JPH10340786A - Organic electroluminecent element material and organic electroluminescent element using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element with high luminous efficiency and high stability in repeated use by using a heterocyclic organic compound in an organic electroluminescent element material. SOLUTION: A compound used in an organic electroluminescent element material is represented by formulas I, II. In the formulas, X<1> and X<2> independently represent N or CH, Y<1> and Y<2> independently represent S, O, N-Z [Z is a hydrogen atom, a substituted or non-substituted alkyl group, a substituted or non-substituted cycloalkyl group, a substituted or non-substituted heterocyclic group]. R<1> -R<4> independently represent respectively a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or non-substituted alkyl group, a substituted or non-substituted aryl group, a substituted or non-substituted alkoxy group, a substituted or non-substituted aryl oxy group, a substituted or non-substituted alkyl thio group, a substituted or non-substituted cycloalkyl group, a substituted or non-substituted heterocyclic group, a substituted or non-substituted amino group, or the like.

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) device used for a flat light source and a display.

[0002]

2. Description of the Related Art An EL device using an organic substance is expected to be used as an inexpensive, large-area, full-color display device of a solid light emitting type, and many developments have been made. Generally EL
Is composed of a light-emitting layer and a pair of opposed electrodes sandwiching the 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, 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.

[0003] Conventional organic EL devices have a higher driving voltage and lower luminous brightness and luminous efficiency than inorganic EL devices.
In addition, the characteristic deterioration was remarkable, and it had not been put to practical use.
2. Description of the Related Art In recent years, an organic EL in which a thin film containing an organic compound having high fluorescence quantum efficiency that emits light at a low voltage of 10 V or less is laminated.
Devices have been reported and are of interest (see Applied Physics Letters, vol. 51, p. 913, 1987). In this method, the metal chelate complex is converted into a phosphor layer,
High brightness green light emission is obtained by using an amine compound for the hole injection layer, and the brightness is 100 c at a DC voltage of 6 to 7 V.
d / m ² and maximum luminous efficiency of 1.5 lm / W,
Has performance close to the practical range. However, organic EL devices up to now have improved light emission intensity due to the improved structure, but do not yet have sufficient light emission luminance.
In addition, there is a major problem that the stability upon repeated use is poor.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an organic compound having high luminous efficiency and excellent stability when used repeatedly.
L element. As a result of intensive studies by the present inventors,
Organic EL using at least one layer of an organic EL device material of a compound represented by the general formula [1] or [2]
The inventors have found that the device has a high luminous efficiency and has excellent stability during repeated use, and has reached the present invention.

That is, the present invention is an organic electroluminescent device material represented by the following general formula [1] or the following general formula [2]. General formula [1]

Embedded image General formula [2]

Embedded image [Wherein X ¹ and X ² are each independently N or CH
Wherein Y ¹ and Y ² are each independently S, O, N-
Z represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted heterocyclic group. R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. An aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group,
A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group,
Represents a substituted or unsubstituted amino group, a substituted or unsubstituted alkylamino group, or a substituted or unsubstituted arylamino group. ]

Further, the present invention is the organic electroluminescent device material described above, wherein R ¹ and R ² are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

Further, the present invention provides an organic electroluminescence device having a plurality of organic compound thin films including a light emitting layer formed between a pair of electrodes, wherein at least one layer is a layer containing the above-mentioned organic electroluminescence device material. It is an electroluminescent element.

Further, the present invention provides an organic electroluminescence device having 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 above-mentioned organic electroluminescence device material. It is an electroluminescent element.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the general formula [1] and the general formula
X of the compound represented by [2]¹And X ^TwoIs German
Stand for N or CH, Y¹And Y^TwoIs German
Stand for S, O, NZ. Where Z is a hydrogen atom,
Substituted or unsubstituted alkyl group, substituted or unsubstituted
Aryl group, substituted or unsubstituted cycloalkyl group,
Represents a substituted or unsubstituted heterocyclic group. Examples of alkyl groups
As methyl, ethyl, propyl, butyl
Group, sec-butyl group, tert-butyl group, pentyl
Group, hexyl group, heptyl group, octyl group, stearyl
Group, trichloromethyl group, etc.
Examples of the body include a cyclopentane ring and a cyclohexane ring.
And the substituted or unsubstituted aryl group is
Phenyl, biphenyl, terphenyl, naphthyl
Group, anthryl group, phenanthryl group, fluorenyl
Group, pyrenyl group, etc., and substituted or unsubstituted heterocyclic ring
As the group, a pyrrole group, a pyrroline group, a pyrazole group,
Pyrazoline, imidazole, triazole, pyri
Gin group, pyridazine group, pyrimidine group, pyrazine group,
Liadin group, indole group, purine group, quinoline group,
Soquinoline, sinoline, quinoxaline, benzoquinoline
Norin, fluorenone, carbazole, oxazo
Group, oxadiazole group, thiazole group, thiadia
Sol group, triazole group, imidazole group, benzoo
Xazole group, benzothiazole group, benzotriazole
Group, benzimidazole group, bisbenzoxazole
Group, bisbenzothiazole group, bisbenzimidazole
Group, anthrone group, dibenzofuran group, dibenzothiophene
Ene group, anthraquinone group, acridone group, phenothia
Gin group, pyrrolidine group, dioxane group, morpholine group
And the like.

Specific examples of the halogen atom of R ^{1 to} R ^{4 in} the compounds represented by the general formulas [1] and [2] in the present invention include chlorine, bromine, iodine and fluorine.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a stearyl group, and a trichloromethyl group. There are specific examples of cycloalkyl such as a cyclopentane ring and a cyclohexane ring.

Specific examples of the alkoxy groups represented by R ^{1 to} R ^{4 in} the compounds represented by the general formulas [1] and [2] in the present invention include methoxy, ethoxy, n-butoxy, tert- Butoxy group, trichloromethoxy group,
Trifluoroethoxy group, pentafluoropropoxy group, 2,2,3,3-tetrafluoropropoxy group,
There are a 1,1,1,3,3,3-hexafluoro-2-propoxy group and a 6- (perfluoroethyl) hexyloxy group, and specific examples of the aryloxy group include a phenoxy group and a p-nitrophenoxy group. Group, p-tert-butylphenoxy group, 3-fluorophenoxy group, pentafluorophenyl group, 3-trifluoromethylphenoxy group and the like.

In the present invention, the general formula [1] and the general formula
R of the compound represented by [2]¹~ R ^FourAlkylthio group of
Specific examples of methylthio, ethylthio, te
rt-butylthio group, hexylthio group, octylthio
Group, trifluoromethylthio group, etc.
Specific examples of the group include a phenylthio group and p-nitrophen.
Nilthio group, p-tert-butylphenylthio group, 3
-Fluorophenylthio group, pentafluorophenylthio
Group, 3-trifluoromethylphenylthio group, etc.
You.

In the present invention, the aryl groups represented by R ^{1 to} R ^{4 in} the compounds represented by the general formulas [1] and [2] include phenyl, biphenyl, terphenyl, naphthyl, anthryl, There are a phenanthryl group, a fluorenyl group, a pyrenyl group, and the like, and examples of the heterocyclic group include a pyrrole group, a pyrroline group, a pyrazole group, a pyrazoline group, an imidazole group, a triazole group, a pyridine group, a pyridazine group, a pyrimidine group, a pyrazine group, and a triazine group. , Indole, purine, quinoline, isoquinoline, sinoline, quinoxaline, benzoquinoline, fluorenone, carbazole, oxazole, oxadiazole, thiazole, thiadiazole, triazole, imidazole, benzo Oxazole group, benzothiazole group, Benzotriazole, benzimidazole, bisbenzoxazole, bisbenzothiazole, bisbenzimidazole, anthrone, dibenzofuran, dibenzothiophene, anthraquinone, acridone, phenothiazine, pyrrolidine, dioxane, morpho There are phosphorus groups and the like.

The general formula [1] and the general formula in the present invention
R of the compound represented by [2]¹~ R ^FourSpecific amino group of
Examples include amino groups, bis (acetoxymethyl) amido
Group, bis (acetoxyethyl) amino group, bisaceto
Xypropyl) amino group, bis (acetoxybutyl) amine
Amino group, and a specific example of an alkylamino group is
Tylamino group, diethylamino group, dipropylamino
Group, dibutylamino group, benzylamino group dibenzyla
There are a mino group and the like, and specific examples of the arylamino group include:
Phenylamino group, (3-methylphenyl) amino group,
(4-methylphenyl) amino group, phenylmethylamido
Group, diphenylamino group, bis (4-phenoxy
Nil) amino group, bis (4-biphenyl) amino group,
[4- (4-tolyl) phenyl] amino group, bis (3
-Methylphenyl) amino group, bis (4-methylphenyi)
L) amino group, naphthylphenylamino group, bis [4-
(Α, α'-dimethylbenzyl) phenyl] amino group and the like
There is.

In the present invention, the aryl group of A ¹ , the heterocyclic group, the alkyl group of Z, the aryl group, the cycloalkyl group, the heterocyclic group, and the alkyl group, aryl group and alkoxy group represented by R ^{1 to} R ⁴ The following substituents are representative examples of groups that may be substituted with an aryloxy group, an alkylthio group, an arylthio group, a cycloalkyl group, an aryl group, a heterocyclic group, an amino group, an alkylamino group, and an arylamino group. is there.

The halogen atom includes chlorine, bromine, iodine and fluorine. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a ter
t-butyl group, pentyl group, hexyl group, heptyl group,
There are an octyl group, a stearyl group, a trichloromethyl group and the like. As the cycloalkyl, a cyclopentane ring, a cyclohexane ring, a 1,3-cyclohexadienyl group, a 2-
Examples thereof include a cyclopenten-1-yl group and a 2,4-cyclopentadiene-1-ylenyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-butoxy group, a tert-butoxy group, a trichloromethoxy group, a trifluoroethoxy group, a pentafluoropropoxy group, a 2,2,3,3-tetrafluoropropoxy group. , 1,1,1,3,3,3-hexafluoro-2-propoxy group, 6- (perfluoroethyl) hexyloxy group and the like.
Phenoxy group, p-nitrophenoxy group, p-tert
-Butylphenoxy group, 3-fluorophenoxy group, pentafluorophenyl group, 3-trifluoromethylphenoxy group and the like.

Examples of the alkylthio group include a methylthio group,
There are an ethylthio group, a tert-butylthio group, a hexylthio group, an octylthio group, a trifluoromethylthio group and the like. As the arylthio group, a phenylthio group, a p-nitrophenylthio group, a p-tert-butylphenylthio group, a 3-fluorophenyl A thio group, a pentafluorophenylthio group, a 3-trifluoromethylphenylthio group, and the like.

Examples of the aryl group include phenyl, biphenyl, terphenyl, naphthyl, anthryl,
There are a phenanthryl group, a fluorenyl group, a pyrenyl group, and the like, and examples of the heterocyclic group include a pyrrole group, a pyrroline group, a pyrazole group, a pyrazoline group, an imidazole group, a triazole group, a pyridine group, a pyridazine group, a pyrimidine group, a pyrazine group, and a triazine group. , Indole, purine, quinoline, isoquinoline, sinoline, quinoxaline, benzoquinoline, fluorenone, carbazole, oxazole, oxadiazole, thiazole, thiadiazole, triazole, imidazole, benzo Oxazole group, benzothiazole group, benzotriazole group, benzimidazole group, bisbenzooxazole group, bisbenzothiazole group, bisbenzimidazole group, anthrone group, dibenzofuran group, dibenzothiophene group Anthraquinone group, acridone group, a phenothiazine group, a pyrrolidine group, dioxane group,
There is a morpholine group and the like.

Examples of the amino group include an amino group, a bis (acetoxymethyl) amino group, a bis (acetoxyethyl) amino group, a bisacetoxypropyl) amino group and a bis (acetoxybutyl) amino group. Examples are ethylamino, diethylamino,
There are a dipropylamino group, a dibutylamino group, a benzylamino group and a dibenzylamino group. Specific examples of the arylamino group include a phenylamino group, a (3-methylphenyl) amino group, and a (4-methylphenyl) amino group. , Phenylmethylamino group, diphenylamino group, bis (4
-Phenoxyphenyl) amino group, bis (4-biphenyl) amino group, bis [4- (4-tolyl) phenyl] amino group, bis (3-methylphenyl) amino group, bis (4-methylphenyl) amino group, A naphthylphenylamino group and a bis [4- (α, α′-dimethylbenzyl) phenyl] amino group.

In the present invention, the general formulas [1] and [2]
Can be produced, for example, by the following method.

A compound represented by the following general formula [3] or [4] is combined with an aldehyde compound represented by the general formulas [5] and [6] and N, N'-dimethylformamide or dimethyl sulfoxide. The compound represented by the general formula [1] or the general formula [2] can be obtained by heating in the air.

General formulas [3] and [4]

Embedded image General formula [5] R ¹ CHO General formula [6] R ² CHO [In the formula, A ¹ , X ¹ , X ² , Y ¹ , Y ² , and R ^{1 to} R ⁴ are the same as described above. ]

The compounds represented by the general formulas [1] and [2] include a carboxylic acid compound represented by the following general formulas [7] and [8] and a general formula [3] or a general formula [3] It can also be obtained by heating the compound represented by [4] in polyphosphoric acid.

Formula [7] R ¹ COOH Formula [8] R ² COOH wherein R ¹ and R ² are the same as above. ]

Hereinafter, typical examples of the compounds of the present invention are specifically shown in Table 1, but the present invention is not limited to the following typical examples.

[0027]

[Table 1]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

The organic EL device is a device in which a single or multilayer organic thin 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. The multilayer type is (anode / hole injection layer / light emitting layer /
There is an organic EL device having a multilayer structure of (cathode), (anode / light-emitting layer / electron injection layer / cathode), and (anode / hole injection layer / light-emitting layer / electron injection layer / cathode). General formula [1] of the present invention
And the compound represented by the general formula [2] is a compound having strong fluorescence in a solid state and excellent in electroluminescence, so that it can be used in a light emitting layer as a light emitting material. The compounds of the general formulas [1] and [2]
By doping a doping material in the light emitting layer at an optimum ratio in the light emitting layer, it is possible to select a high light emitting efficiency and an optimum light emitting wavelength. Further, the compounds of the general formulas [1] and [2] can transport carriers such as holes or electrons, and thus can be used for a hole injection layer or an electron injection layer of an organic EL device. It is.

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

The organic EL element has a multi-layer structure, so that a decrease in luminance and life due to quenching can be prevented. If necessary, a combination of two or more kinds of light emitting materials, doping materials, hole injecting materials for injecting carriers, and electron injecting materials can also be used. Also,
The hole injection layer, the light-emitting layer, and the electron injection layer may each be formed in a layer structure of two or more layers, and an element structure in which holes or electrons are efficiently injected from the electrode and transported in the layer is selected. You.

The conductive material used for the anode of the organic EL element preferably has a work function of more than 4 eV, and may be selected from carbon, aluminum, vanadium, iron, cobalt, and the like.
Nickel, tungsten, silver, gold, platinum, palladium and the like and alloys thereof, ITO substrate, metal oxide such as tin oxide and indium oxide called NESA substrate, and organic conductive resin such as polythiophene and polypyrrole are used. . The conductive material used for the cathode is preferably one having a work function of less 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 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 heating temperature, atmosphere, and degree of vacuum, and an appropriate ratio is selected. The anode and the cathode may be formed by two or more layers if necessary.

In the organic EL device, at least one of them is desirably sufficiently transparent in the emission wavelength region of the device in order to emit light efficiently. Further, it is desirable that the substrate is also transparent. The transparent electrode is set so as to secure a predetermined translucency by a method such as vapor deposition or sputtering using the above conductive material. 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 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 a dry film forming method such as vacuum evaporation and sputtering and a wet film forming method such as spin coating and dipping can be applied. The thickness is not particularly limited, but each layer needs to be set to an appropriate 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 formation method, a material for forming each layer is dissolved or dispersed in an appropriate solvent such as chloroform, tetrahydrofuran, dioxane or the like to form a thin film.
The solvent may be any. In any of the thin films, a suitable resin or additive may be used to improve film forming properties, prevent pinholes in the film, and the like. Examples of such a resin include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, and poly-N-.
Examples include photoconductive resins such as vinyl carbazole and polysilane, and conductive resins such as polythiophene and polypyrrole. Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.

The emission color can be changed by using a doping material together with the general formula [1] or the general formula [2]. Examples of the doping material used together with the general formula [1] or the general formula [2] 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 derivatives thereof, but are not limited thereto.

The hole injecting material has the ability to inject holes, has an excellent hole injecting effect on the light emitting layer or the light emitting material, and has an electron injecting layer or an electron exciton generated in the light emitting layer. Compounds that prevent migration to the injection material and have excellent thin film forming ability are mentioned. Specifically, phthalocyanine compounds, naphthalocyanine compounds, porphyrin compounds, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acylhydrazone, poly Arylalkane, stilbene, butadiene,
Benzidine-type triphenylamine, styrylamine-type triphenylamine, diamine-type triphenylamine and the like, and derivatives thereof, and polyvinyl carbazole,
Although there are polymer materials such as polysilane and conductive polymer,
It is not limited to these.

The electron injecting material has a capability of injecting 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 injecting excitons generated in the light emitting layer. Compounds that prevent transfer to a material and have excellent thin film forming ability are exemplified. For example, quinoline metal complex, oxadiazole, benzothiazole metal complex, benzoxazole metal complex, benzimidazole metal complex, fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxadiazole, thiadiazole, tetrazole, perylenetetracarbon Acid, fluorenylidenemethane, anthraquinodimethane,
Examples include, but are not limited to, anthrones and derivatives thereof. Alternatively, an electron accepting material may be added to the hole injecting material and an electron donating material may be added to the electron injecting material to sensitize the material.

In order to improve the stability of the organic EL device obtained according to the present invention with respect to temperature, humidity, atmosphere, etc., a protective layer is provided on the surface of the device or silicon oil is sealed to protect the entire device. It is also possible.

[0052]

The present invention will be described in more detail with reference to the following examples.

Method for synthesizing compound (3) 6.0 g of 2,5-diamino-1,3-benzenethiol dihydrochloride, 14 g of diphenylaminobenzaldehyde and 100 ml of dimethyl sulfoxide were placed in a flask and stirred at 140 ° C. for 6 hours. did. After cooling, the mixture was poured into water, and the resulting precipitate was collected by filtration. The precipitate was subjected to column purification using silica gel, and then to sublimation purification. NMR, FD
The formation of the compound was confirmed by -MS and IR. FIG. 1 shows an IR spectrum of the compound (3).

Method for synthesizing compound (4) 4.0 g of 2,5-diamino-1,3-benzenethiol dihydrochloride, 8.4 g of anthralaldehyde and 70 ml of dimethyl sulfoxide were placed in a flask and heated at 140 ° C. for 6 hours.
It was time stirring. After cooling, the mixture was poured into water, and the resulting precipitate was collected by filtration. The precipitate was subjected to column purification using silica gel, and then to sublimation purification. The formation of the compound was confirmed by NMR, FD-MS, and IR.

Method for synthesizing compound (26) 4,6-diaminoresorcin dihydrochloride in a flask
0 g, anthralaldehyde 12 g and polyphosphoric acid 70 ml
And stirred at 150 ° C. for 18 hours. After cooling,
The mixture was poured into water, and the resulting precipitate was collected by filtration. The precipitate was subjected to column purification using silica gel, and then to sublimation purification. NM
The formation of the compound was confirmed by R, FD-MS, and IR.

Example 1 N, N '-(3) was placed on a cleaned glass plate with ITO electrodes.
-Methylphenyl) -N, N'-diphenyl-1,1-
Biphenyl-4,4-diamine (TPD) was vacuum-deposited to obtain a hole injection layer having a thickness of 20 nm. Next, the compound (3) was deposited to form a 40-nm-thick light-emitting layer, and a tris (8-hydroxyquinoline) aluminum complex was deposited to obtain a 30-nm-thick electron injection layer. On top of that, an alloy of magnesium and silver mixed at a ratio of 10: 1 with a film thickness of 100 n
m electrodes were formed to obtain an organic EL device. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. This device has a light emission luminance of 110 cd / m ² and a maximum light emission luminance of 25000 cd / m at a DC voltage of 5 V.
Light emission with a luminous efficiency of 4.5 lm / W at ^2.5 and 5 V was obtained. Next, as a result of a life test in which the device was continuously lit at a current density of 3 mA / cm ² , luminescence of １ ／ or more of the initial luminance was maintained for 10000 hours or more.

Examples 2 to 68 Organic EL devices were produced in the same manner as in Example 1 except that the compounds shown in Table 2 were used in place of the compound (1) in the light emitting layer. This device exhibited the emission characteristics shown in Table 2.

[0058]

[Table 2]

[0059]

[0060]

[0061]

Example 69 A compound (24) was vacuum-deposited on a washed glass plate with an ITO electrode to form a 100 nm-thick light-emitting layer, on which an alloy obtained by mixing magnesium and silver at a ratio of 10: 1 was used. An electrode having a thickness of 150 nm was formed to obtain an organic EL device. The light emitting layer and the cathode were deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. This element has a DC voltage of 5
Luminance 60 cd / m ² at V, maximum luminance 1400 c
Light emission with a luminous efficiency of 0.4 lm / W at d / m ² and 5 V was obtained. Next, at a current density of 3 mA / cm ² , as a result of a life test in which the device was continuously emitted, 1 / l of the initial luminance was obtained.
Two or more light emissions were maintained for 5000 hours or more.

Example 70 A compound (3) was placed on a washed glass plate with an ITO electrode.
2) was deposited to form a hole injection layer having a thickness of 80 nm, and then a tris (8-hydroxyquinoline) aluminum complex was deposited to obtain a light emitting layer having a thickness of 20 nm. in addition,
An alloy of magnesium and silver mixed at a ratio of 10: 1 with a film thickness of 10
An 0 nm electrode was formed to obtain an organic EL device. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. This device has a light emission luminance of 90 cd / m ² at a DC voltage of 5 V and a maximum light emission luminance of 8500 cd / m.
Light emission with a luminous efficiency of 0.9 lm / W at ^2.5 and 5 V was obtained. Next, as a result of a life test in which the device was continuously caused to emit light at a current density of 3 mA / cm ² , light emission of 1/2 or more of the initial luminance was maintained for 3000 hours or more.

Example 71 A 50-nm-thick hole injection layer was formed by vapor deposition of TPD on a washed glass plate with an ITO electrode, and then a tris (8-hydroxyquinoline) aluminum complex was vapor-deposited. A 20 nm light emitting layer was obtained. The compound (6) is vapor-deposited to form an electron injection layer having a thickness of 60 nm, and an alloy obtained by mixing magnesium and silver at a ratio of 10: 1 to a thickness of 100 nm.
m electrodes were formed to obtain an organic EL device. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. This device has a light emission luminance of 100 cd / m ² and a maximum light emission luminance of 13000 cd / m at a DC voltage of 5 V.
Light emission with a luminous efficiency of 2.1 lm / W at ^2.5 and 5 V was obtained. Next, as a result of a life test in which the device was continuously caused to emit light at a current density of 3 mA / cm ² , light emission of 1/2 or more of the initial luminance was maintained for 3000 hours or more.

Example 72 N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1 ′ was placed on a washed glass plate with an ITO electrode.
-Biphenyl-4,4'-diamine was vacuum-deposited to obtain a 20-nm-thick hole injection layer. Next, N, N'-
(4-Methylphenyl) -N, N '-(4-n-butylphenyl) -phenanthrene-9,10-diamine and compound (4) were deposited at a weight ratio of 100: 1 to form a film having a thickness of 40.
A light emitting layer having a thickness of 10 nm was formed, and a tris (8-hydroxyquinoline) aluminum complex was deposited thereon to obtain an electron injection layer having a thickness of 10 nm. An electrode having a thickness of 100 nm is formed thereon by using an alloy in which magnesium and silver are mixed at a ratio of 10: 1.
An L element was obtained. The hole injection layer and the light emitting layer are 10 ^-6 Torr
The film was deposited under the condition of room temperature and substrate temperature in a vacuum of r. This device emitted light with a luminance of 350 cd / m ² at a DC voltage of 5 V, a maximum luminance of 54000 cd / m ² , and a luminous efficiency of 4.0 lm / W at 5 V. Next, 3 mA / cm ²
As a result of a life test in which the device was continuously lit at a current density of, light emission of １ ／ or more of the initial luminance was maintained for 10000 hours or more.

Example 73 4, 4 ', 4 "was placed on a washed glass plate with an ITO electrode.
-Tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine was vacuum deposited to a film thickness of 40
As a result, a hole injection layer having a thickness of nm was obtained. Then, 4,4′-bis [N
-(1-Naphthyl) -N-phenylamino] biphenyl was vacuum-deposited to obtain a 10-nm-thick second hole injection layer. Further, the compound (3) is vacuum-deposited to a film thickness of 30 n.
m, a bis (2-methyl-8-hydroxyquinolinato) (1-phenolate) gallium complex was further vacuum-deposited to form a 30-nm-thick electron injection layer,
An electrode having a thickness of 150 nm was formed thereon using an alloy in which aluminum and lithium were mixed at a ratio of 25: 1 to obtain an organic EL device. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. This device has an emission luminance of 260 (cd / m ² ) at a DC voltage of 5 V, a maximum emission luminance of 34000 (cd / m ² ), and an emission efficiency of 5.0.
(Lm / W) was obtained.

Examples 74 to 83 Organic EL devices were prepared in the same manner as in Example 1 except that the compounds shown in Table 4 were used in place of the compound (3) in the light emitting layer. This device exhibited the emission characteristics shown in Table 3.

[0068]

Example 84 Compound (1) was placed on a washed glass plate with an ITO electrode.
4), tris (8-hydroxyquinoline) aluminum
Complex, TPD, polycarbonate resin (PC-A)
Dissolved in tetrahydrofuran in a weight ratio of 3: 2: 3: 8
100nm light emission by spin coating
Layer obtained. Further, magnesium and silver were mixed at a ratio of 10: 1.
An electrode with a thickness of 150 nm is formed from the alloy
Got a child. This element emits 12 cd of light at a DC voltage of 5 V.
/ M^Two, Maximum light emission luminance 3100 cd / m ^TwoAt 5V
Luminous efficiency of 0.5 lm / W was obtained. Then 3mA
/ Cm^TwoThe device was continuously lit at a current density of
As a result of the life test, 300 or more luminescence of initial luminance was 300
It was kept for more than 0 hours.

The organic EL device of the present invention achieves an improvement in luminous efficiency, luminous luminance and a long life, and is used together with a luminescent material, a doping material, a hole injection material, an electron injection material, and a sensitizer. It does not limit the agent, resin, electrode material and the like, and the element manufacturing method.

[0071]

According to the present invention, it is possible to obtain an organic EL device having higher luminous efficiency, higher luminance and longer life than the conventional one.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of compound (3).

Continuation of the front page (72) Inventor Tadashi Ogawa 2-3-113 Kyobashi, Chuo-ku, Tokyo Inside Toyo Ink Manufacturing Co., Ltd. (72) Inventor Toshio Enoda 2-3-13-1 Kyobashi, Chuo-ku, Tokyo Toyo In Niki Manufacturing Co., Ltd.

Claims (4)

[Claims] An organic electroluminescent device material represented by the following general formula [1] or [2]. General formula [1] General formula [2] [Wherein X ¹ and X ² are each independently N or CH
Wherein Y ¹ and Y ² are each independently S, O, N-
Z represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted heterocyclic group. . R ^{1 to} R ⁴ each independently represent a hydrogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy Group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted amino Represents a group, a substituted or unsubstituted alkylamino group, or a substituted or unsubstituted arylamino group. ] 2. The organic electroluminescent device material according to claim 1, wherein R ¹ and R ² are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. 3. An organic electroluminescence device in which a plurality of organic compound thin films including a light emitting layer are formed between a pair of electrodes, wherein at least one layer is a layer containing the organic electroluminescence device material according to claim 1 or 2. Organic electroluminescent element. 4. An organic electroluminescence device in which a plurality of organic compound thin films including a light emitting layer are formed between a pair of electrodes, wherein the light emitting layer is a layer containing the organic electroluminescent device material according to claim 1 or 2. Organic electroluminescent element.