JP4535107B2 - Organic electroluminescence device using new amino compound - Google Patents

Description

  The present invention relates to a novel amino compound, a method for producing the same, and use thereof. The amino compound of the present invention can be used for photosensitive materials, organic photoconductive materials and the like. More specifically, the amino compound of the present invention is useful for an organic electroluminescence element or an electrophotographic photoreceptor used for a surface light source or display.

Organic photoconductive materials that have been developed as photoconductors and charge transport materials have various advantages such as low cost, various processability, and non-polluting properties, and many compounds have been proposed.
For example, organic photoconductive materials such as oxadiazole compounds, hydrazone compounds, pyrazoline compounds, oxazole compounds, arylamine compounds, benzidine compounds, stilbene compounds, and butadiene compounds have been proposed.

One technique using a charge transport material is an electrophotographic photoreceptor. The electrophotographic system is one of image forming methods invented by Carlson.
In this method, after charging the photoconductor by corona discharge, image exposure is performed to form an electrostatic latent image on the photoconductor, and toner is attached to the electrostatic latent image and developed, and the resulting toner image is obtained. Is transferred to paper.
The basic characteristics required of a photoconductor in such an electrophotographic system are that an appropriate potential is maintained in a dark place, there is little charge dissipation in the dark place, and charge is quickly dissipated by light irradiation. To do.

  In the conventional electrophotographic photoreceptors, inorganic photoconductors such as selenium, selenium alloy, zinc oxide, cadmium sulfide have been used. These inorganic photoconductors have advantages such as high durability and a large number of printed sheets, but problems such as high production costs, inferior processability, and toxicity are pointed out. .

  In order to overcome these drawbacks, organic photoconductors have been developed. However, electrophotographic photoreceptors using conventional organic photoconductors as charge transporting materials have characteristics such as chargeability, sensitivity, and residual potential. At present, it cannot be said that the electrophotographic characteristics are always satisfied, and it has been desired to develop a charge transport material having excellent charge transport capability and durability.

  As a technique using a charge transport material, an organic electroluminescence element can be cited. Electrominance elements using organic compounds are promising for use as solid-state, inexpensive, large-area full-color display elements, and many studies have been conducted.

  In general, an organic electroluminescence element 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 and holes are injected from the anode. Furthermore, this electron and hole are recombined in the light emitting layer, and energy is emitted as light when the energy level returns from the conduction band to the valence band.

  Conventional organic electroluminescent elements have a higher driving voltage and lower luminance and luminous efficiency than inorganic electroluminescent elements. In addition, the characteristic deterioration was remarkably not practical.

In recent years, an organic electroluminescence element having a thin film containing an organic compound having a high fluorescence quantum efficiency that emits light at a low voltage of 10 V or less has been reported and attracted attention (Applied Physics Letters, Vol. 51, 913, see 1987).
This method uses a metal chelate complex as a phosphor layer and an amine compound as a hole injection layer to obtain green light emission with high luminance. The luminance is several hundred cd / m ² at a DC voltage of 6 to 7 V, The maximum luminous efficiency is 1.5 l (el) m / W, and the performance is close to the practical range.

However, the organic electroluminescence element up to now has improved luminous efficiency due to the improvement of the configuration, but does not yet have sufficient luminance. Moreover, it has a big problem that it is inferior in stability during repeated use.
Therefore, it is hoped to develop a charge transport material with excellent charge transport capability and durability for the development of an organic electroluminescence device with higher emission brightness and excellent stability during repeated use. It is rare.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel amino compound useful as a durable charge transport material, a production method thereof, and an application thereof. .

That is, the present invention provides a novel amino compound represented by the following general formula (I);

In the above formula, A represents a group represented by the following general formula (II);

Preferred A are:

In general formula (I), Ar ₁ represents an aryl group such as phenyl or diphenyl, or a heterocyclic group such as thienyl, pyryl, furyl, pyridyl or the like. Preferred are phenyl, thienyl, pyridyl, furyl and the like.
These groups may have an alkyl group such as methyl or ethyl, an alkoxy group such as methoxy or ethoxy group, a halogen atom such as chlorine atom, or an amino group such as diphenylamino group as a substituent.

を形成してもよい。好ましくは、フェニル、Ｒ_１とＲ_２が一体となって形成した環；

である。
これらの基は、メチル、エチル等のアルキル基あるいはメトキシ、エトキシ等のアルコキシ基を置換基として有していてもよい。 In the formula (I), independently R _1, R ₂ are each, aralkyl groups such as benzyl, phenyl, aryl or thienyl diphenyl such as pyrryl, furyl, a heterocyclic group such as pyridyl, and R ₁ R ₂ together with the nitrogen atom to which R ₁ and R ₂ are attached is a ring, for example;

May be formed. Preferably, phenyl, a ring formed by combining R ₁ and R ₂ ;

It is.
These groups may have an alkyl group such as methyl or ethyl or an alkoxy group such as methoxy or ethoxy as a substituent.

In general formula (I), R ₃ represents a hydrogen atom or an alkyl group such as methyl or ethyl.

（式中、Ａは一般式（Ｉ）中と同義；Ｘはハロゲン原子を表わす。）
と下記一般式（IV）で表わされるアミノ化合物；

（式中、Ａｒ_ｌ、Ｒ_１、Ｒ_２、Ｒ_３は一般式（Ｉ）と同意義を表わす）
を反応させることによって製造することができる。 The amino compound represented by the general formula (I) can be produced using a specific raw material and utilizing a known chemical reaction. For example, a trihalogen compound represented by the following general formula (III);

(In the formula, A is as defined in formula (I); X represents a halogen atom.)
And an amino compound represented by the following general formula (IV):

(In the formula, Ar ₁ , R ₁ , R ₂ , R ₃ represent the same meaning as in the general formula (I))
Can be made to react.

（式中、Ａ、Ａｒ_１は一般式（Ｉ）と同意義を表わす）
と下記一般式（VI）で表わされるハロゲン化合物；

（式中、Ｘはハロゲン原子を表わし、Ｒ_１、Ｒ_２、Ｒ_３は一般式（Ｉ）と同意義を表わす）
を反応させることによっても製造することができる。 A triamino compound represented by the general formula (V);

(In the formula, A and Ar ₁ are as defined in the general formula (I))
And a halogen compound represented by the following general formula (VI):

(In the formula, X represents a halogen atom, and R ₁ , R ₂ , and R ₃ have the same meaning as in formula (I)).
Can also be produced by reacting.

（式中、Ｘはハロゲン原子を表わし、Ａｒ_１、Ｒ_３は一般式（Ｉ）と同意義を表わす）
と下記一般式（VIII）で表わされるアミノ化合物；

（式中、Ｒ_１、Ｒ_２は一般式（Ｉ）と同意義を表わす。）
を反応させることによっても製造することができる。 As another production method, a trihalogen compound represented by the following general formula (VII):

(In the formula, X represents a halogen atom, and Ar ₁ and R ₃ have the same meaning as in formula (I)).
And an amino compound represented by the following general formula (VIII):

(In the formula, R ₁ and R ₂ are as defined in general formula (I).)
Can also be produced by reacting.

（式中、Ａｒ_１，Ｒ_３は一般式（Ｉ）と同意義を表わす）
と下記一般式（Ｘ）で表されるハロゲン化合物；

（式中、Ｘはハロゲン原子を表わし、Ｒ_１、Ｒ_２はそれぞれ独立して、それぞれ置換基を有してもよいアラルキル基、アリール基または複素環基を表わす）
を反応させることによっても製造することができる。 And a triamino compound represented by the general formula (IX);

(In the formula, Ar ₁ and R ₃ are as defined in the general formula (I))
And a halogen compound represented by the following general formula (X);

(In the formula, X represents a halogen atom, and R ₁ and R ₂ each independently represents an aralkyl group, an aryl group or a heterocyclic group which may have a substituent)
Can also be produced by reacting.

  The amino compound can be synthesized by the Ullmann reaction in the presence of a basic compound or a transition metal compound catalyst and a solvent.

  The basic compounds used for the synthesis of the amino compounds are generally alkali metal hydroxides, carbonates, hydrogen carbonates, alcoholates, etc., but quaternary ammonium compounds, aliphatic amines and aromatic amines. It is also possible to use organic bases such as Of these, alkali metals and quaternary ammonium carbonates and hydrogen carbonates are preferably used. Further, alkali metal carbonates and hydrogen carbonates are most preferable from the viewpoints of reaction rate and thermal stability.

As the transition metal or transition metal compound catalyst used in the synthesis, for example, metals such as Cu, Fe, Co, NI, Cr, V, Pd, Pt, and Ag and their compounds are used. Palladium or compounds thereof are preferred. The copper compound is not particularly limited, and most copper compounds are used, but cuprous iodide, cuprous chloride, cuprous oxide, cuprous bromide, cuprous cyanide, cuprous sulfate , Cupric sulfate, cupric chloride, cupric hydroxide, cupric oxide, cupric bromide, cupric phosphate, cuprous nitrate, cupric nitrate, copper carbonate, first acetic acid Copper, cupric acetate and the like are preferable. Among these, CuCl, CuCl, CuBr, CuBr ₂ , Cul, CuO, Cu ₂ O, CuSO ₄ , and Cu (OCOCH ₃ ) ₂ are particularly preferable because they are easily available. As the palladium compound, halides, sulfates, nitrates, organic acid salts and the like can be used. The amount of the transition metal and its compound used is 0.5 to 500 mol% of the halogen compound to be reacted.

  The solvent used in the synthesis may be a commonly used solvent, but an aprotic polar solvent such as dichlorobenzene, nitrobenzene, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone is preferably used.

  The reaction is generally carried out at a temperature of 100 to 250 ° C. under normal pressure, but it may of course be carried out under pressure. After completion of the reaction, the solid content precipitated in the reaction solution is removed, and then the solvent is removed to obtain the product.

  Specific examples of the amino compound include the following. These exemplifications do not present the amino compounds of the present invention in a restrictive manner, nor are they disclosed with the intention of limiting them.

  The amino compound represented by the general formula (I) has an excellent charge transport function, particularly a hole transport function, and is excellent in durability and heat resistance. Therefore, the amino compound represented by the general formula (I) of the present invention is excellent in use as a charge transport material, and various applications are conceivable using such a function, for example, a photoreceptor or an organic electroluminescence. It can be suitably used as a charge transport material for a sense element.

  First, the case where the amino compound represented by the general formula (I) is used as an electrophotographic photoreceptor will be described.

The amino compound represented by the general formula (I) can be used in any layer of the electrophotographic photosensitive member, but is preferably used as a charge transporting material because of its high charge transporting properties.
The amino compound acts as a charge transport material and can transport charges generated by light absorption or injected from the electrode very efficiently, so that a photoreceptor excellent in sensitivity and high-speed response can be obtained. In addition, since the compound is excellent in ozone resistance and light stability, a photoreceptor having excellent durability can be obtained.

  As an electrophotographic photosensitive member, for example, a photosensitive member formed by forming a photosensitive layer in which a charge generating material and a charge transporting material are dispersed in a resin solution on a conductive support, and charge generation as a photosensitive layer on the support. A photosensitive layer formed by laminating a layer and a charge transport layer, an undercoat layer or a conductive layer formed on a support, and a photosensitive layer formed thereon, or an undercoat layer on a support And a photoreceptor in which a photosensitive layer and a surface protective layer are sequentially laminated.

  As the support, a foil, a plate, or a drum shape made of copper, aluminum, iron, nickel, stainless steel or the like is used. In addition, these metals are vacuum-deposited or electroless-plated on paper or plastic drums, or a conductive compound layer such as conductive polymer, indium oxide or tin oxide is applied or deposited on paper or plastic drums. Things can also be used. Generally, aluminum is used. For example, after extruding, the drawn aluminum pipe is cut, and the outer surface is cut to about 0.2 to 0.3 mm using a cutting tool such as a diamond bite. Finished (cut tube), deep-drawn aluminum disc into cup shape, then finished outer surface by ironing (DI tube), impacted aluminum disc into cup shape Thereafter, the outer surface is finished by ironing (EI pipe), the extrusion process is followed by cold drawing (ED pipe), and the like. Moreover, you may use what cut | disconnected these surfaces further.

  When forming an undercoat layer on a support, an oxide film obtained by anodizing the surface of the support is often used as the undercoat layer. When the support is an aluminum alloy, it is effective to use an alumite layer as the undercoat layer. Further, it is also formed by dispersing a solution in which an appropriate resin is dissolved or a low resistance compound in the solution, applying the solution or dispersion on the conductive support, and drying the solution. In this case, as a material used for the undercoat layer, polyimide, polyamide, nitrocellulose, polyvinyl butyral, polyvinyl alcohol, and the like are suitable, and a low resistance compound may be dispersed in these resins. As the low resistance compound, metal compounds such as tin oxide, titanium oxide, zinc oxide, zirconium oxide, and magnesium fluoride, and organic compounds such as organic pigments, electron-withdrawing organic compounds, and organometallic complexes are preferably used. The thickness of the undercoat layer is 0.1 to 5 μm, preferably about 0.2 to 3 μm.

  A photosensitive layer is formed on the support or the undercoat layer. Hereinafter, a case where a charge generation layer and a charge transport layer are laminated as the photosensitive layer will be described.

  In forming the charge generation layer, the charge generation material is deposited by vacuum evaporation or dissolved in an appropriate solvent, or the pigment is added in an appropriate solvent or, if necessary, in a solution in which a binder resin is dissolved. A coating solution prepared by dispersing is formed by coating and drying. From the viewpoint of adhesiveness, those dispersed in the resin are good. The film thickness of the charge generation layer is 0.01 to 2 μm, preferably about 0.05 to 1 μm. The binder resin used for forming the charge generation layer is preferably 100% by weight or less based on the charge generation material, but is not limited thereto. Two or more kinds of resins may be used in combination.

  Examples of the charge generation material used for the charge generation layer include azo pigments (including bisazo pigments and trisazo pigments), triarylmethane dyes, thiazine dyes, oxazine dyes, xanthene dyes, cyanine dyes, Organic pigments such as styryl dyes, pyrylium dyes, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, bisbenzimidazole pigments, indanthrone pigments, squarylium pigments, phthalocyanine pigments, and the like And dyes. Other than this, any material can be used as long as it absorbs light and generates a charge carrier with a very high probability. In particular, azo (bis-based, tris-based) pigments and phthalocyanine-based materials can be used. Pigments are preferred.

  Examples of the resin used together with the charge generating material include saturated polyester resin, polyamide resin, acrylic resin, ethylene-vinyl acetate copolymer, ion-crosslinked olefin copolymer (ionomer), and styrene-butadiene block copolymer. , Polyarylate, polycarbonate, vinyl chloride-vinyl acetate copolymer, cellulose ester, polyimide, styrene resin, polyacetal resin, phenoxy resin, and other thermoplastic binders, epoxy resin, urethane resin, silicone resin, phenol resin, melamine resin , Xylene resins, alkyd resins, thermosetting binders such as thermosetting acrylic resins, photocurable resins, photoconductive resins such as poly-N-vinylcarbazole, polyvinylpyrene, and polyvinylanthracene can be used.

  Together with these resins, the above charge generating materials are alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, dimethyl Sulfoxides such as sulfoxide, ethers such as tetrahydrofuran, dioxane and ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, carbon tetrachloride and trichloroethylene Or a photosensitive coating solution prepared by dispersing or dissolving in an organic solvent such as benzene, toluene, xylene, ligroin, monochlorobenzene, dichlorobenzene or other aromatics. It was coated on, so that forming the charge generation layer and dried.

  A charge transport layer containing a charge transport material and a binder resin is provided on the charge generation layer formed as described above.

  Examples of the binder resin include polycarbonate, polyarylate, saturated polyester resin, polyamide resin, acrylic resin, ethylene-vinyl acetate copolymer, ion-crosslinked olefin copolymer (ionomer), styrene-butadiene block copolymer, vinyl chloride. -Thermoplastic binders such as vinyl acetate copolymer, cellulose ester, polyimide, styrene resin, polyacetal resin, phenoxy resin, epoxy resin, urethane resin, silicone resin, phenol resin, melamine resin, xylene resin, alkyd resin, heat A thermosetting binder such as a curable acrylic resin, a photocurable resin, a photoconductive resin such as poly-N-vinylcarbazole, polyvinylpyrene, and polyvinylanthracene can be used.

  In forming the charge transport layer of the photoreceptor, a coating solution obtained by dissolving a charge transport material and a binder resin in an appropriate solvent is applied onto the charge generation layer and dried. The thickness of the charge transport layer is 5 to 60 μm, preferably about 10 to 50 μm. Further, the content of the charge transport material in the charge transport layer cannot be defined unconditionally depending on the type, but is generally 0.02 to 2 parts by weight, preferably 0.5 to 1 part by weight based on 1 part by weight of the binder resin. It is desirable to add 2 parts by weight.

As the charge transport material used for the photoreceptor, two or more kinds of compounds represented by the general formula (I) may be used, or they may be used in combination with other charge transport materials.
Other charge transport materials used include hydrazone compounds, pyrazoline compounds, styryl compounds, triphenylmethane compounds, oxadiazole compounds, carbazole compounds, stilbene compounds, enamine compounds, oxazole compounds, triphenylamine compounds, tetraphenylbenzidine Compounds, hole transport materials such as azine compounds, fluorenone compounds, anthraquinodimethane compounds, diphenoquinone compounds, stilbenequinone compounds, thiopyran dioxide compounds, oxadiazole compounds, perylenetetracarboxylic acid compounds, fluorenylidenemethane compounds, Various materials such as an electron transport material such as an anthraquinone compound, anthrone compound, and cyanovinyl compound can be used.

  Examples of the solvent used for forming the charge transport layer include aromatic solvents such as benzene, toluene, xylene, and chlorobenzene, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, alcohols such as methanol, ethanol, and isopropanol, and acetic acid. Examples include esters such as ethyl and ethyl cellosolve, halogenated hydrocarbons such as carbon tetrachloride, carbon tetrabromide, chloroform, dichloromethane, and tetrachloroethane, ethers such as tetrahydrofuran and dioxane, dimethylformamide, dimethylsulfoxide, and diethylformamide. it can. These solvents may be used alone or in combination of two or more.

  In the case of forming the laminated photosensitive layer as described above, the charge transport layer and the charge generation layer can be applied using various coating apparatuses such as known ones. Specifically, various coating methods such as a dip coating method, a spray coating method, a spinner coating method, a blade coating method, a roller coating method, and a wire bar coating method can be used.

  In addition, in the case of the laminated photosensitive layer as described above, particularly in the charge transport layer, an additive for improving the film formability or flexibility, an additive for suppressing the accumulation of residual potential, etc. You may contain a well-known additive.

  Specific examples of these compounds include halogenated paraffin, polychlorinated biphenyl, dimethylnaphthalene, o-terphenyl, m-terphenyl, p-terphenyl, diethylbiphenyl, hydrogenated terphenyl, diisopropylbiphenyl, benzylbiphenyl, and diisopropyl. Plasticizers such as naphthalene, dibenzofuran, 9,10-dihydroxyphenanthrene, chloranil, tetracyanoquinodimethane, tetracyanoethylene, trinitrofluorenone, dicyanobenzoquinone, tetrachlorophthalic anhydride, 3,5 dinitrobenzoic acid, cyanovinyl compounds, etc. Sensitizers such as an electron-withdrawing sensitizer, methyl violet, rhodamine B, cyanine dye, pyrylium salt, thiapyrylium salt can be used.

  The greater the amount of plasticizer added, the lower the internal stress of the layer. Therefore, when the photosensitive layer is composed of a charge transport layer and a charge generation layer, the layer between the charge transport layer and the charge generation layer is used. In the case of a single layer type, the adhesion between the photosensitive layer and the support is improved. However, if the amount is too large, problems such as a decrease in mechanical strength and a decrease in sensitivity occur. Therefore, 1 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 10 to 10 parts by weight with respect to 100 parts by weight of the charge transport material. It is desirable to be about 50 parts by weight. The addition amount of the sensitizer is desirably 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, more preferably about 0.5 to 8 parts by weight with respect to 100 parts by weight of the charge transport material. .

  Furthermore, an antioxidant may be added to the photosensitive layer of the photoreceptor, particularly the charge transport layer, for the purpose of preventing ozone degradation. Examples of the antioxidant include hindered phenols, hindered amines, paraphenylenediamine, hydroquinone, spirochroman, spiroidanone, hydroquinoline and derivatives thereof, organic phosphorus compounds, and organic sulfur compounds.

As the amount of the antioxidant added is increased, the adhesion is improved. However, when the amount is too large, problems such as a decrease in mechanical strength and a decrease in sensitivity occur.
Therefore, it is desirable that the amount be 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, and more preferably about 3 to 20 parts by weight with respect to 100 parts by weight of the charge transport material. When the antioxidant and the plasticizer are used in combination, the total amount is 1 to 120 parts by weight, preferably 5 to 100 parts by weight, more preferably about 10 to 80 parts by weight. When the solubility of the plasticizer or antioxidant is low or the melting point is high, crystal precipitation may occur or the adhesiveness will not improve so much, so a compound having a melting point of the plasticizer or antioxidant of 100 ° C. or lower is used. It is preferable.

  A conductive layer may be provided between the support constituting the photoreceptor and the undercoat layer. As the conductive layer, a material in which a metal such as aluminum, iron or nickel is dispersed in a resin, conductive tin oxide, titanium oxide, antimony oxide, zirconium oxide, ITO (indium, tin oxide solid solution), etc. What disperse | distributed the metal oxide in resin is used suitably.

  Furthermore, a surface protective layer may be provided on the photosensitive layer. The thickness of the surface protective layer is desirably 5 μm or less. As materials used for the surface protective layer, polymers such as acrylic resin, polyaryl resin, polycarbonate resin, urethane resin, thermosetting resin, and photocurable resin are used as they are, or low resistance substances such as tin oxide and indium oxide are dispersed. Can be used. An organic plasma polymerization film may be used as the surface protective layer. The organic plasma polymerized film may appropriately contain oxygen, nitrogen, halogen, and Group 3 and Group 5 atoms of the periodic table as necessary.

  Next, the case where the compound represented by the general formula (I) is used as a material for an organic electroluminescence element will be described.

  1 to 4 schematically show an embodiment of an organic electroluminescence element. In FIG. 1, (1) is an anode, on which an organic hole injecting and transporting layer (2), an organic light emitting layer (3) and a cathode (4) are sequentially laminated. The hole injection transport layer contains an amino compound represented by the above general formula (I).

  In FIG. 2, (1) is an anode, and an organic hole injecting and transporting layer (2), an organic light emitting layer (3), an organic electron injecting and transporting layer (5), and a cathode (4) are sequentially laminated thereon. The organic hole injection transport layer or the organic light emitting layer contains the amino compound represented by the above general formula (I).

  In FIG. 3, (1) is an anode, on which an organic light emitting layer (3), an organic electron injecting and transporting layer (5), and a cathode (4) are sequentially laminated. The layer contains an amino compound represented by the above general formula (I).

  In FIG. 4, (1) is an anode, and an organic light emitting layer (3) and a cathode (4) are sequentially laminated thereon, and the organic light emitting material (6) and The charge transport material (7) is contained, and the amino compound represented by the general formula (I) is used as the charge transport material.

  In the organic electroluminescence device having the above structure, the anode (1) and the cathode (4) are connected by the lead wire (8), and the organic light emitting layer (3) is applied by applying a voltage to the anode (1) and the cathode (4). Emits light.

  For the organic light emitting layer, the organic hole injecting and transporting layer, and the organic electron injecting and transporting layer, if necessary, a known light emitting substance, a light emitting auxiliary material, and a charge transporting material for carrying carriers can be used.

  Since the specific amino compound represented by the general formula (I) has a low ionization potential and a large hole transport capability, the light emission starting voltage required for causing the organic electroluminescence element to emit light may be low and stable. It is thought that it is possible to emit light for a long time. Moreover, when an amino compound is used as an organic light emitter, it is considered that the amino compound itself functions as a light emitter and contributes to thermal stability.

  The conductive material used as the anode (1) of the organic electroluminescence element is preferably a material having a work function larger than 4 eV, and is carbon, aluminum, vanadium, iron, cobalt, nickel, copper, zinc, tungsten, silver. Gold, platinum, etc. and their alloys, conductive metal compounds such as tin oxide, indium oxide, antimony oxide, zinc oxide, zirconium oxide, and organic conductive resins such as polythiophene and polypyrrole are used.

  The metal forming the cathode (4) is preferably one having a work function smaller than 4 eV, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, gadolinium, ytterbium, ruthenium, manganese and alloys thereof are used. .

  If necessary, the anode and the cathode may be formed of two or more layers.

  In the organic electroluminescence element, at least the anode (1) or the cathode (4) needs to be a transparent electrode so that light emission can be seen. At this time, if a transparent electrode is used for the cathode, the transparency is likely to be impaired. Therefore, the anode is preferably a transparent electrode.

  When forming a transparent electrode, the above-described conductive material is used on the transparent substrate, and the desired light transmission is achieved by means such as vapor deposition, sputtering, or the like, or by dispersing and applying in a sol-gel method or resin. It may be formed so as to ensure properties and conductivity.

  The transparent substrate has an appropriate strength and is not particularly limited as long as it is transparent as long as it is transparent without being adversely affected by heat due to vapor deposition or the like during the production of an organic electroluminescence device. It is also possible to use transparent resins such as polyethylene, polypropylene, polyethersulfone, polyetheretherketone and the like. Commercial products such as ITO and NESA are known as transparent electrodes formed on a glass substrate, but these may be used.

  An example of manufacturing an organic electroluminescence element will be described with reference to a configuration in which an amino compound is used for an organic hole injecting and transporting layer (FIG. 1).

First, an organic hole injecting and transporting layer (2) is formed on the anode (1) described above. The organic hole injecting and transporting layer (2) may be formed by vapor-depositing the amino compound represented by the general formula (I), or a solution in which the amino compound is dissolved or a solution in which the amino compound is dissolved together with an appropriate resin. It may be formed by dip coating or spin coating.
When forming by a vapor deposition method, the thickness is 1-500 nm normally, and when forming by the apply | coating method, what is necessary is just to form to about 5-1000 nm.
The thicker the film is formed, the higher the applied voltage for emitting light, and the lower the light emission efficiency, the more likely the deterioration of the organic electroluminescent element. Further, when the film thickness is reduced, the luminous efficiency is improved, but breakdown is easily caused and the life of the organic electroluminescence element is shortened.

  The compound of general formula (I) can be used in combination with other charge transport materials. Specifically, phthalocyanine compound, naphthalocyanine compound, porphyrin compound, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acyl hydrazone, polyarylalkane, Examples include stilbene, butadiene, benzidine type triarylamine, diamine type triarylamine, and derivatives thereof, and polymer materials such as polyvinylcarbazole, polysilane, and conductive polymer. On the other hand, any compound can be used as long as it has an excellent hole injection effect, prevents migration of excitons generated in the light emitting layer to the electron injection layer or the electron transport material, and has an excellent thin film forming ability.

  An organic light emitting layer is formed on the organic hole injecting and transporting layer (2). As an organic light emitting material and a light emitting auxiliary material used for the organic light emitting layer, known materials can be used, for example, epidolidine, 2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl). Thiophene, 2,2 ′-(1,4-phenylenedivinylene) bisbenzothiazole, 2,2 ′-(4,4′-biphenylene) bisbenzothiazole, 5-methyl-2- {2- (4- ( 5-methyl-2-benzoxazolyl) phenyl) vinyl} benzoxazole, 2,5-bis (5-methyl-2-benzoxazolyl) thiophene, anthracene, naphthalene, phenanthrene, pyrene, chrysene, perylene, perinone 1,4-diphenylbutadiene, tetraphenylbutadiene, coumarin, acridine, stilbene, 2- (4-biphenyl) -6-phen Rubenzoxazole, aluminum trisoxine, magnesium bisoxin, bis (benzo-8-quinolinol) zinc, bis (2-methyl-8-quinolinolato) aluminum oxide, indium trisoxine, aluminum tris (5-methyloxin), lithium oxine , Gallium trisoxine, calcium bis (5-chlorooxin), polyzinc-bis (8-hydroxy-5-quinolinolyl) methane, dilithium epindridione, zinc bisoxin, 1,2-phthaloperinone, 1,2-naphthaloperinone And tris (8-hydroxyquinoline) aluminum complex.

  In addition, general fluorescent dyes such as fluorescent macrine dyes, fluorescent perylene dyes, fluorescent pyran dyes, fluorescent thiopyran dyes, fluorescent polymethine dyes, fluorescent mesocyanine dyes, and fluorescent imidazole dyes can also be used. Of these, particularly preferred are chelated oxinoid compounds.

  The organic light emitting layer may have a single layer structure of the light emitting material described above, or may have a multilayer structure in order to adjust characteristics such as light emission color and light emission intensity. Two or more kinds of luminescent materials may be mixed or doped in the luminescent layer.

  The organic light emitting layer (3) may be formed by vapor-depositing a light emitting material as described above, or formed by dip coating or spin coating a solution in which the light emitting material is dissolved or a solution dissolved with an appropriate resin. May be. Moreover, you may use the amino compound represented by general formula (I) as a luminescent substance.

When forming by a vapor deposition method, the thickness is 1-500 nm normally, and when forming by the apply | coating method, what is necessary is just to form to about 5-1000 nm.
The thicker the film is formed, the higher the applied voltage for emitting light, and the lower the light emission efficiency, the more likely the deterioration of the organic electroluminescent element. Further, when the film thickness is reduced, the luminous efficiency is improved, but breakdown is easily caused and the life of the organic electroluminescence element is shortened.

  Next, the above-described cathode is formed on the organic light emitting layer.

  The case where the organic hole-injection transport layer (2), the light emitting layer (3), and the cathode (4) are sequentially laminated on the anode (1) to form the organic luminescence device has been described. ), A light emitting layer (3), an organic hole injecting and transporting layer (2) and an anode are sequentially laminated. On the anode (1), a light emitting layer (3), an organic electron injecting and transporting layer (5) and a cathode are laminated. (4) are sequentially laminated (FIG. 3), or an organic hole injecting and transporting layer (2), a light emitting layer (3), an organic electron injecting and transporting layer (5), and a cathode (4) are formed on the anode (1). Of course, the organic electron injecting and transporting layer (5), the light emitting layer (3), and the anode (4) may be sequentially laminated on the cathode (4).

As shown in FIG. 2, when the electron injection / transport layer is formed on the light emitting layer (3), examples of the electron transport material include fluorenone, anthraquinodimethane, diphenoquinone, stilbenequinone, thiopyran dioxide, oxalate. There are diazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinone, anthrone and their derivatives, but they have the ability to transport electrons and have an excellent electron injection effect on the light-emitting layer or luminescent material, The compound is not limited thereto as long as it is a compound that prevents migration of excitons generated in the light emitting layer to the hole injection layer or the hole transport material and has an excellent thin film forming ability.
Further, it can be sensitized by adding an electron accepting substance or an electron donating substance to the charge transporting material.

  Furthermore, the hole injection / transport layer may have a two-layer structure of a hole injection layer and a hole transport layer by separating the hole injection function and the hole transport function. In this case, it is preferable to use the amino compound of the present invention represented by the general formula (I) for the hole injection layer. The electron injection / transport layer may have a two-layer structure of an electron injection layer and an electron transport layer by separating the electron injection function and the electron transport function.

  A pair of transparent electrodes of a cathode and an anode is connected to each electrode by an appropriate lead wire (8) such as a nichrome wire, a gold wire, a copper wire, a platinum wire, and the organic luminescence device has an appropriate voltage ( Light is emitted by applying Vs).

  The organic electroluminescence element of the present invention can be applied to various display devices or display devices.

  Hereinafter, the present invention will be described with reference to examples. In the examples, “parts” means “parts by weight” unless otherwise specified.

０．５１ｇ（０．００１３モル）、下記化学式で表される化合物（Ｂ）；

２．０ｇ（０．００４３モル）、無水炭酸カリウム１．６ｇ、銅粉０．３７ｇ、１８−クラウン−６エーテル０．０７６ｇ、ｏ−ジクロロベンゼン５ｍｌを混合し、還流温度下で２４時間反応させた。反応生成物をジクロルメタン２００ｍｌで抽出し、不溶分をろ別除去後、濃縮乾固した。これをカラムクロマトによって精製（担体；シリカゲル、溶離液：トルエン／ｎ−ヘキサン＝１／２で展開）して、目的の化合物（５）０．７５ｇを得た（収率４１．４％）。 Synthesis Example 1 (Synthesis of Compound (5))
In a 50 ml three-necked flask equipped with a water-cooled condenser, compound (A) represented by the following chemical formula;

0.51 g (0.0013 mol), a compound (B) represented by the following chemical formula;

2.0 g (0.0043 mol), 1.6 g of anhydrous potassium carbonate, 0.37 g of copper powder, 0.076 g of 18-crown-6 ether and 5 ml of o-dichlorobenzene were mixed and reacted at reflux temperature for 24 hours. It was. The reaction product was extracted with 200 ml of dichloromethane, and insoluble matters were removed by filtration, followed by concentration to dryness. This was purified by column chromatography (carrier: silica gel, eluent: developed with toluene / n-hexane = 1/2) to obtain 0.75 g of the desired compound (5) (yield 41.4%).

The melting point was 310-315 ° C. Moreover, when the molecular formula was analyzed, the following results were obtained. The molecular formula was analyzed using a CHN analyzer. The same applies to the following synthesis examples.
Molecular _formula: C _{102 H} 84 _{N 6}
Calculated value (%) C: 87.93% H: 6.03% N: 6.03%
Analytical value (%) C: 87.99% H: 6.01% N: 6.00%

０．５１ｇ（０．００１３モル）、下記化学式で表される化合物（Ｃ）；

１．９２ｇ（０．００４３モル）、無水炭酸カリウム１．６ｇ、銅粉０．３７ｇ、１８−クラウン−６エーテル０．０７６ｇ、ｏ−ジクロロベンゼン５ｍｌを混合し、還流温度下で２４時間反応させた。反応生成物をジクロルメタン２００ｍｌで抽出し、不溶分をろ別除去後、濃縮乾固した。これをカラムクロマトによって精製（担体；シリカゲル、溶離液：トルエン／ｎ−ヘキサン＝１／２で展開）して、目的の化合物（１２）０．８ｇを得た（収率４５．７％）。 Synthesis Example 2 (Synthesis of Compound (12))
In a 50 ml three-necked flask equipped with a water-cooled condenser, compound (A) represented by the following chemical formula;

0.51 g (0.0013 mol), compound (C) represented by the following chemical formula;

1.92 g (0.0043 mol), 1.6 g of anhydrous potassium carbonate, 0.37 g of copper powder, 0.076 g of 18-crown-6 ether and 5 ml of o-dichlorobenzene were mixed and reacted at reflux temperature for 24 hours. It was. The reaction product was extracted with 200 ml of dichloromethane, and insoluble matters were removed by filtration, followed by concentration to dryness. This was purified by column chromatography (carrier: silica gel, eluent: developed with toluene / n-hexane = 1/2) to obtain 0.8 g of the desired compound (12) (yield 45.7%).

The melting point was 276-281 ° C.
Molecular formula: C ₉₉ H ₇₂ N ₆
Calculated value (%) C: 88.39% H: 5.36% N: 6.25%
Analytical value (%) C: 89.46% H: 5.33% N: 6.21%

０．５１ｇ（０．００１３モル）、下記化学式で表される化合物（Ｄ）；

２．０５ｇ（０．００４３モル）、無水炭酸カリウム１．６ｇ、銅粉０．３７ｇ、１８−クラウン−６エーテル ０．０７６ｇ、ｏ−ジクロロベンゼン５ｍｌを混合し、還流温度下で２４時間反応させた。反応生成物をジクロルメタン２００ｍｌで抽出し、不溶分をろ別除去後、濃縮乾固した。これをカラムクロマトによって精製（担体；シリカゲル、溶離液：トルエン／ｎ−ヘキサン＝１／２で展開）して、目的の化合物（１４）０．９ｇを得た（収率４８．１％）。 Synthesis Example 3 (Synthesis of Compound (14))
In a 50 ml three-necked flask equipped with a water-cooled condenser, compound (A) represented by the following chemical formula;

0.51 g (0.0013 mol), compound (D) represented by the following chemical formula;

2.05 g (0.0043 mol), 1.6 g of anhydrous potassium carbonate, 0.37 g of copper powder, 0.076 g of 18-crown-6 ether and 5 ml of o-dichlorobenzene are mixed and reacted at reflux temperature for 24 hours. It was. The reaction product was extracted with 200 ml of dichloromethane, and insoluble matters were removed by filtration, followed by concentration to dryness. This was purified by column chromatography (carrier: silica gel, eluent: developed with toluene / n-hexane = 1/2) to obtain 0.9 g of the desired compound (14) (yield 48.1%).

The melting point was 150-155 ° C.
Molecular formula: C ₉₉ H ₇₂ N ₆ S ₃
Calculated value (%) C: 82.50% H: 5.00% N: 5.83% S: 6.67%
Analytical value (%) C: 82.57% H: 4.99% N: 5.79% S: 6.65%

０．４５部、ポリエステル樹脂（バイロン２００；東洋紡績社製）０．４５部をシクロヘキサノン５０部とともにサンドミルにより分散させた。得られたトリスアゾ化合物の分散物を８０φのアルミドラム上に浸漬塗布方法を用いて、乾燥膜厚が０．３ｇ／ｍ^２となる様に塗布した後、乾燥させた。 Application of electrophotographic photosensitive member to charge transport material Reference Example 1
Trisazo compound represented by the following general formula (E)

0.45 part and 0.45 part of a polyester resin (Byron 200; manufactured by Toyobo Co., Ltd.) were dispersed together with 50 parts of cyclohexanone by a sand mill. The obtained trisazo compound dispersion was applied onto an 80φ aluminum drum by dip coating so that the dry film thickness was 0.3 g / m ^2, and then dried.

A solution obtained by dissolving 50 parts of the amino compound (1) and 50 parts of a polycarbonate resin (Panlite K-1300; manufactured by Teijin Kasei Co., Ltd.) in 400 parts of 1,4-dioxane on the charge generation layer thus obtained was prepared. The charge transport layer was formed by applying and drying to a dry film thickness of 20 μm.
Thus, an electrophotographic photosensitive member having a photosensitive layer composed of two layers was obtained.

  In order to reduce the initial surface potential Vo (V) and the initial potential to 1/2 by corona charging the photoreceptor obtained in this way at −6 Kv using a commercially available electrophotographic copying machine (Minolta, Inc .; EP-5400). The required exposure amount E1 / 2 (lux · sec) was measured, and the decay rate DDR1 (%) of the initial potential when left in the dark for 1 second was measured.

Reference Examples 2-4
A photoconductor having the same configuration as that of Reference Example 1 except that each of amino compounds (4), (5), and (6) was used instead of amino compound (1) used in Reference Example 1 was prepared. .
For the photoreceptor thus obtained, Vo, E1 / 2, and DDR1 were measured in the same manner as in Reference Example 1.

０．４５部、ポリスチレン樹脂（分子量４００００）０．４５部をシクロヘキサノン５０部とともにサンドミルにより分散させた。 Reference Example 5
Bisazo compound represented by the following general formula (F)

0.45 part and 0.45 part of polystyrene resin (molecular weight 40000) were dispersed by a sand mill together with 50 parts of cyclohexanone.

The resulting dispersion of the bisazo compound was applied on an 80φ aluminum drum so that the dry film thickness was 0.3 g / m ² and then dried.
A solution obtained by dissolving 50 parts of the amino compound (8) and 50 parts of a polyarylate resin (U-100; manufactured by Unitika) in 400 parts of 1,4-dioxane on the charge generation layer thus obtained was dried. The charge transport layer was formed by applying the film so as to have a thickness of 25 μm and drying it.
Thus, an electrophotographic photosensitive member having a photosensitive layer composed of two layers was produced.

Reference Examples 6-8
A photoconductor having the same configuration as that of Reference Example 5 except that each of amino compounds (10), (12), and (16) was used instead of amino compound (8) used in Reference Example 5 was prepared. .
For the photoreceptor thus obtained, Vo, E1 / 2, and DDR1 were measured in the same manner as in Reference Example 1.

Reference Example 9
Polycyclic quinone pigments represented by the following general formula (G)

０．４５部、ポリカーボネート樹脂（パンライトＫ−１３０００；帝人化成社製）０．４５部をジクロルエタン５０部とともにサンドミルにより分散させた。
得られた多環キノン系顔料の分散物を８０φのアルミドラム上に、乾燥膜厚が０．４ｇ／ｍ^２となる様に塗布した後乾燥させた。

0.45 part and 0.45 part of polycarbonate resin (Panlite K-13000; manufactured by Teijin Chemicals Ltd.) were dispersed together with 50 parts of dichloroethane by a sand mill.
The obtained polycyclic quinone pigment dispersion was applied on an 80φ aluminum drum so that the dry film thickness was 0.4 g / m ² and then dried.

A solution obtained by dissolving 60 parts of an amino compound (20) and 50 parts of a polyarylate resin (I-100; manufactured by Unitika) in 400 parts of 1,4-dioxane on the charge generation layer thus obtained was dried. The charge transport layer was formed by applying the film so as to have a thickness of 18 μm and drying it.
Thus, an electrophotographic photosensitive member having a photosensitive layer composed of two layers was produced.

Reference Examples 10-11
A photoconductor having the same configuration as that of Reference Example 10 except that each of amino compounds (23) and (28) was used instead of amino compound (20) used in Reference Example 10 was produced.
For the photoreceptor thus obtained, Vo, E1 / 2, and DDR1 were measured in the same manner as in Reference Example 1.

Reference Example 12
0.45 parts of titanyl phthalocyanine and 0.45 parts of butyral resin (BX-1; manufactured by Sekisui Chemical Co., Ltd.) were dispersed together with 50 parts of dichloroethane by a sand mill.
The obtained dispersion of phthalocyanine pigment was applied on an 80 mm alumite drum using a dip coating method so that the dry film thickness was 0.3 μm, and then dried.

A solution obtained by dissolving 50 parts of the amino compound (45) and 50 parts of a polycarbonate resin (PC-Z; manufactured by Mitsubishi Gas Chemical Company) in 400 parts of 1,4-dioxane was dried on the charge generation layer thus obtained. The charge transport layer was formed by coating so that the film thickness was 18 μm.
Thus, an electrophotographic photosensitive member having a photosensitive layer composed of two layers was produced.

  For the photoreceptor thus obtained, Vo, E1 / 2, and DDR1 were measured in the same manner as in Reference Example 1.

Reference Example 13
50 parts of copper phthalocyanine and 0.2 part of tetranitro copper phthalocyanine are dissolved in 500 parts of 98% concentrated sulfuric acid with sufficient stirring. Then, it was filtered, washed with water, and dried at 120 ° C. under reduced pressure.

10 parts of the photoconductive composition thus obtained was 22.5 parts of thermosetting acrylic resin (Acridic A405; manufactured by Dainippon Ink and Co., Ltd.), 7.5 parts of melamine resin (Super Becamine J820; manufactured by Dainippon Ink, Inc.). Then, 15 parts of the amino compound (33) is placed in a ball mill pot together with 100 parts of a mixed solvent in which methyl ethyl ketone and xylene are mixed in the same amount, and dispersed for 48 hours to prepare a photosensitive coating liquid. A photosensitive layer having a thickness of about 15 μm was formed thereon by spray coating and drying.
In this way, a single layer type photoreceptor was produced.
The photoreceptor thus obtained was subjected to the same method as in Reference Example 1, except that corona charging was performed at +6 Kv, and Vo, E1 / 2, and DDR1 were measured.

Reference Examples 14-15
Photoconductors having the same constitution as in Reference Example 13 except that amino compounds (36) and (48) were used instead of amino compound (33) used in Reference Example 13 were prepared.
For the photoreceptor thus obtained, Vo, E1 / 2, and DDR1 were measured in the same manner as in Reference Example 13.

  Table 1 summarizes the measurement results of Vo, E1 / 2, and DDR1 of the photoreceptors obtained in Reference Examples 1 to 15.

As can be seen from Table 1, the photoreceptor of this reference example is of a laminated type or a single layer type and has sufficient charge retention capability, and the dark decay rate is small enough to be used as a photoreceptor, and is excellent in sensitivity. Yes.
Further, a repeated live-action test at the time of positive charging by a commercially available electrophotographic copying machine (Minolta Co., Ltd .; EP-350Z) was performed on the photoconductor of Reference Example 13; It can be seen that the tone is excellent, there is no change in sensitivity, a clear image is obtained, and the photoreceptor of the present invention has stable repeat characteristics.

Application to organic electroluminescence element Example 1
A 50 nm-thick thin film was formed by vapor deposition of the amino compound (5) as an organic hole injecting and transporting layer on an indium tin oxide-coated glass substrate.
Next, a thin film was formed as an organic light emitting layer by vapor deposition of aluminum trisoxine to a thickness of 50 nm.
Next, a thin film having a thickness of 200 nm was formed by vapor deposition of magnesium as a cathode.
In this way, an organic electroluminescence device was produced.

Examples 2-3 and Reference Example 16
In Example 1, instead of using the compound (5), an example was used except that the amino compound (10) (Example 2), (12) (Example 3), (20) (Reference Example 16) was used instead. An organic electroluminescence element was produced in exactly the same manner as in Example 1.

を蒸着により５０ｎｍの厚さになるように薄膜を形成した。
次に、陰極としてマグネシウムを蒸着により２００ｎｍの厚さになるように薄膜を形成した。
このようにして、有機エレクトロミネセンス素子を作製した。 Reference Example 17
A thin film having a thickness of 70 nm was formed on the indium tin oxide-coated glass substrate by vapor deposition of an amino compound (25) as an organic hole injecting and transporting layer.
Next, a thin film was formed as an organic light emitting layer by vapor deposition of aluminum trisoxine to a thickness of 100 nm.
Next, as the organic electron injecting and transporting layer, the following oxadiazole compound (H);

A thin film was formed by vapor deposition to a thickness of 50 nm.
Next, a thin film having a thickness of 200 nm was formed by vapor deposition of magnesium as a cathode.
In this way, an organic electroluminescence element was produced.

Reference Examples 18-20
An organic electroluminescence device was fabricated in exactly the same manner as in Reference Example 17 except that instead of using Compound (25) in Reference Example 17, the amino compounds (31), (35), and (41) were used.

Reference Example 21
A thin film having a thickness of 50 nm was formed by vapor deposition of an amino compound (45) as an organic light emitting layer on a substrate of indium tin oxide-coated glass.
Next, a thin film was formed as an organic electron injecting and transporting layer by vapor deposition of the oxadiazole compound (H) to a thickness of 20 nm.
Next, a thin film was formed by vapor deposition of Mg and Ag with an atomic ratio of 10: 1 as a cathode to a thickness of 200 nm.
In this way, an organic electroluminescence element was produced.

Reference Example 22
The compound (47) was vacuum-deposited on an indium tin oxide-coated glass substrate to obtain a 20 nm-thick hole injection layer. Furthermore, N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4-diamine was vacuum deposited to obtain a 40 nm-thick hole transport layer. Next, a thin film was formed by vapor deposition of a tris (8-hydroxyquinoline) aluminum complex to a thickness of 50 nm.
Next, a thin film was formed by vapor deposition of Mg and Ag with an atomic ratio of 10: 1 as a cathode to a thickness of 200 nm.
In this way, an organic electroluminescence element was produced.

Reference Example 23
N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4′-diamine is vacuum deposited on a substrate of indium tin oxide-coated glass to form a film. A 60 nm thick hole transport layer was obtained. Next, a light emitting layer was formed by vacuum deposition of tris (8-hydroxyquinoline) aluminum complex and amino compound (51) at a ratio of 3: 1 to a thickness of 60 nm.
Next, a thin film was formed by vapor deposition of Mg and Ag with an atomic ratio of 10: 1 as a cathode to a thickness of 200 nm.
In this way, an organic electroluminescence element was produced.

Reference Example 24
Compound (65) was dissolved in dichloromethane on an indium tin oxide-coated glass substrate, and a hole injection transport layer having a thickness of 50 nm was obtained by spin coating. Further, a light emitting layer was formed by vapor deposition of a tris (8-hydroxyquinoline) aluminum complex to a thickness of 30 nm. Further, an electron injection layer of oxadiazole compound (H) having a film thickness of 20 nm was obtained by a vacuum deposition method.
Next, a thin film was formed by vapor deposition of Mg and Ag with an atomic ratio of 10: 1 as a cathode to a thickness of 200 nm.
In this way, an organic electroluminescence element was produced.

Reference Examples 25-26
In Example 24, an organic electroluminescence device was produced in exactly the same manner as Reference Example 24 except that the compound (65) was used instead of the amino compound (75) or (78).

Reference Example 27
Compound (80), tris (8-hydroxyquinoline) aluminum complex, and polymethyl methacrylate are dissolved in tetrahydrofuran at a ratio of 3: 2: 5 on an indium tin oxide-coated glass substrate, and the film thickness is 100 nm by spin coating. A light emitting layer was obtained.
Next, a thin film was formed by vapor deposition of Mg and Ag with an atomic ratio of 10: 1 as a cathode to a thickness of 200 nm.
In this way, an organic electroluminescence element was produced.

を蒸着により厚さ５０ｎｍの薄膜を形成した。
次に、有機発光層としてアルミニウムトリスオキシンを蒸着により５０ｎｍの厚さになるように薄膜を形成した。
次に、陰極としてマグネシウムを蒸着により２００ｎｍの厚さになるように薄膜を形成した。
このようにして、有機エレクトロミネセンス装置を作製した。 Comparative Example 1
Amino compound (J) as an organic hole injecting and transporting layer on an indium tin oxide coated glass substrate

A thin film having a thickness of 50 nm was formed by vapor deposition.
Next, a thin film was formed as an organic light emitting layer by vapor deposition of aluminum trisoxine to a thickness of 50 nm.
Next, a thin film having a thickness of 200 nm was formed by vapor deposition of magnesium as a cathode.
In this way, an organic electroluminescence device was produced.

Evaluation The organic electroluminescence elements obtained in Examples 1 to 3, Reference Examples 16 to 27 and Comparative Example 1 were subjected to the light emission starting voltage and the maximum light emission luminance when a DC voltage was applied using the glass electrode as an anode and the time. The emission voltage of was measured.
The measurement results are summarized in Table 2.

As can be seen from Table 2, the organic electroluminescent device of this example showed good emission luminance even at a low potential.
Further, when the organic electroluminescent element of Reference Example 22 was continuously emitted at a current density of 1 mA / cm ² , stable emission could be observed for 200 hours or more.

  The organic electroluminescence element of the present invention achieves improvement in light emission efficiency, light emission luminance and long life, and is used together with a light emitting substance, a light emission auxiliary material, a charge transport material, a sensitizer, a resin, and an electrode. It is not limited to the material and the element manufacturing method.

  The present invention provides a novel amino compound having excellent charge transport ability. By using the amino compound, an electrophotographic photoreceptor excellent in initial electrophotographic characteristics such as sensitivity, charge transport characteristics, initial surface potential, dark decay rate, and less fatigue due to repeated use, and a large emission intensity and a light emission starting voltage are obtained. An organic electroluminescence element having low durability and excellent durability can be obtained.

The schematic sectional drawing of one structural example of an organic electroluminescent element. The schematic sectional drawing of one structural example of an organic electroluminescent element. The schematic sectional drawing of one structural example of an organic electroluminescent element. The schematic sectional drawing of one structural example of an organic electroluminescent element.

Explanation of symbols

  1: anode, 2: hole injection transport layer, 3: organic light emitting layer, 4: cathode, 5: electron injection transport layer, 6: organic light emitting material, 7: charge transport material, 8: lead wire

Claims (1)

In an organic electroluminescent element having a light emitting layer or a plurality of organic compound thin layers including a light emitting layer between a pair of electrodes, at least one layer contains an amino compound represented by the following general formula (I): Organic electroluminescence element.

Wherein A represents a group represented by the following general formula (II);

Ar ₁ represents an aryl group or a heterocyclic group, respectively; R ₁ and R ₂ together represent a group that forms a ring represented by Formula (XI) or Formula (XII); Formula; R ₃ represents Represents a hydrogen atom or an alkyl group) ;

(XI) (XII) .

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