96/008536 (WO, A1) (58) Survey Areas (Int.Cl. ⁷ , DB name) C09K 11/06 H05B 33/14 CA (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] 1. An organic electroluminescence device material, which is a compound represented by the following general formula [1]. General formula [1] [In the formula, R ¹ and R ² represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic ring group. R ³
To R ¹² are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted thioalkoxy group, a cyano group, an amino group, a mono- or di-substituted amino group, a hydroxyl group, Represents a mercapto group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted aromatic ring group, a substituted or unsubstituted heterocyclic group, respectively. (By forming a substituted or unsubstituted alkyl ring, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic aromatic ring, or a substituted or unsubstituted heterocycle by combining adjacent substituents with each other. Is also good). ] 2. In an organic electroluminescent device having a light emitting layer or a plurality of organic compound thin films including a light emitting layer formed between a pair of electrodes, at least one layer is a layer containing the organic electroluminescent device material according to claim 1. An organic electroluminescence device characterized by being present. 3. In an organic electroluminescence device in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer are formed between a pair of electrodes, the light emitting layer comprises a metal complex compound and the organic electroluminescence device material according to claim 1. An organic electroluminescence device, which is a layer containing the organic electroluminescence device. 4. An organic electroluminescence device having a light emitting layer or a plurality of organic compound thin films including a light emitting layer formed between a pair of electrodes, wherein the light emitting layer is an aromatic tertiary amine compound and the organic electroluminescence according to claim 1. An organic electroluminescence device, which is a layer containing a device material. 5. The organic electroluminescent device according to claim 4, wherein the aromatic tertiary amine compound is a compound represented by the following general formula [2]. General formula [2] [In the formula, B ^{1 to} B ⁴ each independently represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. G represents a substituted or unsubstituted arylene group. ] 6. An organic electroluminescence device having a light emitting layer or a plurality of organic compound thin films including a light emitting layer formed between a pair of electrodes, wherein the electron injection layer is a metal complex compound and the organic electroluminescent device material according to claim 1. An organic electroluminescence device, which is a layer containing. 7. The organic electroluminescence device according to claim 3, wherein the metal complex compound is a compound represented by the following general formula [3]. General formula [3] [Wherein, Q ¹ and Q ² each independently represent a substituted or unsubstituted hydroxyquinoline derivative or a substituted or unsubstituted hydroxybenzoquinoline derivative, and L is
Halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted nitrogen atom-containing aryl group, -OR (R is a hydrogen atom, a substituted or unsubstituted alkyl group, A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group which may contain a nitrogen atom), -O-
^{Ga-Q 3 (Q 4)} (Q 3 and Q ⁴ represent. The same meanings as Q ¹ and Q ²⁾ represents a ligand represented by. ]