JPH0841451A - Material for organo electroluminescence element and organo electroluminescence element produced by using the material - Google Patents

Abstract

PURPOSE:To obtain the material composed of a quinacridone compound having a specific structure and capable of producing an organo electroluminescence element having higher luminous efficacy and higher luminous brightness compared with the conventional material, excellent in the stability of repeated use and having a long life. CONSTITUTION:This material is composed of a compound of the formula [Q is a quinacridone residue; R<1> and R<2> are each H, (substituted) alkyl, etc.; X and Y are each O, S, etc.; m=0-20; n=1-4]. The compound of the formula is obtained, e.g. by subjecting a quinacridone pigment to chlorosulfonation and reacting the chlorosulfonated product with an amine compound such as dimethylamine. Further, the use of tris(8-hydroxyquinoline)aluminum complex as a luminous material in a luminous layer and the compound of the formula as a luminescence assistant material is preferable because it enables the production of an element excellent in luminous brightness and the stability of repeated use.

Description

Detailed Description of the Invention

[0001]

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

[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, the metal chelate complex is added to the phosphor layer,
High-luminance green light emission is obtained by using an amine compound in the hole injection layer, and the luminance is 100c at a DC voltage of 6 to 7V.
d / m ² , maximum luminous efficiency of 1.5 lm / W is achieved,
It has the performance close to the practical range. However, although the organic EL devices to date have improved the emission intensity due to the improved structure, they 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 of forming a light emitting layer by doping a host material as a light emitting material with a guest material has been disclosed. For example, an organic EL device in which 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, Volume 65,
Pp. 3610, 1989), 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. For the above reasons, under the present circumstances, there is a demand for the development of an organic EL device having a larger emission brightness and excellent stability in repeated use.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic EL device having a large emission intensity and excellent stability in repeated use. As a result of diligent study by the present inventors, an organic EL device using at least one layer of an organic EL device material of the quinacridone compound represented by the general formula [1] has a large light emission intensity, The inventors have found that the stability is also excellent and have reached the present invention.

[0006]

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

General formula [1]

[Chemical 2][In the formula, Q is a quinacridone residue which may have a substituent.
Represents a group, R¹, R²Are each independently a hydrogen atom,
Substituted or unsubstituted alkyl group, substituted or unsubstituted
Cycloalkyl group, substituted or unsubstituted carbocyclic aromatic
Represents a cyclic group or a substituted or unsubstituted heterocyclic group (R¹When
R²And may form a substituted or unsubstituted heterocycle.
Yes. ), X, Y are each independently directly bonded, or
-O-, -S-, -NH-, -SO₂-, -CO-,-
SO₂NH-, -CONH-, -CH ₂NHCOCH₂N
Represents H-, m is an integer from 0 to 20, and n is an integer from 1 to 4.
Indicates a number. ]

The second 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, at least one of which is represented by the general formula [1]. It is an organic electroluminescence device which is a layer containing a device material.

A third invention is an organic electroluminescence device having a light emitting layer or a plurality of organic compound thin films including the light emitting layer formed between a pair of electrodes, wherein the light emitting layer is represented by the general formula [1]. It is an organic electroluminescence device which is a layer containing a device material.

A fourth aspect of the present invention is an organic electroluminescence device having a light emitting layer or a plurality of organic compound thin films including the light emitting layer formed between a pair of electrodes, wherein the light emitting layer is represented by the quinoline metal complex and the general formula [1]. The organic electroluminescence element is a layer containing the organic electroluminescence element material.

In a fifth aspect of the present invention, the light emitting layer of an organic electroluminescent device, in which a light emitting layer or a plurality of organic compound thin films including the light emitting layer are formed between a pair of electrodes, is an organic electroluminescent device represented by the general formula [1]. 0.001 wt% to 5% by weight of element material based on quinoline metal complex
It is an organic electroluminescence device containing 0% by weight.

The chemical structure of the quinacridone residue of the quinacridone compound of the general formula [1] used in the present invention is shown below.

Formula [2]

[Chemical 3]

Formula [3]

[Chemical 4]

Formula [4]

Embedded image

Formula [5]

[Chemical 6]

Formula [6]

[Chemical 7]

Here, the number and position of nitrogen atoms constituting the quinacridone residue are not particularly limited, and the quinacridone residue may have the following substituents. The number of substitutions and the substitution position of the substituent are not particularly limited.

Examples of the substituent bonded to the quinacridone residue in the present invention include hydrogen atom, halogen atom, cyano group, nitro group, amino group, mono- or di-substituted amino group, acylamino group, ester group, hydroxyl group and alkoxy. Group, mercapto group, alkyloxy group, alkylthio group, aryloxy group, arylthio group, siloxy group,
Substitution of acyl group, carbamoyl group, carboxylic acid group, sulfonic acid group, or methyl group, ethyl group, propyl group, butyl group, sec-butyl group, tert-butyl group, trifluoromethyl group, trifluoroethyl group, or the like. Unsubstituted alkyl group, cyclopropyl group, cyclohexyl group, 1,3-cyclohexadienyl group, 2-cyclopenten-1-yl group, 2,4-cyclopentadiene-1
-Substituted or unsubstituted cycloalkyl group such as iridenyl group, phenyl group, biphenyl group, triphenyl group, tetraphenylenyl group, 2-methylphenyl group, 3-nitrophenyl group, 4-methylthiophenyl group, 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 Group, phenalenyl group, fluorenyl group, anthryl group, anthraquinonyl group, 3-methylanthryl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group,
2-ethyl-1-chrysenyl group, picenyl group, perylenyl group, 6-chloroperenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group, hepta Substituted or unsubstituted carbocyclic aromatic ring group such as phenyl group, heptaenyl group, pyrantrenyl group, ovarenyl group, thienyl 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, flazanyl group, phenoxazinyl group, benzothiazolyl group, benzoxazolyl group , A benzimidazolyl group, a 2-methylpyridyl group, a 3-cyanopyridyl group, and the like, which are substituted or unsubstituted heterocyclic groups, but are not limited to these substituents. Further, adjacent substituents may form a substituted or unsubstituted cycloalkyl ring, a substituted or unsubstituted carbocyclic aromatic ring, or a substituted or unsubstituted heterocycle.

R ¹ and R ² in the general formula [1] are each independently a hydrogen atom or a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a tert-butyl group, a trifluoromethyl group, Substituted or unsubstituted alkyl group such as trifluoroethyl group, cyclopropyl group,
Cyclohexyl group, 1,3-cyclohexadienyl group,
Substituted or unsubstituted cycloalkyl group such as 2-cyclopenten-1-yl group, 2,4-cyclopentadiene-1-yridenyl group, phenyl group, biphenyl group, triphenyl group, tetraphenylenyl group, 2-methyl Phenyl group, 3-nitrophenyl group, 4-methylthiophenyl group, 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,
Heptacenyl group, pyrantrenyl group, substituted or unsubstituted carbocyclic aromatic ring group such as ovarenyl group, thienyl 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, flazanyl group, phenoxazinyl group, benzothiazolyl group, benzoxazolyl group , A benzimidazolyl group, a 2-methylpyridyl group, a 3-cyanopyridyl group, and the like, which are substituted or unsubstituted heterocyclic groups, but are not limited to these substituents. Further, R ¹ and R ² may contain N, or may further contain N, O or S to form a substituted or unsubstituted 5- or 6-membered heterocycle.

A typical method for synthesizing the quinacridone compound of the general formula [1] of the present invention is to chlorosulfonate the quinacridone pigment by a conventional method and then react it with an amine compound, or to nitrate the quinacridone pigment by a conventional method. There is a method of introducing a specific substituent after reduction, but the method is not limited to these.

The amine compound used in the method of reacting an amine compound is, for example, dimethylamine, diethylamine, N-ethylisopropylamine, N-ethylpropylamine, N-methylbutylamine, N-methylisobutylamine, N-butylethylamine. , N-tert
-Butylethylamine, diisopropylamine, dipropylamine, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N-isobutyl-sec-butylamine, diisoamylamine, dihexylamine, di (2- Ethylhexyl) amine, dioctylamine, N-methyloctadecylamine, didecylamine, diallylamine, N-
Ethyl-1,2-dimethylpropylamine, N-methylhexylamine, 2-hydroxymethylaminoethanol, dioleylamine, distearylamine, N, N-
Dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N- Diethylaminopropylamine,
N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine,
N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine,
N, N-ethyl-hexylaminoethylamine, N, N
-Distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-
Lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonicopetate, ethyl isonicopetinate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-
4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-
Aminopropylmorpholine, N-methylpiperazine, N
-Butylpiperazine, N-methylhomopiperazine, 1-
Examples include cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

In Table 1, the quinacridone residue component of the quinacridone compound of the general formula [1] is shown in Table 2 as a representative example of the amine component, but not limited thereto.

[0024]

[Table 1]

[0025]

[0026]

[0027]

[Table 2]

[0028]

[0029]

[0030]

1 to 3 show the organic EL used in the present invention.
An example of a schematic view of the device is shown. In the figure, generally, the electrode A 2 is an anode, and the electrode B 6 is a cathode. There is also an organic EL device having a layer structure of (electrode A / light emitting layer / electron injection layer / electrode B), and the quinacridone compound of the general formula [1] can be preferably used in any device structure. In addition, since this compound has strong fluorescence, it can be used as a light emitting material. However, by doping the light emitting material as an auxiliary light emitting material at an optimum ratio, high luminous efficiency and Optimal selection of emission wavelength has become possible. In particular, a quinoline 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 quinacridone compound of the general formula [1] is used as a light emission auxiliary material (guest substance). It was possible to obtain an organic EL device having high stability and excellent stability during repeated use.

The luminescent material is preferably a quinoline metal complex, and more preferably a tris (8-hydroxyquinoline) aluminum complex.
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, lithium 8-hydroxyquinoline, tris (5-chloro-8-hydroxyquinoline) gallium and the like.

The quinacridone compound of the general formula [1] is contained in the light emitting layer in an amount of 0.001% by weight based on the host material.
Is preferably contained in the range of
Further, the range of 0.01% by weight to 5% by weight is effective. Moreover, since the quinacridone compound of the general formula [1] is an n-type semiconductor, it can be used as an electron transporting material. For example, use as an electron transport material in the light emitting layer,
Alternatively, it can be preferably used as a material forming the electron injection layer. Since the quinacridone compound of the general formula [1] of the present invention has an amine component defined by the general formula [1] in its chemical structure, it has low solubility in a solvent by a wet film-forming method such as spin coating. Since the material is highly amorphous in a dry film forming method such as a vapor deposition method, it is uniformly present in each layer used. Therefore, even when the light emitting material is doped in the light emitting layer, for example, the carriers injected from the electrodes can be recombined uniformly, and the organic E having high brightness and long life can be obtained.
It can be said that it is extremely effective for producing an L element.

In the light emitting layer 4 of FIG. 1, 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.

In the structure of FIG. 2, since the light emitting layer 4 and the hole injecting layer 3 are separated, the hole injecting efficiency from the hole injecting layer 3 to the light emitting layer 4 is improved, and the emission brightness and the light emitting efficiency are improved. Can be increased. In this case, in order to improve the luminous efficiency,
It is desirable that the light emitting material used in the light emitting layer itself has an electron transporting property or that the light emitting layer has an electron transporting property by adding an electron transporting material.

The structure of FIG. 3 has an electron injection layer 5 in addition to the hole injection layer 3 to improve the efficiency of recombination of holes and electrons in the light emitting layer 4. As described above, by forming the organic EL element into a multi-layer structure, it is possible to prevent a decrease in brightness and life due to quenching. In the elements of FIGS. 2 and 3, if necessary, a light emitting material, a light emission assisting material, a hole transporting material for carrier transport, and an electron transporting material can be used in combination. In addition, the hole injection layer, the light emitting layer, and the electron injection layer may each be formed of a layer structure of two or more layers, and have a device structure in which holes or electrons are optimally injected from the electrode and are transported in the layer. Any one will do.

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, at least one of the electrode A represented by 2 and the electrode B represented by 6 is preferably sufficiently transparent in the emission wavelength region of the device in order to efficiently emit light. Further, it is desirable that the substrate 1 is also transparent. The transparent electrode is made of the above-mentioned conductive material and is set by a method such as vapor deposition or sputtering so as to ensure a predetermined translucency. The electrode that takes out the emitted light is
It is desirable that the light transmittance is 10% or more.

The substrate 1 is not limited as long as it has mechanical and thermal strength and is transparent or translucent, but examples of usable materials include a glass substrate, a polyethylene plate, and a polyether sulfone. Examples include plates and polypropylene plates.

Each layer of the organic EL element according to the present invention can be formed by a method such as a dry film forming method such as vacuum deposition or sputtering, or a wet film forming method such as spin coating or dipping. It is necessary to set the film thickness 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 5 nm to 1
A range of 0 μm is preferable, but 10 nm to 0.2 μm
Is more preferable.

In the case of the wet film forming method, a thin film is formed by using a liquid in which the material forming each layer is dissolved or dispersed in an appropriate solvent such as chloroform, tetrahydrofuran, dioxane, etc., which solvent is used. May be. Further, in any of the organic layers, an appropriate resin or additive may be used in order to improve the film-forming property and prevent pinholes in the film. Suitable resins include polystyrene, polycarbonate, polyarylate, polyester, polyamide, urethane, polysulfone, polymethylmethacrylate,
Examples thereof include insulating resins such as polymethyl acrylate, photoconductive resins such as poly-N-vinylcarbazole and polysilane, and conductive resins such as polythiophene and polypyrrole. Examples of the additives include antioxidants, ultraviolet absorbers, plasticizers and the like.

Known light-emitting materials or auxiliary materials for light-emitting materials 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, etc. and their derivatives, but not limited to Not intended to be.

The hole-transporting material has the ability to transport 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 has a hole-injecting layer or hole-transporting layer for excitons generated in the light-emitting 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, perylene tetracarboxylic acid, fluorenylidene methane, anthraquinodimethane,
Examples include, but are not limited to, anthrone and derivatives thereof. 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.

In the organic EL device shown in FIGS. 1, 2 and 3, the quinacridone compound of the general formula [1] of the present invention is used in the light emitting layer as a light emitting material or as a light emitting auxiliary material of the light emitting material. Desirably, at least one of a light emitting material, a light emission assisting material, a hole transporting material and an electron transporting material may be contained in the same 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 quinacridone compound of the general formula [1] is used for the organic EL device, the emission brightness can be increased. In addition, this device is extremely stable against heat and current, and can obtain practically usable emission brightness at low drive voltage. Can be greatly improved. INDUSTRIAL APPLICABILITY The organic EL device of the present invention may be applied to a flat panel display such as a wall-mounted TV, a light source for a copying machine, a printer, etc., a light source for a liquid crystal display, instruments, a display plate, a marker lamp, etc. , Its industrial value is very large.

[0048]

The present invention will be described in more detail based on the following examples. Examples 1 to 40 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-hydroxyquinoline) aluminum complex and the quinacridone compound described in Table 2 were vacuum-co-evaporated at a weight ratio of 1: 0.01 to form a light-emitting layer having a thickness of 50 nm.
Then, an electrode having a film thickness of 150 nm was formed from an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain an organic EL device shown in FIG. The hole injection layer, the light emitting layer and the cathode are
Deposition was performed under the conditions of a substrate temperature of room temperature in a vacuum of 10 ⁻⁶ Torr. With this device, the emission luminance shown in Table 2 was obtained at a DC voltage of 5V.

[0049]

[Table 3]

[0050]

Comparative Examples 1 to 6 Organic EL devices were prepared in the same manner as in Examples 1 to 40 except that the quinacridone compound was changed from the quinacridone compound shown in Table 3 to the quinacridone compounds shown in Table 3, and the emission luminance was measured.
With this device, the emission luminance shown in Table 3 was obtained at a DC voltage of 5V.

[0052]

[Table 4]

Examples 41 to 44 Organic EL was prepared in the same manner as in Examples 1 to 40 except that the quinacridone compound (1) was co-evaporated in vacuum at the weight ratio shown in Table 4.
A device was prepared and the emission brightness was measured. With this device, the emission luminance shown in Table 4 was obtained at a DC voltage of 5V.

[0054]

[Table 5]

Example 45 On a cleaned glass plate with ITO electrodes, 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 (4) was dissolved and dispersed in chloroform, and a light emitting layer having a film thickness of 500 nm was obtained by a spin coating method. An electrode having a film thickness of 150 nm was formed thereon with an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain an organic EL element having the structure shown in FIG. 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 element is 53 cd / m ² at a DC voltage of 5 V.
The emission luminance of was obtained.

Example 46 A tris (8-hydroxyquinoline) aluminum complex, a quinacridone compound (20), and N, N '-(4-methylphenyl)-were prepared on a washed glass plate with an ITO electrode.
N, N '-(4-n-butylphenyl) -phenanthrene-9,10-diamine and poly-N-vinylcarbazole were dissolved and dispersed in chloroform at a ratio of 3: 0.05: 2: 5, and spin coating was performed. Film thickness is 100 nm
To obtain a light emitting layer. On top of that, add magnesium and silver 10:
An electrode having a film thickness of 150 nm was formed from the alloy mixed in 1 to obtain the organic EL device shown in FIG. 1 for the light emitting layer and the cathode
Deposition was performed under the conditions of a substrate temperature of room temperature in a vacuum of 0 ^-6 Torr. This device provided a light emission luminance of 380 cd / m ² at a DC voltage of 5V.

Comparative Example 7 An organic EL device was prepared in the same manner as in Example 46 except that the quinacridone compound was omitted, and the emission luminance was measured. This device provided a light emission luminance of 200 cd / m ² at a DC voltage of 5V.

Example 47 N, N'-diphenyl-N, N '-(3-methylphenyl) -1,1'-on a cleaned glass plate with an ITO electrode
Biphenyl-4,4'-diamine was vacuum-deposited to obtain a hole injection layer having a film thickness of 50 nm. Then, a light emitting layer of quinacridone compound (33) having a film thickness of 30 nm was formed by a vacuum deposition method, and an electrode having a film thickness of 100 nm was formed on the light emitting layer with an alloy in which magnesium and silver were mixed at a ratio of 10: 1. The organic EL element shown was obtained. 10 for the hole injection layer and the light emitting layer
Deposition was carried out in a vacuum of ^-6 Torr at a substrate temperature of room temperature. This device provided a light emission luminance of 110 cd / m ² at a DC voltage of 5V.

Example 48 N, N'-diphenyl-N, N '-(3-methylphenyl) -1,1'-on a washed glass plate with an ITO electrode
Biphenyl-4,4'-diamine was vacuum-deposited to obtain a hole injection layer having a film thickness of 30 nm. Then, a 20 nm-thick light-emitting layer of the quinacridone compound (38) was formed by a vacuum evaporation method, and further, [2- (4-ter
t-butylphenyl) -5- (biphenyl) -1,3
An electron injection layer having a thickness of 20 nm of [4-oxadiazole] was obtained. 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 device shown in FIG. The hole injecting layer, the light emitting layer, the electron injecting layer, and the cathode were vapor-deposited under the conditions of the substrate temperature and room temperature in a vacuum of 10 ⁻⁶ Torr. This element has a DC voltage of 5V and is approximately 15
An emission luminance of 00 cd / m ² was obtained.

Example 49 [2- (4-tert-Butylphenyl) was used for the electron injection layer.
-5- (Biphenyl) -1,3,4-oxadiazole] was used in place of the quinacridone compound (24), and an organic EL device was prepared in the same manner as in Example 44, and the emission luminance was measured. . This element has a DC voltage of 5V and is 165
An emission luminance of 0 cd / m ² was obtained.

When all the organic EL devices shown in this example were continuously made to emit light at 1 mA / cm ² , 10
It was possible to observe stable light emission for more than 00 hours, but the organic EL element of the comparative example produced under the same conditions had a luminance of less than half of the initial emission luminance in the emission time of 500 hours or less. The effect of the device was clear. The organic EL device of the present invention achieves improvement in luminous efficiency, luminous brightness and long life, and is used together with a light emitting substance, a light emission auxiliary material, a hole transporting material, an electron transporting material, a sensitizer, The resin, the electrode material and the like and the method for manufacturing the element are not limited.

[0062]

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.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a schematic structure of an organic EL element used in Examples and Comparative Examples.

FIG. 2 is a cross-sectional view showing a schematic structure of organic EL elements used in Examples and Comparative Examples.

FIG. 3 is a sectional view showing a schematic structure of an organic EL element used in an example.

[Explanation of symbols]

 1. Substrate 2. Electrode A 3. Hole injection layer 4. Light emitting layer 5. Electron injection layer 6. Electrode B

Claims (5)

[Claims] 1. From a compound represented by the following general formula [1]
Organic electroluminescent device material General formula
[1][In the formula, Q is a quinacridone residue which may have a substituent.
Represents a group, R¹, R²Are each independently a hydrogen atom,
Substituted or unsubstituted alkyl group, substituted or unsubstituted
Cycloalkyl group, substituted or unsubstituted carbocyclic aromatic
Represents a cyclic group or a substituted or unsubstituted heterocyclic group (R¹When
R²And may form a substituted or unsubstituted heterocycle.
Yes. ), X, Y are each independently directly bonded, or
-O-, -S-, -NH-, -SO₂-, -CO-,-
SO₂NH-, -CONH-, -CH ₂NHCOCH₂N
Represents H-, m is an integer from 0 to 20, and n is an integer from 1 to 4.
Indicates a number. ] 2. In 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, at least one layer is a layer containing the organic electroluminescence device material according to claim 1. An organic electroluminescence device characterized by the above. 3. 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, wherein the light emitting layer is a layer containing the organic electroluminescent device material of claim 1. An organic electroluminescence device characterized by the above. 4. An organic electroluminescent device having a light emitting layer or a plurality of organic compound thin films including the light emitting layer formed between a pair of electrodes, wherein the light emitting layer contains a quinoline metal complex and the organic electroluminescent device material according to claim 1. An organic electroluminescent element, which is a layer having 5. A light emitting layer of an organic electroluminescent device, comprising 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 organic electroluminescent device material according to claim 1 is used for a quinoline metal complex. And an organic electroluminescent device containing 0.001% by weight to 50% by weight.